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Strongly Polarized π‑Extended 1,4-Dihydropyrrolo[3,2‑b]pyrroles

Fused with Tetrazolo[1,5‑a]quinolines
Mohammad B. Teimouri,* Irena Deperasinś ka, Matt Rammo, Marzena Banasiewicz, Charles W. Stark,
Łukasz Dobrzycki, Michał K. Cyranś ki,* Aleksander Rebane,* and Daniel T. Gryko*
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ABSTRACT: A straightforward route to 1,4-dihydropyrrolo[3,2-b]pyrroles

comprised of two electron-withdrawing quinoline or tetrazolo[1,5-a]quinoline
scaffolds has been developed. The versatile multicomponent reaction
affording 1,4-dihydropyrrolo[3,2-b]pyrroles combined with intramolecular
Downloaded via 77.65.81.89 on April 19, 2025 at 11:26:53 (UTC).

direct arylation enables assembly of these products in just three steps from
anilines with overall yields exceeding 30%. The planarized, ladder-type
heteroacenes possess up to 14 conjugated rings. These nominally quadrupolar
materials exhibit efficient fluorescence with wavelengths spanning most of the
visible spectrum from green−yellow for the dyes possessing biaryl bridges and
orange−red for the fully fused systems. In many cases, the fluorescence
quantum yields are large, the solvatofluorochromic effects are strong, and the fluorescence is maintained even in crystalline state.
Analysis of the electronic structure of these molecular architectures using quantum chemical methods suggests that the character and
position of the flanking heterocycle determine the shape of HOMO and LUMO and their extension to N-aryl substituents,
influencing the values of molar absorption coefficient. An experimental study of the two-photon absorption (2PA) properties has
revealed that it occurs in the 700−800 nm range with apparent deviation from the Laporte parity selection rule, which may be
attributed to Hertzberg−Teller contribution to vibronically allowed 2PA transition.

■ INTRODUCTION
Modern chemistry and materials science of complex
the mitochondrial TET1 protein,9 direct solvent probing via
H-bonding interactions,10 photochromic analysis of halocar-
conjugated functional dyes often implies controlled modu- bons,11 high-performance organic field-effect transistors,12 dye-
lation of the optoelectronic properties achieved by fine-tuning sensitized solar cells,13 and many others.14−22
the π-system. Extending the π-conjugation by linking two or The exceptional feature of DHPPs is that a convenient one-
pot synthesis enables the assembly of the heterocyclic scaffold
more unsaturated hydrocarbons at the periphery of a
possessing four arenes linked via biaryl linkages.23,24 The
conjugated architecture is a powerful method for targeted
variety of these arenes is quite vast especially considering that
modification of the available π-cloud, leading to changes in the
by adding just one more synthetic step, e.g., direct arylation,
local or global delocalization character.1 The π-electron
the otherwise weakly coupled dye can be efficiently trans-
distribution within a molecule can also be manipulated using
formed into a fused planar compound possessing 8, 10, or 12
both simple substituted aryl groups and exotic heteroaromatic
conjugated aromatic rings.25 These advantages provide organic
motifs.2
chemists a unique and versatile toolbox that currently has few
The 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) motif, com-
if any analogs, at least in the area of centrosymmetric
prised of two fused pyrrole units in a centrosymmetric
quadrupolar dyes.
orientation, is not only the strongest known electron donor
Tetrazole is a five-membered, fully conjugated nitrogen-rich
among 10π-electron heteropentalenes but can also be obtained
6π-azaheterocycle consisting of a single carbon and four
through an easily accessible one-pot synthesis.3 The available
consecutive nitrogen atoms,26 which render the system very
facile synthesis of tetraaryl-1,4-dihydropyrrolo[3,2-b]pyrroles
electron deficient. Interestingly, tetrazole has the highest
(TAPPs), combined with promising photophysical properties,
is making TAPP scaffold-based organic chromophores
attractive for many research applications.4 Received: December 20, 2023
Over the past decade, the versatility of 1,4-dihydropyrrolo- Revised: February 28, 2024
[3,2-b]pyrroles has been demonstrated in an expansive range Accepted: March 11, 2024
of areas of research including two-photon absorption (2PA),5 Published: March 26, 2024
ground- and excited-state symmetry breaking,6 solvatofluor-
ochromism,7 tunable single-molecule conductance,8 targeting
© 2024 The Authors. Published by
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nitrogen content among the stable five-membered hetero- Scheme 1. Synthesis of 2,5-Bis(2-chloroquinoline)-1,4-
cycles. Despite the high nitrogen content, tetrazole and most of diaryl pyrrolo[3,2-b]pyrroles (CQPPs)
its derivatives remain relatively stable under the influence of
heat or microwave radiation.27 Furthermore, the related
compounds are able to withstand a wide range of chemical
environments such as strongly acidic and basic media,
alkylating agents, dienophiles, as well as oxidizing and reducing
conditions.27 Even though tetrazoles28 and their annulated
derivatives have received considerable attention over the past
years in fields of medicine, agriculture, and material science, it
is still surprising that applications of tetrazoloquinoline-
containing compounds as functional dyes have been rarely
investigated to date.29
Our objective is to use unique features of TAPPs’ chemistry
for the synthesis of large, structurally unique, heavily N-doped
nanographenes, possessing tetrazole scaffolds. We reasoned
that incorporation of moderately electron-withdrawing moi-
eties such as tetrazolo[1,5-a]quinoline and quinoline at
strongly conjugated positions 2 and 5 can be utilized to
endow resulting dyes with desired photophysical properties.

■ RESULTS AND DISCUSSION

Design and Synthesis. The synthesis of centrosymmetric
quadrupolar TAPPs possessing fused tetrazole moieties starts
from the preparation of the corresponding aldehyde. We were
attracted by the exceptional simplicity of the Meth-Cohn
synthesis of 2-chloro-3-formylquinolines, which enables the
assembly of building blocks possessing the exact functionality
required (in two steps from commercial arylamines).30 The
tetrazolo[1,5-a]quinolines precursors were obtained from the
corresponding 2-chloroquinolines and NaN3 via a general
method involving the two-step process of SNAr/ring−chain
azido-tautomerization (see Supporting Information for de-
tails).31
Having 2-chloro-3-formylquinolines (1a−e) and tetrazolo-
[1,5-a]quinoline-4-carbaldehyde (5a−d) in hand, we subjected
them to our multicomponent reaction with primary aromatic
amines 2a−f and butane-2,3-dione (3), resulting in the
formation of the corresponding 2,5-bis(2-chloroquinoline)-
1,4-diaryl-pyrrolo[3,2-b]pyrroles (CQPPs) 4a−4l and 2,5-
bis(tetrazoloquinoline)-1,4-diaryl-pyrrolo[3,2-b]pyrroles
(TQPPs) (6a−6q) in moderate to good yields (Schemes 1 and
2). Furthermore, the molecular structures of 4k and 6j were
confirmed by X-ray crystallography (Figure 1b,c). The DHPP approaches is that in the case of quinoline-fused dyes, halogen
core in 4k is perfectly planar, and the torsional angles between atoms were placed on substituents at positions 2 and 5,
the peripheral substituted benzene rings attached to nitrogen whereas for tetrazoloquinoline-fused TAPPs, N-aryl substitu-
atoms and DHPP core are 42° (Figure 1b). Chloroquinoline ents possessed bromine atoms. Dyes 6o and 6p were
moieties attached to C-2 and C-5 atoms are both twisted at transformed into TQFPPs 11a and 11b via double intra-
51°. On the other hand, the dihedral angle between molecular palladium-catalyzed direct arylation. High yields
tetrazoloquinolinyl substituent and the DHPP core in 6j is achieved for all these transformations encouraged us to
only 27° (Figure 1c). Noteworthy, this angle is only 35° for attempt the synthesis of new TQFPPs incorporating [n]-
unsubstituted benzene in the ground state.3,4 helicenes with hope to obtain the molecules with interesting
Having a CQPP family with chlorine atoms and benzene photophysical properties. To achieve this goal, the chosen
rings strategically placed in respect to the central DHPP core building blocks were 1-amino-2-bromonaphthalene and 9-
in hand, precursors 4h, 4i, and 4l were transformed in good amino-10-bromophenanthrene as the arylamine components
yields into a ladder-type quinoline-fused pyrrolo[3,2-b]pyrroles and tetrazolo[1,5-a]quinoline-4-carbaldehyde bearing hexyl or
(QFPPs) 10a−10c utilizing double intramolecular direct octyl substituents as the aldehyde. Consequently, the
arylation (Scheme 3). Unambiguous evidence for the proposed brominated TQPPs 6q and 6r were prepared using appropriate
structure of 10 was finally obtained by single crystal X-ray starting materials using our optimized three-component
diffraction analysis in the case of 10a (Figure S3). condensation (Scheme 4).
The analogous concept has been employed to obtain The 2-fold cyclization of TQPP 6q was carried out to give
centrosymmetric, planarized tetrazoloquinoline-fused pyrrolo- the symmetric helicene 11c, including four [4]azasubhelicenes
[3,2-b]pyrroles (TQFPPs). The pivotal difference in these two and two [5]azasubhelicenes in 39% yield. When TQPP 6r was
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Scheme 2. Synthesis of 2,5-Bis(tetrazoloquinoline)-1,4- the substrate, whereas debromination via a protodepalladation

diaryl pyrrolo[3,2-b]pyrroles (TQPPs) mechanism occurred on the other side, giving an unsym-
metrical pyrrolopyrrole-containing triple azahelicene 11d
(Figure 1a) isolated in 26% yield (Scheme 4).
Photophysical Results. Spectroscopic properties of all
prepared dyes were measured in toluene (if solubility allowed)
(dielectric constant ε = 2.38) and dichloromethane (DCM, ε =
8.93). Spectroscopic properties of representative dyes 4a, 4g,
6a, 6g, 6r, 10a, 10c, 11a, 11c, and 11d are shown in Figures 2
and 3 and summarized in Table 1 (see Table S1 for
comprehensive results). The absorption spectra of CQPPs
(dyes 4a−4k) are dominated by a strong band at around 390
nm, with the peak extinction coefficient values in the range ε =
15000−30000 M−1·cm−1. Comparison of the peak absorption
wavelength of CQPPs with that of structurally related 2,5-
bis(quinolin-2-yl)pyrrolo[3,2-b]pyrroles25b shows that in
toluene the former dyes absorb wavelengths ca. 30−50 nm
lower. This is attributed to the presence of chloro-substituent
located ortho- to DHPP core, which, for steric reasons
(confirmed by X-ray, Figure 1b), effectively disturbs ground
state electronic coupling between the core and the periphery of
the molecule. On the other hand, the absorption maxima of
CQPPs are bathochromically shifted by ca. 30 nm compared to
those of 2,5-bis(naphth-2-yl)pyrrolo[3,2-b]pyrroles,24b sug-
gesting that the electron-withdrawing character of quinoline
substituents is, nevertheless, clearly manifested. This behavior
is even more pronounced for tetrazole-bearing TQPPs, which
typically exhibit absorption maxima at 455−464 nm (dyes 6a−
6q), with a vibronic shoulder at ca. 20 nm lower. The only
exception from this pattern is dye 6r, for which the vibronic
band is stronger than the origin band. The redshift observed
for TQPPs was expected due to the significant increase in
acceptor character of the substituents at positions 2 and 5 from
weakly to strongly electron withdrawing. Additionally, the lack
of an ortho-chloro substituent allows better planarization/
electronic coupling in the ground state, which is confirmed by
X-ray studies (Figure 1a). TQPPs also exhibit much higher
extinction coefficients and fluorescence quantum yields (Φfl)
than CQPPs, despite the presence of heavy atoms and
nitrogen-rich aromatic rings, which often lead to very efficient
intersystem crossing and quenching of fluorescence.32
Needless to say, rigid and planar QFPPs and 11a−c display
remarkably different characteristics compared to parent TAPP
molecules. A significant ≈100 nm bathochromic shift of
absorption were observed for dye 10a (when compared to 4h),
as well as for dye 11a (when compared to 6i) (Figures 2 and
3). Further consequences of planarization were larger Φfl
(reaching 100% in DCM in the case of dye 11a) and smaller
Stokes shifts observed for fused dyes, which are results of more
restricted molecular motion comparing to the parent dyes. As
expected, the properties of monocoupling product 11d stand
in the middle between those of substrates and the bis-coupled
products.
As far as the solid-state emission is concerned, both groups
of examined quadrupolar dyes, 4 and 6, exhibit strikingly
different properties. The analysis of solid-state spectra reveals
that in the case of 4d, 4h, and 4i, absorption is only slightly
bathochromically shifted, i.e., to 425 nm, whereas emission is
hypsochromically shifted (450−475 nm) compared to data
collected in toluene. The only exception from this trend is
max
found in the case of 4k ( em = 515 nm), and it is presumably
subjected to selective intramolecular direct arylation, to our related to the presence of sterically encumbered substituents
surprise, the desired cyclization took place only on one side of (four tert-butyl groups), which impact packing. On the other
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Figure 1. X-ray crystal structures of dyes 11d (a), 4k (b), 6j (c), and 10a (d). OTRTEP plot of molecules drawn at 50% probability level.
Hydrogen molecules omitted for clarity.

hand, dyes 6a, 6e, 6i, and 6o do have bathochromically shifted Computational Studies. DFT and TDDFT/M06/6-
both absorption and emission to 525 and 575 nm, respectively 31G(d,p) calculations with the optimization of molecular
(see Supporting Information for details). For all these dyes, the structures in the ground electronic state S0 and the lowest
fluorescence intensity is moderate ranging from 2.9% to 20%. electronic excited state S1 were performed for the description
Two-Photon Absorption. Figure 4 presents the two- of the spectroscopic properties of molecules 4, 6, 10, and 11
photon absorption (2PA) cross-section spectra in GM units (1 (for results, see Table 2). These dyes have been chosen since
GM = 10−50 cm4 s−1 photon) of representative dyes 4h, 6h, they constitute model dyes for the four groups of compounds
and 10a in toluene measured with 120 fs laser pulses tuned in studied in this project. The calculations also included the
the wavelength range λ2PA= 630−1040 nm (red line, lower molecule 10-x−regioisomer 10, which is topologically similar
horizontal scale) and through the fluorescence excitation to 11. The M06 calculation method was chosen as it best
method, which consists of scaling the reference-corrected 2PA reproduces the experimental results (Table S7 and Figure S7).
spectral profiles according to absolute 2PA cross-section values Calculations were performed using the Gaussian 16 package.35
determined at select wavelengths (black symbols). The linear The effect of solvent was described in the PCM procedure.
absorption spectra of 4h, 6h, and 10a in toluene are shown for The SOC elements were also calculated using the Orca
comparison on a 2× expanded wavelength scale (blue line, program.36
upper horizontal axis). Table 2 contains the calculated energies and oscillator
In all three dyes, the 2PA shows distinct features with the strengths for the absorption (S0 → S1) and fluorescence (S1 →
maximum cross-section values, σ2PA = 50 GM (770 nm) and S0), characterizing structures optimized in the S0 and S1 states.
Two of the considered molecules, 4 and 6, are nonplanar
43 GM (660 nm) in 4h, σ2PA = 250 GM (775 nm) in 6h, and
systems. The angle between the planes of the peripheral arenes
σ2PA = 5 GM (930 nm) and 25 GM (700 nm) in 10a. The
possessing electron-withdrawing character and the DHPP
experimental observation that the TQPP 6h shows almost 1
center in 4, optimized in the S0 ground state, is 43°, and is 20°
order of magnitude larger peak σ2PA value compared to the in the case of compound 6. In the S1 excited state, the angle
CQPP and QFPP-type compounds correlates well with a values slightly decrease to 32° and 18°, respectively. The
stronger-acting electron-withdrawing ability of the attached planes between N-aryl substituents also form large angles with
tetrazole moiety. As a further testimony to the quadrupolar the DHPP plane: 43° and 45° in the S0 and S1 states of
nature of these chromophores, none of the 2PA spectral molecule 4, and 48° and 49° in the case of 6, respectively,
profiles coincide with underlying 1PA transition profiles. which is corroborated by X-ray data (Figure 1).
Nevertheless, the ratio of σ2PA vs ε1PA (dashed black lines) The computational results, given in Table 2, capture the
remains finite even for the longest wavelength part of the experimental facts, such as the red shifts of spectra of dye 6
spectra. Such apparent deviation from the Laporte parity relative to TAPP 4 and of dye 11 relative to TAPP 10 (i.e., in
selection rule has been previously observed for a number of the context of the changing the acceptor), as well as 10 relative
nominally inversion-symmetric diketopyrrolopyrroles33 and is to 4 and 11 relative to 6 (i.e., in context fused vs nonfused
most likely due to Hertzberg−Teller contribution to vibroni- system).
cally allowed 2PA transition.22 It is worth to point out that The calculations reveal that electronic transitions between
much larger values of σ2PA were reached for various strongly the S0 and S1 states in all tested compounds are described by
pyrrole derivatives bearing strongly polarized donor−acceptor the electronic configuration {HOMO, LUMO}, where HOMO
structure.34 and LUMO have a specific structure, resembling “exciplex”
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Scheme 3. Synthesis of Ladder-Type Quinoline-Fused Therefore, the electronic transitions between the S0 and S1
Pyrrolo[3,2-b]pyrroles (QFPPs) via Intramolecular Double states in all the tested compounds are qualitatively of the same
Direct Arylation nature: a multicenter CT transition with a charge shift between
the central DHPP scaffold and two symmetrically arranged
acceptor moieties at the periphery. Referring to the symbolic
record of the CT transition energy ECT = ID − EA +
Eint(D,A,R), it implies that the quantitative differences in the
spectroscopic properties of these molecules are dictated by the
interplay of several factors: differences in the electron affinity
of acceptors and differences in interaction energy, resulting
from variability in the mutual orientation of the donor and
acceptors and the role played by the N-aryl substituents. The
red shifts of the absorption and fluorescence spectra of 6
relative to 4 (and 11 relative to dye 10) are in correspondence
with the change in the electron affinity of the acceptor (≈1800
cm−1, Table S8).
However, differences in the electron affinity of the acceptor
are not the only reason for differences in spectroscopic
properties of the tested molecules. In the case of such complex
molecules, with the possibility of rotation of the components
around the bonds connecting them, an important factor
influencing the spectroscopic properties of these compounds is
the mutual orientation of the planes of the individual elements.
An interesting observation can be derived from probing the
changes in the energy and the oscillator strength of the
absorption depending on the mutual orientation of the donor
and acceptors using compound 4 as an example (Figure 6).
According to the results of the optimization of the molecular
structure, the energy minimum for this compound corresponds
to the geometry in which the angle between the planes of
acceptors and donor is 43°. That means that in this geometry,
a balance is achieved between the stabilizing role of
interactions between donor and acceptors and the destabilizing
role of steric interactions. This dye absorbs in DCM at 424 nm
with an oscillator strength of 0.815 (Table 2). Both quantities
change when moving away from equilibrium by changing the
donor−acceptor angle (see Figure 6). In the case of
orthogonality of the donor and acceptor planes (the system
practically is not stabilized by the interactions between them),
the absorption transition would be at higher energy at 418 nm
with zero oscillator strength. In turn, in the planar case, the
interaction of the donor with the acceptors is the strongest,
which is reflected in the absorption at 460 nm with f = 1.389.
The planar arrangement is destabilized by strong steric
interactions (see the potential energy curve in Figure 6).
Collectively, these results highlight that those attractive
spectroscopic properties, such as low transition energy and
high oscillator strength should emerge upon the formation of a
fused system, i.e., 10. The photophysical data gathered in
Tables 1 and S7 corroborate this prediction.
The values of absorption energy and oscillator strength for
compound 10 (Table 2) are close to those predicted based on
calculations for the planarized version of 4 (Figure 6). This is
not true, however, for the pair 6 and 11. Despite the red shift
EDA systems. Meaning, the HOMO orbital is created from the of 11 relative to 6, the oscillator strength of the transition
HOMO of the DHPP donor with an admixture of HOMO between S0 and S1 in 11 is f = 1.02 and is smaller than the
orbitals of both acceptors, and the LUMO orbitals are created oscillator strength in 6 ( f = 1.79). These computational
from a combination of LUMO orbitals of both acceptors with predictions are fully corroborated by comparison of exper-
an admixture of the donor’s LUMO orbital (see Figures 5 and imental molar absorption coefficients (Tables 1 and S7).
S8; the orbitals of individual elements are shown in Table S8). Therefore, when creating a fused system, an additional
Interestingly, formation of fully π-conjugated systems 10 and circumstance appears that affects its spectroscopic properties.
11 is accompanied by spreading both HOMO and LUMO into The oscillator strength is a quantity strongly determined by
N-aryl substituents (see Figure 5). the shape of the molecular orbitals. Therefore, the reasons for
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Scheme 4. Synthesis of Pyrrolopyrrole-Containing Multiple Azahelicene 11a−11d via Intramolecular Palladium-Catalyzed

Direct Arylation

Figure 2. Molar extinction spectrum (solid line) and normalized Figure 3. Molar extinction spectrum (solid line) and normalized
fluorescence emission spectrum (dashed-dotted line) of compounds fluorescence emission spectrum (dashed-dotted line) of compounds
4h (blue) and 10a (red) in DCM. 6i (blue) and 11a (red) in DCM.

such discrepancies can be sought in differences in the and 4 are similar as the relations between 11 with 6 (see Table
extension of the charge distribution to atoms of moieties 2). Comparison of the orbitals 10 and 10-x is given in Table S9
originating from electron-withdrawing moieties, which occurs and indicates that the orbitals of 10-x are more spread to the
in fused dyes. To confirm this, calculations were performed for N-aryl substituents than the orbital of 10.
the compound 10-x (Figure 7), which is an isomer of 10 with a
geometric structure analogous to 11 (for comparison of the
both structures see Table S3).The calculated oscillator strength
■ CONCLUSIONS
We have provided experimental evidence that the efficient
(f = 0.748) for fused system in geometry (10-x) is smaller than synthesis of quinoline derivatives enables not only preparation
oscillator strength (f = 0.815) for nonfused molecule 4 and of 1,4-dihydropyrrrolo[3,2-b]pyrroles possessing planarized
smaller than f = 1.203 for fused 10. Therefore, the relationships structures based on tetrazole but also previously inaccessible
between the transition energies and oscillator strengths of 10-x large planar N-doped nanographenes based on quinolines. The
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Table 1. Spectroscopic Properties of Compounds 4a, 4g, 6a, 6g, 6r, 10a, 10c, 11a, 11c, and 11d Obtained in Toluene and DCM
in DCM in toluene
λmax (Ab) ε@λmax λmax (Em) Stokes shift λmax (Ab) ε@λmax λmax (Em) Stokes shift
entry (nm) (M−1 cm−1) (nm) (cm−1) Φfl (nm) (M−1cm−1) (nm) (cm−1) Φfl
4a 397 14700 540 6700 0.13 399 15100 480 4200 0.19
4g 390 20800 533 6900 0.15 398 19800 472 3900 0.19
6a 456 55400 495 1700 0.56 463 52100 488 1100 0.55
6g 458 58100 501 1900 0.55 459 -a 494 1500 0.51
6r 434 32500 486 2500 0.13 460 34600 480 900 0.16
10a 474 32800 581 3900 0.64 501 36900 532 1200 0.52
10c 483 31600 589 3700 0.26 485 33600 554 2600 0.49
11a 561 19100 590 900 1.0 563 40600 586 700 0.79
11c 590 13000 622 900 0.27 591 38100 621 800 0.45
11d 505 16600 611 3400 0.21 509 19700 591 2700 0.16
a
Solubility was too low to reliably measure ε.

emission range of these prepared centrosymmetric, polarized sized according to literature procedures. All reactions requiring
TAPPs can be modulated from green to yellow, orange, and heating were carried out using an oil bath. Reaction progress
red, and their efficiency are typically moderate to high. was monitored by thin layer chromatography (TLC), which
Planarization of the chromophore structure results in was performed on aluminum foil plates, covered with Silica gel
considerable red shift of the emission wavelength (quinoline- 60 F254 (Merck). The identity and purity of prepared
derived dyes show strong yellow fluorescence and dyes compounds were proved by 1H NMR and 13C NMR
possessing two tetrazoloquinoline units exhibit red emission). spectroscopy, as well as by MS spectrometry (via APCI-MS
The two-photon absorption spectrum follows, in most cases, or EI-MS). NMR spectra were measured on Varian 500 MHz
the Laporte rule, which is in accord with the inversion- and Varian 600 MHz instruments. Chemical shifts for 1H
symmetric structure, with the peak cross-section values NMR are expressed in parts per million (ppm) relative to
reaching σ2PA = 250 GM in the case of TAPP possessing tetramethylsilane (δ 0.00 ppm), CDCl3 (δ 7.26 ppm), CD2Cl2
two tetrazoloquinoline substituents at positions 2 and 5. (δ 5.32 ppm), tetrachloroethane-[D2] (δ 5.91 ppm), C6D6 (δ
Critically, subtle changes in geometry of these π-extended dyes 7.16 ppm), and THF-[D8] (δ 1.73 and 3.58 ppm). Chemical
have a profound effect on their photophysics. Computational shifts for13C NMR are expressed in ppm relative to CDCl3 (δ
studies suggest that intersystem crossing yield is responsible for
77.2 ppm), CD2Cl2 (δ 54.0 ppm), tetrachloroethane-[D2] (δ
variation for modulation of fluorescence intensity, thus
73.7 ppm), C6D6 (δ 128.4 ppm), and THF-[D8] (δ 25.4 and
confirming the notion that planarization of the geometry of
67.6 ppm). Data are reported as follows: chemical shift,
polarized centrosymmetric dyes affords control over the
molecular excited state. The change in the absorption strength multiplicity (s = singlet, d = doublet, dd = doublet of doublets,
between weakly coupled (biaryl bridges) and fused quad- t = triplet, td = triplet of doublets, q = quartet, quint = quintet,
rupolar, centrosymmetric dyes is different for quinoline sex = sextet, br. s = broad singlet, m = multiplet), coupling
derivatives and for tetrazoloquinoline derivatives. In the latter constant (in Hz), and integration. Because of the very low
case, the molar absorption coefficient actually decreases after solubility of compounds 6a, 6c−6e, 6g, and 10a, their 13C
planarization of the entire chromophore. The computational NMR spectra have been measured at high temperature in
investigation enabled us to postulate that this striking tetrachloroethane-[D2]. Compounds 6f and 10b are not
difference has its origin in different orientation of the sufficiently soluble in common NMR solvents such as
electron-deficient heterocyclic moiety, which causes the spread CDCl3, acetone-[D6], DMSO-[D6], CD3CN, methanol-[D4],
of the localization of both HOMO and LUMO on N-aryl and tetrachloroethane-[D2] (even after heating) to allow for
moiety leading in turn to decrease in molar absorptivity. The measurement of 13C NMR spectra.
relative position of singlet and triplet excited states plays a All melting points for crystalline products were measured
dominant role in determining the fate of the molecules after with automated melting point apparatus EZ-MELT and were
excitation. In particular, it is responsible for relatively small given without correction.
fluorescence quantum yield for bis(quinolinyl)dyes. Collec- Spectrophotometric grade solvents were used without
tively, this work demonstrates that a tetrazole scaffold can be further purification. All photophysical studies were performed
efficiently incorporated into the structure of quadrupolar, with freshly prepared, air equilibrated solutions at room
centrosymmetric functional dyes furnishing the latter with temperature. Steady-state fluorescence measurements were
outstanding photophysical characteristics. performed in standard 1 cm quartz cuvettes with dilute
solutions (10−6 M, optical density <0.1) to minimize inner
■ EXPERIMENTAL SECTION
General Information. All chemicals were bought from
filter effects and/or aggregation. Absorption spectra were
measured using a UV−vis Shimadzu UV-3600i Plus
Sigma-Aldrich, TCI, Ambeed, and AlfaAesar and were used as spectrophotometer. The calculation of molar absorption
received unless otherwise noted. All solvents used for reactions coefficient was conducted from Beer−Lambert’s law equation.
were analysis grade and were used without further purification. Emission spectra were measured using Edinburgh Instruments
2-Chloroquinoline-3-carbaldehyde derivatives 1,37 tetrazolo- FS5 spectrofluorometer equipped with photomultiplier Hama-
[1,5-a]quinoline-4-carbaldehyde 5,38 2-bromo-4-dodecylani- matsu R123456. Fluorescence quantum yields (Φ) were
line,39 and 9-amino-10-bromophenanthrene40 were synthe- calculated from the equation:
4663 https://doi.org/10.1021/acs.joc.3c02916
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The Journal of Organic Chemistry pubs.acs.org/joc Article

Table 2. TDDFT/M06/6-31G(d,p) Calculated Energies and

Oscillator Strengths of the Absorption S0 → Si and
Fluorescence S1 → S0 Transitions
absorption fluorescence
comp. solvent (nm) f (nm) f
4 toluene 422 0.742 483 1.024
DCM 424 0.815 492 1.289
6 toluene 471 1.706 531 1.930
DCM 478 1.798 551 2.060
10 toluene 479 0.965 546 1.045
DCM 489 1.203 563 1.286
11 toluene 550 0.849 642 0.876
DCM 560 1.021 661 1.041
(10-x) toluene 502 0.593 588 0.627
DCM 510 0.748 603 0.783

Figure 5. Shape of HOMO and LUMO orbitals of investigated dyes.

Similarity and differences between HOMO and LUMO orbitals of
nonfused and fused dyes, 6 and 11 − orbitals of 11 are spreading to
N-aryl substituents.

Figure 4. 2PA cross-section spectra of 4h, 6h, and 10a in toluene

solution in GM (red line, left vertical and lower horizontal scale).
Black symbols�absolute 2PA cross sections measured at select
wavelengths. Blue line�molar extinction spectra in toluene (blue line,
upper horizontal axis). Dashed black line�ratio between the 2PA and
1PA spectral profiles (in arbitrary units).

(1 10 Ast) ·n2 ·S
= st ·
(1 10 A) ·nst2 · Sst (1)

where A denotes absorbance, n is a refractive index of a

solvent, and S is an integrated fluorescence intensity.
Typical Procedure for the Synthesis of 3,3′-(1,4-Bis(4-
(tert-butyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole- Figure 6. Potential energy curve of molecule 4 in S0 state as a
2,5-diyl)bis(2-chloroquinoline) (4a). Glacial acetic acid (2 function of changes in the mutual orientation of the planes of the
mL), toluene (2 mL), 2-chloroquinoline-3-carbaldehyde (383 DHPP donor and acceptors. At the top, the absorption energy values
mg, 2 mmol, 2 equiv), and 4-(tert-butyl)aniline (299 mg, 2 together with the oscillator strengths, corresponding to the minimum
mmol, 2 equiv) were placed in a 50 mL round-bottom flask geometry and extreme cases of coplanar and orthogonal donor and
equipped with a magnetic stir bar. The mixture reacted at 50 acceptor planes.
°C for 1 h. After that time, Fe(ClO4)3·xH2O (22 mg, 6 mol %)
was added, followed by butane-2,3-dione (87 μL, 1 mmol, 1 and 5 mL of methanol was added to the reaction mixture, and
equiv). The resulting mixture was stirred at 50 °C (oil bath) in the resulting mixture was stirred for 10 min. The precipitate
an open flask under air for 2 h. Next, the heater was removed, was filtered, washed with methanol (3 mL) and diethyl ether
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The Journal of Organic Chemistry pubs.acs.org/joc Article

3,3′-(1,4-Bis(4-heptylphenyl)-1,4-dihydropyrrolo[3,2-b]-
pyrrole-2,5-diyl)bis(2-chloro-6-methylquinoline) (4e). Off-
white solid (282 mg, 35%); m.p.: 253−254 °C; 1H NMR
(600 MHz, CDCl3) δ 7.99 (s, 2H), 7.93 (d, J = 8.6 Hz, 2H),
7.55 (dd, J = 8.6, 1.9 Hz, 2H), 7.46 (s, 2H), 7.17 (d, J = 8.1
Hz, 4H), 7.08 (d, J = 8.1 Hz, 4H), 6.59 (s, 2H), 2.54 (t, J = 7.8
Hz, 4H), 2.51 (s, 6H), 1.58−1.55 (m, 4H), 1.30−1.23 (m,
16H), 0.86 (t, J = 6.8 Hz, 6H); 13C{1H} NMR (126 MHz,
CDCl3) δ 149.5, 145.0, 140.6, 139.7, 137.4, 137.1, 132.8,
130.8, 130.8, 129.2, 127.8, 127.3, 126.8, 126.3, 124.1, 97.4,
35.4, 31.8, 31.2, 29.2, 29.1, 22.6, 21.6, 14.1; HRMS (APCI):
Figure 7. Structure of dye 10-x designed for computational purpose. m/z calculated for C52H55Cl2N4: 805.3804 [M + H]+; found:
805.3807.
3,3′-(1,4-Bis(4-decylphenyl)-1,4-dihydropyrrolo[3,2-b]-
(5 mL), and recrystallized from a dichloromethane/hexane pyrrole-2,5-diyl)bis(2-chloroquinoline) (4f). Off-white solid
mixture and dried under vacuum affording 278 mg (40%) of (311 mg, 36%); m.p.: 203−204 °C; 1H NMR (500 MHz,
pure product 4a as a yellow solid. CDCl3) δ 8.08 (s, 2H), 8.02 (d, J = 8.2 Hz, 2H), 7.73−7.70
The procedure for the synthesis of compounds 4b−4l is (m, 4H), 7.54 (t, J = 7.4 Hz, 2H), 7.17 (d, J = 8.0 Hz, 4H),
similar to that of compound 4a. 7.08 (d, J = 8.0 Hz, 4H), 6.61 (s, 2H), 2.54 (t, J = 7.8 Hz, 4H),
3,3′-(1,4-Bis(4-(tert-butyl)phenyl)-1,4-dihydropyrrolo[3,2- 1.59−1.53 (m, 4H), 1.30−1.24 (m, 28H), 0.87 (t, J = 6.8 Hz,
b]pyrrole-2,5-diyl)bis(2-chloroquinoline) (4a). Yellow solid 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 150.5, 146.5, 140.6,
(278 mg, 40%); m.p.: 333−334 °C; 1H NMR (600 MHz, 140.2, 137.1, 130.9, 130.7, 130.5, 129.2, 128.3, 127.5, 127.4,
CDCl3) δ 8.11 (d, J = 0.9 Hz, 2H), 8.03 (td, J = 8.8, 0.9 Hz, 127.2, 126.8, 124.1, 97.4, 35.4, 31.9, 31.2, 29.6, 29.6, 29.5, 29.3,
2H), 7.74−7.70 (m, 4H), 7.55−7.52 (m, 2H), 7.28 (d, J = 9.0 29.3, 22.7, 14.1; HRMS (APCI): m/z calculated for
Hz, 4H), 7.18 (d, J = 9.0 Hz, 4H), 6.59 (s, 2H), 1.26 (s, 18H); C56H63Cl2N4: 861.4430 [M + H]+; found: 861.4433.
13
C{1H} NMR (151 MHz, CDCl3) δ 150.5, 148.7, 146.4, 3,3′-(1,4-Bis(4-octylphenyl)-1,4-dihydropyrrolo[3,2-b]-
140.2, 136.9, 130.9, 130.6, 130.5, 128.2, 127.5, 127.5, 127.3, pyrrole-2,5-diyl)bis(2-chloro-6-hexylquinoline) (4g). Yellow
126.8, 126.2, 123.7, 97.6, 34.5, 31.3; HRMS (APCI): m/z solid (390 mg, 40%); m.p.: 121−122 °C; 1H NMR (500 MHz,
calculated for C44H39Cl2N4: 693.2552 [M + H]+; found: CDCl3) δ 8.02 (s, 2H), 7.91 (d, J = 8.6 Hz, 2H), 7.56 (dd, J =
693.2549. 8.7, 2.0 Hz, 2H), 7.46 (d, J = 1.9 Hz, 2H), 7.17 (d, J = 8.2 Hz,
3,3′-(1,4-Bis(4-(tert-butyl)phenyl)-1,4-dihydropyrrolo[3,2- 4H), 7.08 (d, J = 8.1 Hz, 4H), 6.58 (s, 2H), 2.76 (t, J = 7.8 Hz,
b]pyrrole-2,5-diyl)bis(2-chloro-6-methylquinoline) (4b). Yel- 4H), 2.54 (t, J = 7.8 Hz, 4H), 1.60−1.53 (m, 4H), 1.71−1.66
low solid (267 mg, 37%); m.p.: 324−325 °C; 1H NMR (600 (m, 4H), 1.37−1.24 (m, 32H), 0.91−0.85 (m, 12H); 13C{1H}
MHz, CDCl3) δ 8.02 (s, 2H), 7.90 (d, J = 8.6 Hz, 2H), 7.54 NMR (126 MHz, CDCl3) δ 149.6, 145.4, 142.2, 140.5, 139.7,
(dd, J = 8.6, 1.9 Hz, 2H), 7.47 (s, 2H), 7.27 (d, J = 8.7 Hz, 137.2, 132.0, 130.9, 130.8, 129.2, 128.0, 127.3, 126.8, 125.7,
4H), 7.18 (d, J = 8.6 Hz, 4H), 6.57 (s, 2H), 2.50 (s, 6H), 1.26 124.0, 97.3, 35.9, 35.4, 31.9, 31.7, 31.2, 31.1, 29.4, 29.3, 29.2,
(s, 18H); 13C{1H} NMR (151 MHz, CDCl3) δ 149.6, 148.6, 29.0, 22.6 (2 signals), 14.1 (2 signals); HRMS (APCI): m/z
145.2, 139.6, 137.3, 137.0, 132.7, 130.8, 130.8, 127.9, 127.4, calculated for C64H79Cl2N4: 973.5682 [M + H]+; found:
126.9, 126.3, 126.2, 123.6, 97.5, 34.4, 31.3, 21.6; HRMS 973.5696.
(APCI): m/z calculated for C46H43Cl2N4: 721.2859 [M + H]+; 3,3′-(1,4-Bis(4-octylphenyl)-1,4-dihydropyrrolo[3,2-b]-
found: 721.2862. pyrrole-2,5-diyl)bis(2-chloro-6-hexylquinoline) (4h). Pale yel-
3,3′-(1,4-Bis(3,4,5-trimethoxyphenyl)-1,4-dihydropyrrolo- low solid (348 mg, 32%); m.p.: 108−109 °C; 1H NMR (600
[3,2-b]pyrrole-2,5-diyl)bis(2-chloroquinoline) (4c). Yellow MHz, CDCl3) δ 8.01 (s, 2H), 7.91 (d, J = 8.6 Hz, 2H), 7.55
solid (343 mg, 45%); m.p.: 330−331 °C; 1H NMR (600 (d, J = 8.6 Hz, 2H), 7.45 (s, 2H), 7.16 (d, J = 7.9 Hz, 4H),
MHz, CDCl3) δ 8.14 (s, 2H), 8.04 (d, J = 8.6 Hz, 2H), 7.76− 7.06 (d, J = 7.9 Hz, 4H), 6.57 (s, 2H), 2.75 (t, J = 7.7 Hz, 4H),
7.73 (m, 4H), 7.57 (t, J = 7.5 Hz, 2H), 6.60 (s, 2H), 6.50 (s, 2.53 (t, J = 7.9 Hz, 4H), 1.70−1.65 (m, 4H), 1.56−1.52 (m,
4H), 3.80 (s, 6H), 3.58 (s, 12H); 13C{1H} NMR (126 MHz, 4H), 1.36−1.23 (m, 48H), 0.98−0.84 (m, 12H); 13C{1H}
CDCl3) δ 153.5, 150.6, 146.6, 140.3, 136.1, 135.1, 130.9, NMR (151 MHz, CDCl3) δ 149.6, 145.3, 142.3, 140.5, 139.7,
130.9, 130.4, 128.3, 127.5, 127.5, 127.4, 126.6, 101.9, 97.4, 137.2, 132.0, 130.8, 130.8, 129.2, 127.9, 127.3, 126.8, 125.7,
61.0, 56.1; HRMS (APCI): m/z calculated for 124.0, 97.3, 35.9, 35.4, 31.9, 31.7, 31.2, 31.1, 29.6, 29.6, 29.6,
C42H35Cl2N4O6: 761.1934 [M + H]+; found: 761.1932. 29.4, 29.3, 29.3, 29.0, 22.7, 22.6, 14.1 (2 signals); HRMS
3,3′-(1,4-Bis(4-heptylphenyl)-1,4-dihydropyrrolo[3,2-b]- (APCI): m/z calculated for C72H95Cl2N4: 1085.6934 [M +
pyrrole-2,5-diyl)bis(2-chloroquinoline) (4d). Off-white solid H]+; found: 1085.6943.
(241 mg, 31%); m.p.: 206−207 °C; 1H NMR (500 MHz, 3,3′-(1,4-Bis(4-dodecylphenyl)-1,4-dihydropyrrolo[3,2-b]-
CDCl3) δ 8.09 (s, 2H), 8.04 (d, J = 8.5 Hz, 2H), 7.73−7.70 pyrrole-2,5-diyl)bis(2-chloro-7-(methylthio)quinoline) (4i).
(m, 4H), 7.54 (t, J = 7.5 Hz, 2H), 7.17 (d, J = 8.0 Hz, 4H), Off-white solid (394 mg, 39%); m.p.: 133−134 °C; 1H
7.08 (d, J = 8.0 Hz, 4H), 6.61 (s, 2H), 2.54 (t, J = 7.8 Hz, 4H), NMR (600 MHz, CDCl3) δ 7.96 (s, 2H), 7.68 (s, 2H), 7.54
1.59−1.53 (m, 4H), 1.30−1.22 (m, 16H), 0.87 (t, J = 6.9 Hz, (d, J = 8.6 Hz, 2H), 7.36 (d, J = 8.6 Hz, 2H), 7.16 (d, J = 7.9
6H); 13C{1H} NMR (126 MHz, CDCl3) δ 150.4, 146.4, 140.7, Hz, 4H), 7.07 (d, J = 8.0 Hz, 4H), 6.58 (s, 2H), 2.59 (s, 6H),
140.2, 137.1, 130.9, 130.7, 130.5, 129.2, 128.2, 127.5, 127.4, 2.54 (t, J = 7.9 Hz, 4H), 1.59−1.52 (m, 4H), 1.27−1.24 (m,
127.3, 126.8, 124.1, 97.5, 35.4, 31.8, 31.2, 29.2, 29.1, 22.6, 36H), 0.87 (t, J = 6.8 Hz, 6H) 13C{1H} NMR (126 MHz,
14.1; HRMS (APCI): m/z calculated for C50H51Cl2N4: CDCl3) δ 151.0, 147.2, 143.1, 140.6, 139.8, 137.1, 130.8,
777.3491 [M + H]+; found: 777.3497. 130.7, 129.2, 127.2, 126.4, 126.3, 124.2, 124.1, 121.6, 97.3,
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The Journal of Organic Chemistry pubs.acs.org/joc Article

35.4, 31.9, 31.2, 29.7, 29.6 (3 signals), 29.5, 29.3 (2 signals), 4,4′-(1,4-Bis(4-(tert-butyl)phenyl)-1,4-dihydropyrrolo[3,2-
22.7, 14.9, 14.1; HRMS (APCI): m/z calculated for b]pyrrole-2,5-diyl)ditetrazolo[1,5-a]quinoline (6a). Brown
C62H75Cl2N4S2: 1009.4810 [M + H]+; found: 1009.4819. solid (431 mg, 61%); m.p.: 310−311 °C (dec.); 1H NMR
3,3′-(1,4-Bis(3,5-di-tert-butylphenyl)-1,4-dihydropyrrolo- (600 MHz, CDCl3) δ 8.61 (d, J = 7.8 Hz, 2H), 7.71 (td, J =
[3,2-b]pyrrole-2,5-diyl)bis(2-chloro-6-hexylquinoline) (4j). 7.7, 1.1 Hz, 2H), 7.63 (s, 2H), 7.55 (td, J = 7.7, 1.1 Hz, 2H),
Pale yellow solid (400 mg, 41%); m.p.: 294−295 °C; 1H 7.50 (d, J = 8.6 Hz, 4H), 7.44 (d, J = 7.9 Hz, 2H), 7.40 (d, J =
NMR (500 MHz, CDCl3) δ 8.04 (s, 2H), 7.88 (d, J = 8.6 Hz, 8.6 Hz, 4H), 7.18 (s, 2H), 1.40 (s, 18H); 13C{1H} NMR (126
2H), 7.53 (d, J = 8.7 Hz, 2H), 7.45 (s, 2H), 7.17 (s, 2H), 7.09 MHz, tetrachloroethane-[D2]) δ 150.5, 146.9, 136.6, 135.0,
(s, 4H), 6.58 (s, 2H), 2.76 (t, J = 7.6 Hz, 4H), 1.70−1.64 (m, 130.0, 129.8, 128.6, 128.6, 128.3, 128.0, 126.9, 125.4, 124.2,
4H), 1.35−1.25 (m, 12H), 1.11 (s, 36H), 0.88 (t, J = 6.6 Hz, 118.0, 116.5, 99.7, 34.7, 31.4; HRMS (APCI): m/z calculated
6H); 13C{1H} NMR (151 MHz, THF-D8) δ 151.5, 149.8, for C44H39N10: 707.3359 [M + H]+; found: 707.3362.
145.7, 141.9, 139.8, 139.1, 131.6, 131.1, 130.3, 127.8 (2 4,4′-(1,4-Bis(4-(tert-butyl)phenyl)-1,4-dihydropyrrolo[3,2-
signals), 126.9, 125.7, 118.8 (2 signals), 96.3, 35.6, 34.5, 31.7, b]pyrrole-2,5-diyl)bis(7-methyltetrazolo[1,5-a]quinoline)
31.1, 30.6, 28.8, 22.5, 13.5; HRMS (APCI): m/z calculated for (6b). Brown solid (500 mg, 68%); m.p.: 318−319 °C (dec.);
1
C64H79Cl2N4: 973.5682 [M + H]+; found: 973.5690. H NMR (500 MHz, CDCl3) δ 8.49 (d, J = 8.5 Hz, 2H), 7.61
3,3′-(1,4-Bis(3,5-di-tert-butylphenyl)-1,4-dihydropyrrolo- (s, 2H), 7.53 (dd, J = 8.5, 1.7 Hz, 2H), 7.49 (d, J = 8.5 Hz,
[3,2-b]pyrrole-2,5-diyl)bis(2-chloro-6-methylquinoline) (4k). 4H), 7.39 (d, J = 8.5 Hz, 4H), 7.21 (s, 2H), 7.11 (s, 2H), 2.47
Pale yellow solid (392 mg, 47%); m.p.: 381−382 °C; 1H NMR (s, 6H), 1.40 (s, 18H); 13C{1H} NMR (126 MHz, CDCl3) δ
(500 MHz, CDCl3) δ 8.05 (s, 2H), 7.88 (d, J = 8.6 Hz, 2H), 150.3, 146.8, 138.2, 137.1, 135.1, 131.2, 129.9, 127.9, 127.4,
7.53 (dd, J = 8.6, 1.9 Hz, 2H), 7.17 (t, J = 1.8 Hz, 2H), 7.48 (s, 126.9, 126.8, 125.6, 124.4, 118.2, 116.4, 100.0, 34.7, 31.4, 21.4;
2H), 7.10 (d, J = 1.8 Hz, 4H), 6.58 (s, 2H), 2.52 (s, 6H), 1.12 HRMS (APCI): m/z calculated for C46H43N10: 735.3672 [M +
(s, 36H); 13C{1H} NMR (126 MHz, CDCl3) δ 151.8, 149.9, H]+; found: 735.3674.
145.2, 139.7, 138.7, 137.2, 132.7, 131.0, 130.3, 127.8, 127.6, 4,4′-(1,4-Bis(3,4,5-trimethoxyphenyl)-1,4-dihydropyrrolo-
126.8, 126.2, 119.2, 119.1, 96.6, 34.8, 31.2, 21.6; HRMS [3,2-b]pyrrole-2,5-diyl)ditetrazolo[1,5-a]quinoline (6c).
(APCI): m/z calculated for C54H59Cl2N4: 833.4117 [M + H]+; Cream solid (504 mg, 65%); m.p.: 322−323 °C (dec.); 1H
found: 833.4122. NMR (500 MHz, CDCl3) δ 8.63 (d, J = 8.3 Hz, 2H), 7.75 (dt,
3,3′-(1,4-Di(naphthalen-1-yl)-1,4-dihydropyrrolo[3,2-b]- J = 8.5, 4.2 Hz, 2H), 7.68 (s, 2H), 7.59 (d, J = 4.2 Hz, 4H),
pyrrole-2,5-diyl)bis(2-chloro-6-octylquinoline) (4l). Pale yel- 7.33 (s, 2H), 6.72 (s, 4H), 3.97 (s, 6H), 3.77 (s, 12H);
13
low solid (272 mg, 30%); m.p.: 208−209 °C; 1H NMR (600 C{1H} NMR (126 MHz, tetrachloroethane-[D2]) δ 153.6,
MHz, CDCl3, mixture of atropisomers) δ 8.28 (d, J = 8.4 Hz, 146.2, 136.8, 134.4, 134.2, 129.8, 129.2, 128.2, 128.0, 127.8,
1H), 8.11 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 7.87 127.1, 123.4, 117.1, 116.0, 103.2, 99.0, 60.6, 56.0; HRMS
(d, J = 8.0 Hz, 1H), 7.83 (s, 1H), 7.81 (s, 1H), 7.79−7.75 (m, (APCI): m/z calculated for C42H35N10O6: 775.2741 [M +
3H), 7.59 (t, J = 7.9 Hz, 1H), 7.57−7.47 (m, 3H), 7.45−7.40 H]+; found: 775.2742.
(m, 2H), 7.38 (t, J = 7.8 Hz, 1H), 7.30 (t, J = 7.9 Hz, 1H), 4,4′-(1,4-Bis(2,4-dimethoxyphenyl)-1,4-dihydropyrrolo-
[3,2-b]pyrrole-2,5-diyl)ditetrazolo[1,5-a]quinoline (6d). Yel-
7.25 (s, 3H), 7.21 (s, 1H), 7.19 (s, 1H), 6.38 (s, 1H), 6.36 (s,
low solid (443 mg, 62%); m.p.: 316−317 °C (dec.); 1H NMR
1H), 2.64 (t, J = 7.9 Hz, 4H), 1.62−1.57 (m, 4H), 1.34−1.17
(500 MHz, tetrachloroethane-[D2], mixture of atropisomers) δ
(m, 20H), 0.86 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (126 MHz,
7.92 (d, J = 8.3 Hz, 2H), 7.08 (dt, J = 8.4, 4.1 Hz, 2H), 6.89−
CDCl3, mixture of atropisomers) δ 149.3, 145.0, 142.0, 139.1,
6.94 (m, 4H), 6.72−6.79 (m, 3H), 6.64 (d, J = 6.7 Hz, 2H),
135.8, 134.5, 132.9, 132.7, 131.8, 129.9, 129.7, 128.3, 128.2, 6.58 (d, J = 8.6 Hz, 1H), 6.06 (d, J = 2.6 Hz, 1H), 5.96−6.00
127.8, 127.6, 126.7, 126.5, 126.5, 125.6, 125.4, 124.2, 124.1, (m, 2H), 5.89 (dd, J = 8.5, 2.6 Hz, 1H), 3.25 (s, 3H), 3.23 (s,
98.4, 97.9, 35.8, 31.8, 31.1, 29.4, 29.2, 29.2, 22.6, 14.1; HRMS 3H), 3.14 (s, 3H), 2.96 (s, 3H); 13C{1H} NMR (126 MHz,
(APCI): m/z calculated for C60H59Cl2N4: 905.4117 [M + H]+; tetrachloroethane-[D2], mixture of atropisomers) δ 159.7,
found: 905.4118. 154.8, 146.3, 134.8, 134.6, 130.5, 130.4, 129.2, 128.8, 128.6,
Typical Procedure for the Synthesis of 4,4′-(1,4-Bis(4- 128.2, 127.9, 127.6, 125.6, 125.0, 123.8, 120.9, 120.8, 118.2,
(tert-butyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole- 118.0, 115.9, 104.7, 99.8, 99.7, 99.0, 98.3, 55.6, 55.4, 55.3;
2,5-diyl)ditetrazolo[1,5-a]quinoline (6a). Glacial acetic HRMS (APCI): m/z calculated for C40H31N10O4: 715.2530
acid (10 mL), toluene (10 mL), tetrazolo[1,5-a]quinoline-4- [M + H]+; found: 715.2524.
carbaldehyde (396 mg, 2 mmol, 2 equiv), and 4-(tert- 4,4′-(1,4-Bis(2-bromo-4-(tert-butyl)phenyl)-1,4-
butyl)aniline (299 mg, 2 mmol, 2 equiv) were placed in a 50 dihydropyrrolo[3,2-b]pyrrole-2,5-diyl)ditetrazolo[1,5-a]-
mL round-bottom flask equipped with a magnetic stir bar. The quinoline (6e). Orange solid (363 mg, 42%); m.p.: 328−329
mixture reacted at 50 °C for 1 h. After that time, Fe(ClO4)3· °C (dec.); 1H NMR (500 MHz, tetrachloroethane-[D2],
xH2O (22 mg, 6 mol %) was added, followed by butane-2,3- mixture of atropisomers) δ 8.47 (d, J = 8.3 Hz, 2H), 7.72 (s,
dione (87 μL, 1 mmol, 1 equiv). The resulting mixture was 1H), 7.68−7.61 (m, 3H), 7.53−7.42 (m, 6H), 7.40−7.30 (m,
stirred at 80 °C (oil bath) in an open flask under air for 2 h. 4H), 6.97 (s, 2H), 1.31 (s, 18H); 13C{1H} NMR (126 MHz,
Next, the heater was removed, and 5 mL of methanol was tetrachloroethane-[D2], mixture of atropisomers) δ 154.3,
added to the reaction mixture, and the resulting mixture was 154.2, 146.9, 136.3, 136.3, 135.2, 134.9, 131.5, 131.5, 131.4,
stirred for 10 min. The precipitate was filtered, washed with 130.2, 129.8, 129.7, 128.8, 128.6, 126.7, 126.6, 126.3, 126.1,
methanol (5 mL) and diethyl ether (5 mL), recrystallized from 124.6, 122.4, 122.2, 118.6, 118.4, 116.8, 100.6, 100.2, 35.2,
dichloromethane/hexane mixture, and dried under vacuum 31.5; HRMS (APCI): m/z calculated for C44H37Br2N10:
affording 431 mg (61%) of pure product 6a as a brown solid. 863.1569 [M + H]+; found: 863.1560.
The procedure for the synthesis of compounds 6b−6r is 4,4′-(1,4-Bis(2-bromo-4-(tert-butyl)phenyl)-1,4-
similar to that of compound 6a. dihydropyrrolo[3,2-b]pyrrole-2,5-diyl)bis(7-methyltetrazolo-
4666 https://doi.org/10.1021/acs.joc.3c02916
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The Journal of Organic Chemistry pubs.acs.org/joc Article

[1,5-a]quinoline) (6f). Orange solid (179 mg, 20%); m.p.: (APCI): m/z calculated for C48H47N10: 763.3985 [M + H]+;
338−339 °C; 1H NMR (600 MHz, tetrachloroethane-[D2], found: 763.3988.
mixture of atropisomers) δ 8.38 (d, J = 1.3 Hz, 1H), 8.37 (d, J 4,4′-(1,4-Bis(4-hexylphenyl)-1,4-dihydropyrrolo[3,2-b]-
= 1.6 Hz, 1H), 7.74 (d, J = 2.1 Hz, 1H), 7.69 (d, J = 2.1 Hz, pyrrole-2,5-diyl)bis(7-methyltetrazolo[1,5-a]quinoline) (6k).
1H), 7.53 (d, J = 8.2 Hz, 1H), 7.49 (d, J = 2.6 Hz, 2H), 7.48 Yellow solid (475 mg, 60%); m.p.: 256−257 °C; 1H NMR
(s, 1H), 7.47−7.45 (m, 2H), 7.40 (d, J = 2.0 Hz, 1H), 7.37 (d, (600 MHz, CDCl3) δ 8.47 (d, J = 8.5 Hz, 2H), 7.57 (s, 2H),
J = 8.2 Hz, 1H), 7.12 (s, 1H), 7.10 (s, 1H), 6.93 (s, 1H), 6.92 7.51 (dd, J = 8.5, 1.8 Hz, 2H), 7.36 (d, J = 8.3 Hz, 4H), 7.26
(s, 1H), 2.40 (s, 6H), 1.34 (s, 9H), 1.34 (s, 9H); HRMS (d, J = 8.3 Hz, 4H), 7.22 (s, 2H), 7.11 (s, 2H), 2.69 (t, J = 7.6
(APCI): m/z calculated for C46H41Br2N10: 891.1882 [M + Hz, 4H), 2.46 (s, 6H), 1.68 (m, 4H), 1.40−1.26 (m, 12H),
H]+; found: 891.1869. 0.89 (t, J = 6.9 Hz, 6H); 13C{1H} NMR (151 MHz, CDCl3) δ
Dimethyl 2,2′-(2,5-bis(7-methyltetrazolo[1,5-a]quinolin- 146.6, 141.9, 138.1, 137.3, 135.1, 131.1, 129.8, 129.8, 127.8,
4-yl)pyrrolo[3,2-b]pyrrole-1,4-diyl)dibenzoate (6g). Yellow 127.4, 126.7, 125.8, 124.1, 118.0, 116.2, 99.9, 35.5, 31.7, 31.4,
solid (377 mg, 51%); m.p.: 249−250 °C (dec.); 1H NMR 28.9, 22.6, 21.3, 14.1; HRMS (APCI): m/z calculated for
(500 MHz, tetrachloroethane-[D2], mixture of atropisomers) δ C50H51N10: 791.4298 [M + H]+; found: 791.4305.
7.81 (d, J = 4.2 Hz, 2H), 7.79 (d, J = 4.3 Hz, 2H), 7.29 (dt, J = 4,4′-(1,4-Bis(3,5-di-tert-butylphenyl)-1,4-dihydropyrrolo-
7.9, 1.7 Hz, 2H), 7.00 (dd, J = 3.2, 1.3 Hz, 2H), 6.95−6.88 (m, [3,2-b]pyrrole-2,5-diyl)ditetrazolo[1,5-a]quinoline (6l). Yel-
4H), 6.73 (d, J = 1.1 Hz, 2H), 6.58 (d, J = 5.6 Hz, 2H), 6.40 low solid (524 mg, 64%); m.p.: 323−324 °C (dec.); 1H
(s, 1H), 6.39 (s, 1H), 2.90 (s, 3H), 2.87 (s, 3H), 1.82 (s, 6H); NMR (600 MHz, CDCl3) δ 8.61 (d, J = 8.3 Hz, 2H), 7.53 (td,
13
C{1H} NMR (126 MHz, tetrachloroethane-[D2], mixture of J = 8.4, 1.3 Hz, 2H), 7.66 (s, 2H), 7.53 (td, J = 8.4, 1.3 Hz,
atropisomers) δ 166.0, 165.8, 145.9, 145.9, 138.0, 138.0, 137.9, 2H), 7.47 (t, J = 1.8 Hz, 2H), 7.38 (d, J = 6.6 Hz, 2H), 7.32 (d,
134.5, 134.2, 133.0, 131.1, 131.0, 130.5, 128.9, 128.3, 128.3, J = 1.8 Hz, 4H), 7.12 (s, 2H), 1.27 (s, 36H); 13C{1H} NMR
128.1, 127.7, 127.5, 127.1, 126.7, 126.2, 123.6, 123.6, 117.0, (151 MHz, CDCl3) δ 152.8, 147.0, 138.8, 134.8, 129.7, 129.6,
116.9, 115.7, 98.8, 98.6, 52.1, 52.0, 20.8; HRMS (APCI): m/z 128.6, 128.3, 127.9, 127.3, 124.1, 120.9, 120.7, 118.3, 116.6,
calculated for C42H31N10O4: 739.2530 [M + H]+; found: 99.5, 35.0, 31.4; HRMS (APCI): m/z calculated for
739.2525. C52H55N10: 819.4611 [M + H]+; found: 819.4608.
4,4′-(1,4-Bis(4-dodecylphenyl)-1,4-dihydropyrrolo[3,2-b]- 4,4′-(1,4-Bis(3,5-di-tert-butylphenyl)-1,4-dihydropyrrolo-
pyrrole-2,5-diyl)ditetrazolo[1,5-a]quinoline (6h). Off-white [3,2-b]pyrrole-2,5-diyl)bis(7-methyltetrazolo[1,5-a]-
solid (559 mg, 60%); m.p.: 183−184 °C; 1H NMR (500 quinoline) (6m). Yellow solid (443 mg, 61%); m.p.: 307−308
°C (dec.); 1H NMR (600 MHz, CDCl3, mixture of
MHz, CDCl3) δ 8.55 (d, J = 8.2 Hz, 2H), 7.68 (t, J = 7.8 Hz,
atropisomers) δ 8.49 (d, J = 8.4 Hz, 2H), 7.61 (s, 2H), 7.52
2H), 7.58 (s, 2H), 7.51 (t, J = 7.5 Hz, 2H), 7.42 (d, J = 7.5 Hz,
(d, J = 8.4 Hz, 2H), 7.45 (t, J = 1.9 Hz, 2H), 7.31 (s, 4H), 7.16
2H), 7.37 (d, J = 7.8 Hz, 4H), 7.27 (d, J = 7.8 Hz, 4H), 7.14
(s, 2H), 7.09 (s, 2H), 2.48 (s, 6H), 1.27 (s, 36H); 13C{1H}
(s, 2H), 2.69 (t, J = 7.6 Hz, 4H), 1.73−1.63 (m, 4H), 1.40−
NMR (151 MHz, CDCl3, mixture of atropisomers) δ 152.7,
1.34 (m, 8H), 1.33−1.19 (m, 28H), 0.87 (t, J = 6.8 Hz, 6H);
13 146.9, 138.8, 138.0, 134.6, 131.2, 129.6, 127.7, 127.4, 126.8,
C{1H}NMR (126 MHz, CDCl3) δ 146.8, 142.1, 137.2, 124.1, 120.8, 120.5, 118.2, 116.4, 99.5, 35.0, 31.3, 21.4; HRMS
135.2, 129.8, 129.6, 128.6, 128.4, 127.9, 127.5, 125.9, 124.2, (APCI): m/z calculated for C54H59N10: 847.4924 [M + H]+;
118.1, 116.5, 100.0, 35.5, 31.9, 31.4, 29.7 (4 signals), 29.6, found: 847.4923.
29.4, 29.3, 22.7, 14.1; HRMS (APCI): m/z calculated for 4,4′-(1,4-Bis(2-bromo-4-(tert-butyl)phenyl)-1,4-
C60H71N10: 931.5863 [M + H]+; found: 931.5862. dihydropyrrolo[3,2-b]pyrrole-2,5-diyl)bis(7-hexyltetrazolo-
4,4′-(1,4-Bis(4-dodecylphenyl)-1,4-dihydropyrrolo[3,2-b]- [1,5-a]quinoline) (6n). Yellow solid (496 mg, 48%); m.p.:
pyrrole-2,5-diyl)bis(7-methyltetrazolo[1,5-a]quinoline) (6i). 291−292 °C (dec.); 1H NMR (500 MHz, CDCl3) δ 8.49 (s,
Off-white solid (624 mg, 65%); m.p.: 238−239 °C; 1H 1H), 8.47 (s, 1H), 7.86 (d, J = 2.1 Hz, 1H), 7.76 (d, J = 2.1
NMR (500 MHz, CDCl3) δ 8.39 (d, J = 8.4 Hz, 2H), 7.55 (s, Hz, 1H), 7.62 (d, J = 2.8 Hz, 2H), 7.57 (d, J = 8.2 Hz, 1H),
2H), 7.48 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 7.8 Hz, 4H), 7.26 7.52 (s, 1H), 7.51 (s, 1H), 7.39 (dd, J = 8.3, 2.1 Hz, 1H), 7.28
(d, J = 8.1 Hz, 4H), 7.16 (s, 2H), 7.04 (s, 2H), 2.69 (t, J = 7.6 (s, 1H), 7.17 (s, 1H), 7.13 (s, 1H), 6.98 (s, 1H), 6.97 (s, 2H),
Hz, 4H), 2.46 (s, 6H), 1.73−1.63 (m, 4H), 1.41−1.34 (m, 2.71 (t, J = 6.9 Hz, 4H), 1.67−1.59 (m, 4H), 1.42 (s, 9H), 1.41
8H), 1.32−1.21 (m, 28H), 0.87 (t, J = 6.8 Hz, 6H); 13C{1H} (s, 9H), 1.34−1.26 (m, 12H), 0.88 (t, J = 6.4 Hz, 6H);
NMR (126 MHz, CDCl3) δ 146.6, 141.9, 138.1, 137.3, 135.1, 13
C{1H} NMR (126 MHz, CDCl3) δ 153.7, 153.6, 146.6,
131.1, 129.9, 129.8, 127.8, 127.4, 126.7, 125.8, 124.2, 118.0, 146.6, 143.2, 143.2, 136.5, 136.4, 135.0, 134.6, 131.2, 131.2,
116.3, 99.9, 35.5, 31.9, 31.4, 29.7, 29.7, 29.7, 29.5, 29.4, 29.2, 131.1, 130.6, 130.6, 129.8, 129.7, 127.3, 127.2, 127.1, 127.0,
22.7, 21.3, 14.1; HRMS (APCI): m/z calculated for 126.2, 126.1, 126.0, 125.6, 124.5, 122.2, 122.1, 118.4, 118.1,
C62H75N10: 959.6176 [M + H]+; found: 959.6185. 116.4, 116.4, 100.8, 100.0, 35.7, 35.0, 35.0, 31.6, 31.2, 28.8,
4,4′-(1,4-Bis(4-hexylphenyl)-1,4-dihydropyrrolo[3,2-b]- 28.8, 22.5, 14.0; HRMS (APCI): m/z calculated for
pyrrole-2,5-diyl)ditetrazolo[1,5-a]quinoline (6j). Yellow solid C56H61Br2N10: 1031.3442 [M + H]+; found: 1031.3451.
(473 mg, 62%); m.p.: 262−263 °C; 1H NMR (600 MHz, 4,4′-(1,4-Bis(2-bromo-4-dodecylphenyl)-1,4-
CDCl3) δ 8.60 (d, J = 8.8 Hz, 2H), 7.71 (ddd, J = 8.4, 7.2, 1.3 dihydropyrrolo[3,2-b]pyrrole-2,5-diyl)bis(7-methyltetrazolo-
Hz, 2H), 7.59 (s, 2H), 7.52 (ddd, J = 8.4, 7.2, 1.3 Hz, 2H), [1,5-a]quinoline) (6o). Yellow solid (581 mg, 52%); m.p.:
7.46 (d, J = 7.1 Hz, 2H), 7.37 (d, J = 8.3 Hz, 4H), 7.27 (d, J = 271−272 °C; 1H NMR (500 MHz, CDCl3) δ 8.49 (d, J = 8.3
8.3 Hz, 4H), 7.18 (s, 2H), 2.68 (t, J = 7.6 Hz, 4H), 1.69−1.64 Hz, 2H), 7.69 (s, 1H), 7.60 (s, 3H), 7.56 (d, J = 7.6 Hz, 1H),
(m, 4H), 1.40−1.28 (m, 12H), 0.90 (t, J = 6.9 Hz, 6H); 7.54 (s, 1H), 7.52 (s, 1H), 7.32 (d, J = 7.9 Hz, 1H), 7.24 (s,
13
C{1H} NMR (151 MHz, CDCl3) δ 146.8, 142.0, 137.2, 2H), 7.23−7.16 (m, 2H), 7.03 (s, 2H), 2.74 (t, J = 7.4 Hz,
135.1, 129.8, 129.6, 128.6, 128.4, 127.9, 127.4, 125.9, 124.1, 2H), 2.72 (t, J = 7.4 Hz, 2H), 2.49 (s, 6H), 1.77−1.66 (m,
118.1, 116.5, 100.0, 35.5, 31.7, 31.4, 28.9, 22.6, 14.1; HRMS 4H), 1.46−1.36 (m, 8H), 1.35−1.21 (m, 28H), 0.90 (t, J = 6.7
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The Journal of Organic Chemistry pubs.acs.org/joc Article

Hz, 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 145.3, 138.1, mol %). Then, dry m-xylene (3 mL) was added, and the
136.6, 135.1, 134.7, 133.9, 131.2, 130.0, 129.0, 128.0, 126.1, resulting mixture was degassed 3 times (by evacuation and
125.4, 124.5, 118.3, 116.4, 100.8, 100.0, 35.3, 31.9, 31.2, 29.7, refilling with argon) and stirred at 160 °C overnight. After
29.7, 29.7, 29.6, 29.5, 29.4, 29.2, 22.7, 21.3, 14.1; HRMS cooling to around 80 °C, toluene (10 mL) was added, and the
(APCI): m/z calculated for C62H73Br2N10: 1115.4386 [M + resulting suspension was passed through a pad of Celite. Next,
H]+; found: 1115.4421. the product was washed from the Celite pad with boiling
4,4′-(1,4-Bis(2-bromo-4-dodecylphenyl)-1,4- toluene, all filtrates were concentrated to ca. 2 mL and 36.5 mg
dihydropyrrolo[3,2-b]pyrrole-2,5-diyl)bis(7-octyltetrazolo- (90%) of 10a as orange solid was filtered off. The dried
[1,5-a]quinoline) (6p). Pale yellow solid (618 mg, 47%); m.p.: product 10a obtained was pure enough for all analytical
245−246 °C (dec.); 1H NMR (500 MHz, CDCl3, mixture of purposes.
atropisomers) δ 8.57−8.46 (m, 2H), 7.70−7.52 (m, 6H), The procedure for the synthesis of compounds 10b and 10c
7.34−7.18 (m, 6H), 7.08−7.02 (m, 2H), 2.83−2.65 (m, 8H), is similar to that of compound 10a.
1.77−1.63 (m, 8H), 1.46−1.16 (m, 56H), 0.95−0.81 (m, 7,19-Didodecyl-2,14-dihexyldibenzo[b,h]benzo[5′,6’]-
12H); 13C{1H} NMR (126 MHz, CDCl3, mixture of quino[2″,3″:7′,8’]indolizino[3′,2′:4,5]pyrrolo[2,1-f ]-1,6-
atropisomers) δ 146.6 (2 signals), 145.4, 145.3, 143.2, 143.1, naphthyridine (10a). Orange solid (36.5 mg, 90%); m.p.:
139.1, 136.6, 135.1, 134.6, 133.9 (2 signals), 131.3, 131.2, 305−306 °C (dec.); 1H NMR (500 MHz, Benzene-d6) δ 9.35
130.5 (2 signals), 130.0, 129.9, 129.1, 128.9, 127.4, 127.3, (d, J = 7.2 Hz, 2H), 8.30 (dd, J = 8.5, 3.9 Hz, 2H), 8.05 (d, J =
127.0, 126.3, 125.6, 124.5, 124.4, 122.1, 122.0, 118.4, 118.2, 8.4 Hz, 2H), 7.81−7.78 (m, 2H), 7.47−7.43 (m, 4H), 7.31−
116.5, 116.4, 100.8, 100.0, 35.7, 35.3, 31.9, 31.8, 31.4, 31.3 (2 7.29 (m, 2H), 6.97 (s, 1H), 6.96 (d, J = 11.0 Hz, 1H), 2.79 (t, J
signals), 29.7 (3 signals), 29.6 (2 signals), 29.4 (2 signals), = 7.9 Hz, 4H), 2.71 (t, J = 7.8 Hz, 4H), 1.84−1.79 (m, 4H),
29.3, 29.2, 22.7, 22.6, 14.1 (2 signals); HRMS (APCI): m/z 1.74−1.71 (m, 4H), 1.53−1.24 (m, 48H), 0.97 (t, J = 6.8 Hz,
calculated for C76H101Br2N10: 1311.6577 [M + H]+; found: 6H), 0.91 (t, J = 6.8 Hz, 6H); 13C{1H} NMR (126 MHz,
1311.6583. tetrachloroethane-[D2]) δ 145.7, 143.9, 141.0, 137.7, 134.6,
4,4′-(1,4-Bis(2-bromonaphthalen-1-yl)-1,4- 130.6, 130.3, 129.2, 127.8, 126.8, 126.4, 125.7, 125.1, 122.2,
dihydropyrrolo[3,2-b]pyrrole-2,5-diyl)bis(7-hexyltetrazolo- 120.4, 114.8, 99.7, 89.3, 36.0, 35.7, 31.9, 31.8, 31.4, 30.8, 29.7,
[1,5-a]quinoline) (6q). Pale yellow solid (439 mg, 43%); m.p.: 29.6 (2 signals), 29.3, 29.1, 22.6, 14.0, 13.9; HRMS (APCI):
227−228 °C (dec.); 1H NMR (500 MHz, CDCl3, mixture of m/z calculated for C72H93N4: 1013.7400 [M + H]+; found:
atropisomers) δ 8.38 (dd, J = 8.5, 2.8 Hz, 2H), 7.98 (d, J = 8.8 1013.7426.
Hz, 2H), 7.95 (d, J = 8.8 Hz, 2H), 7.90 (d, J = 8.8 Hz, 1H), 7,19-Didodecyl-3,15-bis(methylthio)dibenzo[b,h]benzo-
7.87 (d, J = 8.8 Hz, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.61 (d, J = [5′,6’]quino[2″,3″:7′,8’]indolizino[3′,2′:4,5]pyrrolo[2,1-f ]-1,6-
4.7 Hz, 2H), 7.59−7.51 (m, 3H), 7.48 (d, J = 7.7 Hz, 2H), naphthyridine (10b). Red solid (14.7 mg, 39%); m.p.: 323−
7.44 (d, J = 8.2 Hz, 2H), 6.96 (s, 1H), 7.00 (s, 1H), 6.93 (s, 324 °C (dec.); 1H NMR (500 MHz, tetrachloroethane-[D2]) δ
1H), 6.90 (s, 1H), 2.66−2.58 (m, 4H), 1.62−1.51 (m, 4H), 8.76 (s, 2H), 8.06−8.20 (br. s, 2H), 7.71−7.69 (m, 4H), 7.55−
1.33−1.22 (m, 12H), 0.83−0.87 (m, 6H); 13C{1H} NMR (126 7.48 (br. s, 2H), 7.44 (d, J = 8.2 Hz, 2H), 7.29 (d, J = 8.2 Hz,
MHz, CDCl3, mixture of atropisomers) δ 146.3, 143.1, 135.3, 2H), 6.85−6.99 (br. s, 2H), 2.83 (t, J = 7.9 Hz, 4H), 2.64 (s,
135.0, 134.9, 133.4 (2 signals), 132.8, 132.7, 132.5, 132.4, 6H), 1.82−1.85 (m, 4H), 1.50−1.55 (m, 4H), 1.43−1.49 (m,
130.5 (2 signals), 130.1, 128.8 (2 signals), 128.3, 127.3 (2 4H), 1.26−1.40 (m, 28H), 0.87 (t, J = 6.8 Hz, 6H); HRMS
signals), 127.0, 124.8, 124.7, 124.3, 123.3, 123.1, 122.4, 122.3, (APCI): m/z calculated for C62H73N4S2: 937.5277 [M + H]+;
118.1, 116.3, 100.2, 100.1, 35.6, 31.6, 31.3, 28.8, 22.6, 14.1; found: 937.5278.
HRMS (APCI): m/z calculated for C56H49Br2N10: 1019.2508 2,16-Dioctylbenzo[b]naphtho[1,2-h]naphtho[1″,2″:5′,6’]-
[M + H]+; found: 1019.2520. quino[2″,3″:7′,8’]indolizino[3′,2′:4,5]pyrrolo[2,1-f ]-1,6-
4,4′-(1,4-Bis(10-bromophenanthren-9-yl)-1,4- naphthyridine (10c). Orange solid (11.7 mg, 35%); m.p.:
dihydropyrrolo[3,2-b]pyrrole-2,5-diyl)bis(7-octyltetrazolo- 295−296 °C (dec.); 1H NMR (500 MHz, CDCl3) δ 9.25 (d, J
[1,5-a]quinoline) (6r). Brown solid (424 mg, 36%); m.p.: = 7.1 Hz, 2H), 9.20 (d, J = 8.6 Hz, 2H), 8.52 (s, 2H), 8.07 (d,
231−232 °C (dec.); 1H NMR (500 MHz, CDCl3) δ 9.23 (s, J = 8.6 Hz, 2H), 8.05 (dd, J = 8.6, 2.4 Hz, 2H), 7.90 (d, J = 8.6
2H), 8.91 (s, 2H), 8.63 (d, J = 8.2 Hz, 4H), 8.50 (d, J = 8.6 Hz, 2H), 7.75−7.72 (m, 4H), 7.62 (s, 2H), 7.52 (dd, J = 8.6,
Hz, 2H), 8.39 (d, J = 8.0 Hz, 2H), 7.87 (d, J = 8.2 Hz, 2H), 1.9 Hz, 2H), 7.21 (s, 2H), 2.80 (t, J = 7.8 Hz, 4H), 1.76−1.73
7.83 (s, 2H), 7.89−7.63 (m, 8H), 7.49 (t, J = 7.5 Hz, 2H), 2.75 (m, 4H), 1.44−1.24 (m, 20H), 0.88 (t, J = 6.7 Hz, 6H);
13
(t, J = 7.7 Hz, 4H), 1.74−1.62 (m, 4H), 1.40−1.22 (m, 20H), C{1H} NMR (126 MHz, CDCl3) δ 146.2, 144.4, 141.3,
0.88 (t, J = 6.7 Hz, 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 135.6, 133.1, 131.9, 131.8, 130.8, 129.3, 128.5, 127.8, 127.4,
160.2, 146.7, 146.3, 143.7, 133.5, 132.0, 130.6, 129.8, 129.6, 126.2, 125.4, 124.8, 124.6, 124.5, 123.4, 122.8, 121.1, 120.8,
129.3 (2 signals), 128.4, 127.9, 127.5, 127.2, 127.1, 126.4, 95.5, 36.0, 31.9, 31.1, 29.5, 29.4, 29.3, 22.7, 14.1; HRMS
124.6, 123.6, 122.8, 122.6, 120.5, 116.6, 108.6, 35.6, 31.8, 31.1, (APCI): m/z calculated for C60H57N4: 833.4583 [M + H]+;
29.4, 29.2 (2 signals), 22.7, 14.1; HRMS (APCI): m/z found: 833.4585.
calculated for C68H61Br2N10: 1175.3442 [M + H]+; found: Typical Procedure for the Synthesis of 10,24-
1175.3443. Didodecyl-7,21-dimethyldibenzo[c,f ]benzo[5′,6’]-
Typical Procedure for the Synthesis of 7,19-Dido- tetrazolo[1‴,5‴:1″,2″]quino[4″,3″:7′,8’]indolizino-
decyl-2,14-dihexyldibenzo[b,h]benzo[5′,6’]quino- [3′,2′:4,5]pyrrolo[2,1-a]tetrazolo[1,5-h]-2,7-naphthyri-
[2″,3″:7′,8’]indolizino[3′,2′:4,5]pyrrolo[2,1-f ]-1,6-naph- dine (11a). A Schenk flask was charged with dibrominated
thyridine (10a). A Schenk flask was charged with tetrazoloquinoline-containing pyrrolopyrrole 6o (90.0 mg, 0.08
chloroquinoline-containing pyrrolopyrrole 4h (44.0 mg, 0.04 mmol, 1 equiv), Ph3P (21.0 mg, 0.08 mmol, 1 equiv), Cs2CO3
mmol, 1 equiv), Ph3P (10.5 mg, 0.04 mmol, 1 equiv), Cs2CO3 (117.0 mg, 0.36 mmol, 4.5 equiv), and Pd(OAc)2 (7.2 mg, 40
(58.5 mg, 0.18 mmol, 4.5 equiv), and Pd(OAc)2 (3.6 mg, 40 mol %). Then, dry m-xylene (6 mL) was added, the resulting
4668 https://doi.org/10.1021/acs.joc.3c02916
J. Org. Chem. 2024, 89, 4657−4672
The Journal of Organic Chemistry pubs.acs.org/joc Article

mixture degassed 3 times (by evacuation and refilling with (11d). Purple solid (21.2 mg, 26%); m.p.: 286−287 °C (dec.);
1
Argon) and stirred at 160 °C for 20 h. After cooling to around H NMR (600 MHz, CDCl3) δ 9.40−9.38 (m, 1H); 8.87−
80 °C, toluene (10 mL) was added and resulting suspension 7.29 (complex multiplets, 24H), 6.83 (d, J = 8.4 Hz, 1H),
was passed through a pad of Celite. Next, the product was 2.53−2.48 (m, 4H), 1.50−1.43 (m, 4H), 1.31−1.17 (m, 20H),
washed from the Celite pad with boiling toluene, and all 0.88−0.83 (m, 6H); 13C{1H}NMR (126 MHz, CD2Cl2) δ
filtrates were concentrated to ca. 1 mL. Next, 1 mL of 145.3, 143.2, 141.6, 140.0, 139.8, 135.6, 134.6, 131.9, 131.6,
chloroform was added, and the flask with reaction mixture was 131.3, 130.8, 130.5, 130.4, 130.4, 130.2, 129.8, 129.5, 129.4,
moved to the fridge. Upon 8 h, 35.0 mg (45%) of compound 129.1, 129.0, 127.9, 127.8, 127.7, 127.6, 127.5, 127.4, 127.4,
11a was filtered as dark purple fine crystals. The dried product 127.3, 127.2, 127.1, 126.8, 126.7, 126.3, 126.2, 126.2, 125.6,
11a obtained was pure enough for all analytical purposes. 124.7, 124.5, 124.0, 124.0, 123.8, 123.5, 123.3, 122.9, 122.1,
The procedure for the synthesis of compounds 11b−11d is 117.9, 116.7, 116.0, 112.5, 105.3, 105.0, 91.4, 91.2, 35.8, 35.4,
similar to that of compound 11a, except that compounds 11c 31.8, 31.8, 31.2, 29.7, 29.3, 29.3, 29.1, 29.1, 29.1, 22.6, 22.6,
and 11d were purified by column chromatography (SiO2, 13.9, 13.8; HRMS (APCI): m/z calculated for C68H61N10:
EtOAc:hexanes, 20:80, than 25:75). 1017.5081 [M + H]+; found: 1017.5085.
10,24-Didodecyl-7,21-dimethyldibenzo[c,f ]benzo[5′,6’]-
tetrazolo[1‴,5‴:1″,2″]quino[4″,3″:7′,8’]indolizino[3′,2′:4,5]-
pyrrolo[2,1-a]tetrazolo[1,5-h]-2,7-naphthyridine (11a). Dark
■ ASSOCIATED CONTENT
Data Availability Statement
purple solid (35.0 mg, 45%); m.p.: 296−297 °C (dec.); 1H The data underlying this study are available in the published
NMR (600 MHz, CDCl3) δ 8.40 (s, 2H), 8.33 (d, J = 8.1 Hz, article and its Supporting Information.
2H), 8.08 (s, 2H), 7.89 (s, 2H), 7.76 (d, J = 8.1 Hz, 2H), 7.43
(d, J = 8.2 Hz, 2H), 7.23 (d, J = 8.2 Hz, 2H), 2.68 (t, J = 7.9 *
sı Supporting Information

Hz, 4H), 2.58 (s, 6H), 1.75−1.70 (m, 4H), 1.44−1.40 (m, The Supporting Information is available free of charge at
4H), 1.39−1.24 (m, 32H), 0.88 (t, J = 6.9 Hz, 6H); 13C{1H} https://pubs.acs.org/doi/10.1021/acs.joc.3c02916.
NMR (126 MHz, CDCl3) δ 144.5, 137.5, 137.1, 133.2, 130.7, Theoretical data; typical procedure for the synthesis of
129.9, 128.4, 127.7, 127.2, 127.0, 124.0, 122.6, 121.8, 117.0, 4a, 6a, 10a, 11a; spectral data, 1H and 13C NMR spectra,
115.7, 111.7, 92.7, 35.6, 31.9, 31.4, 31.4, 30.2, 29.8, 29.7, 29.7, optical properties, and photophysical data of 4a−4l, 6a−
29.4, 29.4, 22.7, 21.9, 14.1; HRMS (APCI): m/z calculated for 6r, 10a−10c, 11a−11d; crystallographic data of 4k, 6j,
C62H71N10: 955.5863 [M + H]+; found: 955.5852. 10a, 11d (PDF)
10,24-Didodecyl-7,21-dioctyldibenzo[c,f ]benzo[5′,6’]-
tetrazolo[1‴,5‴:1″,2″]quino[4″,3″:7′,8’]indolizino[3′,2′:4,5]- Accession Codes
pyrrolo[2,1-a]tetrazolo[1,5-h]-2,7-naphthyridine (11b). Dark CCDC 2297032, 2297034−2297035, and 2297398 contain the
purple solid (43.3 mg, 47%); m.p.: 312−313 °C (dec.); 1H supplementary crystallographic data for this paper. These data
NMR (500 MHz, CDCl3) δ 8.42 (s, 2H), 8.37 (d, J = 8.2 Hz, can be obtained free of charge via www.ccdc.cam.ac.uk/
2H), 8.11 (s, 2H), 7.98 (s, 2H), 7.87 (d, J = 8.2 Hz, 2H), 7.45 data_request/cif, or by emailing [email protected].
(dd, J = 8.3, 1.5 Hz, 2H), 7.31 (d, J = 8.2 Hz, 2H), 2.80 (t, J = uk, or by contacting The Cambridge Crystallographic Data
7.9 Hz, 4H), 2.71 (t, J = 7.9 Hz, 4H), 1.83−1.78 (m, 4H), Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
1.76−1.70 (m, 4H), 1.52−1.25 (m, 56H), 0.91 (t, J = 7.2 Hz, 1223 336 033.
6H), 0.86 (t, J = 7.2 Hz, 6H); 13C{1H} NMR (126 MHz,
CDCl3) δ 144.3, 142.3, 136.9, 133.0, 130.6, 129.1, 128.0,
127.8, 127.5, 127.2, 126.8, 122.4, 121.6, 118.0, 116.8, 115.5,
■ AUTHOR INFORMATION
Corresponding Authors
111.4, 92.6, 36.2, 35.7, 32.0, 31.9, 31.7, 31.5, 29.8, 29.8, 29.8, Mohammad B. Teimouri − Institute of Organic Chemistry,
29.7, 29.7, 29.6, 29.5, 29.4, 29.4, 22.7, 22.7, 14.1, 14.2; HRMS Polish Academy of Sciences, Warsaw 01-224, Poland; Faculty
(APCI): m/z calculated for C76H98N10: 1150.7976 [M]+; of Chemistry, Kharazmi University, Tehran 15719-14911,
found: 1150.7977. Iran; orcid.org/0000-0003-4178-9995;
7,23-Dihexylbenzo[c]naphtho[2,1-f ]naphtho[1″,2″:5′,6’]- Email: [email protected]
tetrazolo[1‴,5‴:1″,2″]quino[4″,3″:7′,8’]indolizino[3′,2′:4,5]- Michał K. Cyrański − Faculty of Chemistry, University of
pyrrolo[1,2-h]tetrazolo[5,1-a]-2,7-naphthyridine (11c). Pur- Warsaw, Warsaw 02-093, Poland; Email: mkc@
ple solid (26.8 mg, 39%); m.p.: 301−302 °C (dec.); 1H NMR chem.uw.edu.pl
(500 MHz, CDCl3) δ 8.97 (d, J = 8.7 Hz, 2H), 8.95 (s, 2H), Aleksander Rebane − National Institute for Chemical Physics
8.58 (d, J = 8.4 Hz, 2H), 8.40 (d, J = 8.9 Hz, 2H), 7.71 (dd, J = and Biophysics, Tallinn 12618, Estonia; Department of
8.2, 1.6 Hz, 2H), 7.63 (d, J = 8.0 Hz, 2H), 7.59 (d, J = 8.8 Hz, Physics, Montana State University, Bozeman, Montana
2H), 7.44−7.39 (br. s, 2H), 7.35 (t, J = 7.7 Hz, 2H), 7.29 (t, J 59717, United States; orcid.org/0000-0003-4330-5544;
= 7.7 Hz, 2H), 3.14 (t, J = 7.8 Hz, 4H), 2.09−2.04 (m, 4H), Email: [email protected]
1.70−1.64 (m, 4H), 1.58−1.55 (m, 2H), 1.53−1.51 (m, 2H), Daniel T. Gryko − Institute of Organic Chemistry, Polish
1.49−1.42 (m, 4H), 0.98 (t, J = 7.2 Hz, 6H); 13C{1H} NMR Academy of Sciences, Warsaw 01-224, Poland; orcid.org/
(151 MHz, CD2Cl2) δ 149.1, 144.6, 142.9, 133.1, 132.1, 130.1, 0000-0002-2146-1282; Email: [email protected]
128.9, 128.6, 128.5, 127.9, 127.7, 124.8, 124.4, 124.0, 123.8,
123.5, 122.7, 120.3, 117.6, 113.4, 111.7, 95.5, 36.6, 32.2, 31.9, Authors
29.6, 23.2, 14.3; HRMS (APCI): m/z calculated for Irena Deperasińska − Institute of Physics of Polish Academy of
C56H47N10: 859.3985 [M + H]+; found: 859.3992. Sciences, Polish Academy of Sciences, Warsaw 02-668,
7-Octyl-19-(7-octyltetrazolo[1,5-a]quinolin-4-yl)-20-(9- Poland
phenanthryl)-20H-benzo[c]phenanthro[9,10-f ]pyrrolo- Matt Rammo − National Institute for Chemical Physics and
[2′,3′:4,5]pyrrolo[1,2-h]tetrazolo[5,1-a]-2,7-naphthyridine Biophysics, Tallinn 12618, Estonia
4669 https://doi.org/10.1021/acs.joc.3c02916
J. Org. Chem. 2024, 89, 4657−4672
The Journal of Organic Chemistry pubs.acs.org/joc Article

Marzena Banasiewicz − Institute of Physics of Polish Academy homojunction single-material organic solar cells. J. Mater. Chem. C
of Sciences, Polish Academy of Sciences, Warsaw 02-668, 2022, 10, 5716−5726. (b) Wang, Y.; Michinobu, T. Benzothiadiazole
Poland; orcid.org/0000-0002-8251-5440 and its π-extended, heteroannulated derivatives: useful acceptor
Charles W. Stark − National Institute for Chemical Physics building blocks for high-performance donor−acceptor polymers in
and Biophysics, Tallinn 12618, Estonia; orcid.org/0000- organic electronics. J. Mater. Chem. C 2016, 4, 6200−6214. (c) Wang,
0002-8998-8638 Y.-F.; Lu, H.-Y.; Chen, C.; Li, M.; Chen, C.-F. 1,8-Naphthalimide-
based circularly polarized TADF enantiomers as the emitters for
Łukasz Dobrzycki − Faculty of Chemistry, University of
efficient orange-red OLEDs. Organic Mater. 2019, 70, 71−77.
Warsaw, Warsaw 02-093, Poland; orcid.org/0000-0002- (d) Eftaiha, A. F.; Sun, J.-P.; Hill, I. G.; Welch, G. C. Recent
4426-963X advances of non-fullerene, small molecular acceptors for solution
Complete contact information is available at: processed bulk heterojunction solar cells. J. Mater. Chem. A 2014, 2,
https://pubs.acs.org/10.1021/acs.joc.3c02916 1201−1213.
(3) Stecko, S.; Gryko, D. T. Multifunctional Heteropentalenes:
Author Contributions From Synthesis to Optoelectronic Applications. JACS Au 2022, 2,
The manuscript was written through contributions of all 1290−1305.
(4) Sanil, G.; Koszarna, B.; Poronik, Y. M.; Vakuliuk, O.; Szymański,
authors. All authors have given approval to the final version of
B.; Kusy, D.; Gryko, D. T. The chemistry of 1,4-dihydropyrrolo[3,2-
the manuscript. b]pyrroles. Adv. Heterocycl. Chem. 2022, 138, 335−409.
Notes (5) Liu, H.; Ye, J.; Zhou, Y.; Fu, L.; Lu, Q.; Zhang, C. New
The authors declare no competing financial interest. pyrrolo[3,2-b]pyrrole derivatives with multiple-acceptor substitution:

■ ACKNOWLEDGMENTS
This work was supported by the Polish National Science
Efficient fluorescent emission and near-infrared two-photon absorp-
tion. Tetrahedron Lett. 2017, 58, 4841−4844.
(6) Ivanov, A. I.; Dereka, B.; Vauthey, E. A simple model of solvent-
induced symmetry-breaking charge transfer in excited quadrupolar
Center, Poland (grants OPUS 2020/37/B/ST4/00017 and
molecules. J. Chem. Phys. 2017, 146, 164306.
HARMONIA 2018/30/M/ST5/00460), the Foundation for (7) Friese, D. H.; Mikhaylov, A.; Krzeszewski, M.; Poronik, Y. M.;
Polish Science (TEAM POIR.04.04.00-00-3CF4/16-00). This Rebane, A.; Ruud, K.; Gryko, D. T. Pyrrolo[3,2- b ]pyrroles�From
project has received funding from the European Union’s Unprecedented Solvatofluorochromism to Two-Photon Absorption.
Horizon 2020 research and innovation programme under the Chem.-Eur. J. 2015, 21, 18364−18374.
Marie Skłodowka-Curie grant agreement No 101007804. (8) Wu, D.; Zheng, J.; Xu, C.; Kang, D.; Hong, W.; Duan, Z.;
Calculations were performed at the Interdisciplinary Center Mathey, F. Phosphindole fused pyrrolo[3,2-b]pyrroles: a new single-
for Mathematical and Computational Modeling (ICM) molecule junction for charge transport. Dalton Trans. 2019, 48,
University of Warsaw under computational allocation G95- 6347−6352.
1734. M.B.T. thanks Kharazmi University Research Council (9) Antonyová, V.; Tatar, A.; Brogyányi, T.; Kejík, Z.; Kaplánek, R.;
for the financial support of his sabbatical leave. The authors Vellieux, F.; Abramenko, N.; Sinica, A.; Hajduch, J.; Novotný, P.;
also thank Dr David C. Young for proofreading the manuscript. et al.et al. Targeting of the Mitochondrial TET1 Protein by
Pyrrolo[3,2-b]pyrrole Chelators. Int. J. Mol. Sci. 2022, 23, 10850−

■ REFERENCES
(1) (a) Messersmith, R. E.; Siegler, M. A.; Tovar, J. D. Aromaticity
10875.
(10) Dereka, B.; Vauthey, E. Direct local solvent probing by
transient infrared spectroscopy reveals the mechanism of hydrogen-
Competition in Differentially Fused Borepin-Containing Polycyclic bond induced nonradiative deactivation. Chem. Sci. 2017, 8, 5057−
Aromatics. J. Org. Chem. 2016, 81, 5595−5605. (b) Tamba, S.; Nitani, 5066.
N.; Seo, T.; Nitta, H.; Tanaka, K.; Hagiya, H.; Aso, Y.; Ie, Y. (11) Wu, J.-Y.; Yu, C.-H.; Wen, J.-J.; Chang, C.-L.; Leung, M.
Tetrazolo[1,5-a]pyridine-Containing π-Conjugated Systems: Syn- Pyrrolo[3,2-b]pyrroles for Photochromic Analysis of Halocarbons.
thesis, Properties, and Semiconducting Characteristics. Org. Lett.
Anal. Chem. 2016, 88, 1195−1201.
2022, 24, 3792−3796. (c) Borissov, A.; Maurya, Y. K.; Moshniaha, L.;
(12) Wu, H.; Wang, Y.; Qiao, X.; Wang, D.; Yang, X.; Li, H.
Wong, W.-S.; Ż yła-Karwowska, M.; Stępień, M. Recent Advances in
Pyrrolo[3,2-b]pyrrole-Based Quinoidal Compounds For High Per-
Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic
formance n-Channel Organic Field-Effect Transistor. Chem. Mater.
Compounds. Chem. Rev. 2022, 122, 565−788. (d) Oki, K.; Takase,
2018, 30, 6992−6997. Zhao, B.; Xu, Y.; Liu, S.; Li, C.; Fu, N.; Wang,
M.; Mori, S.; Shiotari, A.; Sugimoto, Y.; Ohara, K.; Okujima, T.; Uno,
H. Synthesis, Structures, and Properties of Core-Expanded Azacor- L. Non-Fullerene Receptor Material Based on Tetrarylpyrrole Nuclear
onene Analogue: A Twisted π-System with Two N-Doped Heptagons. and Its Application in Organic Solar Cell Device. CN 108,912,125 A,
J. Am. Chem. Soc. 2018, 140, 10430−10434. (e) Wagner, J.; Crocomo, 2018.
P. Z.; Kochman, M. A.; Kubas, A.; Data, P.; Lindner, M. Modular (13) Wang, J.; Chai, Z.; Liu, S.; Fang, M.; Chang, K.; Han, M.;
Nitrogen-Doped Concave Polycyclic Aromatic Hydrocarbons for Hong, L.; Han, H.; Li, Q.; Li, Z. Organic Dyes Based on Tetraaryl-
High-Performance Organic Light-Emitting Diodes with Tunable 1,4-dihydropyrrolo[3,2-b]pyrroles for Photovoltaic and Photocatalysis
Emission Mechanisms. Angew. Chem., Int. Ed. 2022, 61, Applications with the Suppressed Electron Recombination. Chem.-
No. e202202232. (f) Qiu, Z.-L.; Chen, X.-W.; Huang, Y.-D.; Wei, Eur. J. 2018, 24, 18032−18042.
R.-J.; Chu, K.-S.; Zhao, X.-J.; Tan, Y.-Z. Nanographene with Multiple (14) Peng, Z.; Feng, X.; Tong, B.; Chen, D.; Shi, J.; Zhi, J.; Dong, Y.
Embedded Heptagons: Cascade Radical Photocyclization. Angew. The selective detection of chloroform using an organic molecule with
Chem., Int. Ed. 2022, 61, No. e202116955. (g) Barker, J. E.; Dressler, aggregation-induced emission properties in the solid state as a
J. J.; Valdivia, A. C.; Kishi, R.; Strand, E. T.; Zakharov, L. N.; fluorescent sensor. Sens. Actuators, B 2016, 232, 264−268.
MacMillan, S. N.; Gómez-García, C. J.; Nakano, M.; Casado, J.; (15) Domínguez, R.; Montcada, N. F.; de la Cruz, P.; Palomares, E.;
Haley, M. M. Molecule Isomerism Modulates the Diradical Properties Langa, F. Pyrrolo[3,2-b]pyrrole as the Central Core of the Electron
of Stable Singlet Diradicaloids. J. Am. Chem. Soc. 2020, 142, 1548− Donor for Solution-Processed Organic Solar Cells. ChemPluschem
1555. 2017, 82, 1096−1104.
(2) (a) Terenti, N.; Giurgi, G.-I.; Crişan, A. P.; Anghel, C.; Bogdan, (16) Zhou, Y.; Zhang, M.; Ye, J.; Liu, H.; Wang, K.; Yuan, Y.; Du, Y.-
A.; Pop, A.; Stroia, I.; Terec, A.; Szolga, L.; Grosu, I.; Roncali, J. Q.; Zhang, C.; Zheng, C.-J.; Zhang, X.-H. Efficient Solution-Processed
Structure−properties of small donor−acceptor molecules for Red Organic Light-Emitting Diode Based on an Electron-Donating

4670 https://doi.org/10.1021/acs.joc.3c02916
J. Org. Chem. 2024, 89, 4657−4672
The Journal of Organic Chemistry pubs.acs.org/joc Article

Building Block of Pyrrolo[3,2-b]pyrrole. Org. Electron. 2019, 65, 110− (27) Frija, L. M. T.; Ismael, A.; Cristiano, M. L. S. Photochemical
115. Transformations of Tetrazole Derivatives: Applications in Organic
(17) Balasubramanyam, R. K. C.; Kumar, R.; Ippolito, S. J.; Synthesis. Molecules 2010, 15, 3757−3774.
Bhargava, S. K.; Periasamy, S. R.; Narayan, R.; Basak, P. Quadrupolar (28) (a) Dhiman, N.; Kaur, K.; Jaitak, V. Tetrazoles as anticancer
(A-π-D-π-A) Tetra-Aryl 1,4-Dihydropyrrolo[3,2-b]Pyrroles as Single agents: A review on synthetic strategies, mechanism of action and
Molecular Resistive Memory Devices: Substituent Triggered Ampho- SAR studies. Bioorg. Med. Chem. 2020, 28, 115599−115621. (b) Jin,
teric Redox Performance and Electrical Bistability. J. Phys. Chem. C S. C. Y.; Xia, H.; Wang, K.; Liu, Y.; Zhang, Q. Synthesis of fused
2016, 120, 11313−11323. tetrazolo[1,5-b]pyridazine-based energetic compounds. Energy Mater.
(18) (a) Ji, Y.; Peng, Z.; Tong, B.; Shi, J.; Zhi, J.; Dong, Y. Front. 2020, 1, 16−25.
Polymorphism-dependent aggregation-induced emission of pyrrolo- (29) (a) Ponnuvel, K.; Padmini, V.; Sribalan, R. A new tetrazole
pyrrole-based derivative and its multi-stimuli response behaviors. Dyes based turn-on fluorescence chemosensor for Zn2+ ions and its
Pigm. 2017, 139, 664−671. (b) Li, K.; Liu, Y.; Li, Y.; Feng, Q.; Hou, application in bioimaging. Sens. Actuators, B 2016, 222, 605−611.
H.; Tang, B. Z. 2,5-Bis(4-alkoxycarbonylphenyl)-1,4-diaryl-1,4- (b) Hata, T.; Hayashi, Y.; Hasegawa, Y.; Iwai, M.; Ishii, A.; Hasegawa,
dihydropyrrolo[3,2-b]pyrrole (AAPP) AIEgens: Tunable RIR and M.; Shigeta, M.; Urabe, H. Preparation of Tetrazole-fused π-
TICT Characteristics and Their Multifunctional Applications. Chem. Conjugated Molecules and Their Fluorescence Behavior. Chem.
Lett. 2019, 48, 662−665. (c) Arslan, B. S.; Derin, Y.; Mısır, B. A.;
Sci. 2017, 8, 7258−7267. (c) Ma, Y.; Zhang, Y.; Kong, L.; Yang, J.
Kaya, S.; Ş işman, I.;̇ Tutar, A.; Nebioğlu, M. Effect of electron donors
Mechanoresponsive Material of AIE-Active 1,4-Dihydropyrrolo[3,2-
on the photophysical and theoretical properties of BODIPY dyes
b]pyrrole Luminophores Bearing Tetraphenylethylene Group with
based on tetrazolo[1,5-a]quinoline. J. Mol. Struct. 2022, 1267,
Rewritable Data Storage. Molecules 2018, 23, 3255. 133608−133618. (d) West, A.-K.; Kaylor, L. J.; Subir, M.; Rayat, S.
(19) Hryniewicka, A.; Breczko, J.; Siemiaszko, G.; Papathanassiou, Synthesis, photophysical and nonlinear optical properties of push−
A. N.; Góra-Marek, K.; Tarach, K. A.; Brzezinski, K.; Ilnicka, A.; pull tetrazoles. RSC Adv. 2022, 12, 22331−22341. (e) Derin, Y.;
Terzyk, A. P.; Markiewicz, K. H.; et al.et al. Three-dimensional Arslan, B. S.; Mısır, B. A.; Ş işman, I.;̇ Nebioğlu, M.; Tutar, A.
organization of pyrrolo[3,2-b]pyrrole-based triazine framework using Synthesis and photophysical investigation of AIEgen dyes bearing
nano structural spherical carbon: enhancing electrochemical perform- quinoline and BODIPY scaffolds. Chem. Heterocycl. Compd. 2020, 56,
ance of materials for supercapacitors. Sci. Rep. 2023, 13, 10737. 1542−1547.
(20) Balasubramanyam, R. K. C.; Kandjani, A. E.; Harrison, C. J.; (30) (a) Meth-Cohn, O.; Narine, B.; Tarnowski, B. A. A versatile
Rashid, S. S. A. A. H.; Sabri, Y. M.; Bhargava, S. K.; Narayan, R.; new synthesis of quinolines and related fused pyridines, Part 5. The
Basak, P.; Ippolito, S. J. 1,4-Dihydropyrrolo[3,2-b]pyrroles as a Single synthesis of 2-chloroquinoline-3-carbaldehydes. J. Chem. Soc., Perkin
Component Photoactive Layer: A New Paradigm for Broadband Trans. 1981, 1, 1520−1530. (b) Meth-Cohn, O.; Narine, B. A
Detection. ACS Appl. Mater. Interfaces 2017, 9, 27875−27882. versatile new synthesis of quinolines, thienopyridines and related
(21) Hawes, C. S.; Ó Máille, G. M.; Byrne, K.; Schmitt, W.; fused pyridines. Tetrahedron Lett. 1978, 19, 2045−2048.
Gunnlaugsson, T. Tetraarylpyrrolo[3,2- b ]pyrroles as versatile and (31) (a) Kategaonkar, A. H.; Pokalwar, R. U.; Sonar, S. S.; Gawali, V.
responsive fluorescent linkers in metal−organic frameworks. Dalton U.; Shingate, B. B.; Shingare, M. S. Synthesis, in vitro antibacterial and
Trans. 2018, 47, 10080−10092. antifungal evaluations of new α-hydroxyphosphonate and new α-
(22) Duan, L.-s.; Wu, Q.-p.; Xu, Y.-y.; Wang, H.; Sun, Z.; Chen, Y.; acetoxyphosphonate derivatives of tetrazolo [1,5-a] quinoline. Eur. J.
Xue, S. One-pot synthesis of tetraarylpyrrolo[3,2-b]pyrrole dopant- Med. Chem. 2010, 45, 1128−1132. (b) Barad, H. A.; Sutariya, T. R.;
free hole-transport materials for inverted perovskite solar cells. Chin. J. Brahmbhatt, G. C.; Parmar, N. J.; Lagunes, I.; Padrón, J. M.;
Chem. Phys. 2021, 34, 217−226. Murumkar, P.; Sharma, M. K.; Yadav, M. R. A catalyst- and solvent-
(23) (a) Clark, J. C.; Kusy, D.; Vakuliuk, O.; Krzeszewski, M.; free multicomponent synthesis and docking study of some new
Kochanowski, K. J.; Koszarna, B. K.; O’Mari, O.; Jacquemin, D.; antiproliferative N5-allyl-quinolylpyrido[2,3-b][1,4]benzodiazepinone
Gryko, D. T.; Vullev, V. I. The magic of biaryl linkers: the electronic precursors. New J. Chem. 2016, 40 (6), 4931−4939.
coupling through them defines the propensity for excited-state (32) Valeur, B.; Berberan-Santos, M. N. Molecular Fluorescence:
symmetry breaking in quadrupolar acceptor−donor−acceptor fluo- principles and Applications, 2nd ed.; Wiley-VCH: Weinheim, 2012.
rophores. Chem. Sci. 2023, 14, 13537−13550. (b) Banasiewicz, M.; (33) Stark, C. W.; Rammo, M.; Trummal, A.; Uudsemaa, M.;
Stężycki, R.; Kumar, G. D.; Krzeszewski, M.; Tasior, M.; Koszarna, B.; Pahapill, J.; Sildoja, M.-M.; Tshepelevitsh, S.; Leito, I.; Young, D. C.;
Janiga, A.; Vakuliuk, O.; Sadowski, B.; Gryko, D. T.; Jacquemin, D. Szymański, B.; et al.et al. On-off-on Control of Molecular Inversion
Electronic Communication in Pyrrolo[3,2-b]pyrroles Possessing Symmetry via Multi-stage Protonation: Elucidating Vibronic Laporte
Sterically Hindered Aromatic Substituents. Eur. J. Org. Chem. 2019, Rule. Angew. Chem., Int. Ed. 2022, 61, No. e202212581.
(34) (a) Li, Q.; Huang, J.; Zhong, A.; Zhong, C.; Peng, M.; Liu, J.;
2019, 5247−5253.
Pei, Z.; Huang, Z.; Qin, J.; Li, Z. N-Arylpyrrole-Based Chromophores
(24) (a) Tasior, M.; Chotkowski, M.; Gryko, D. T. Extension of
of Donor-π-Donor Type Displaying High Two-Photon Absorption. J.
Pyrrolopyrrole π-System: Approach to Constructing Hexacyclic
Phys. Chem. B 2011, 115, 4279−4285. (b) Abbotto, A.; Beverina, L.;
Nitrogen-Containing Aromatic Systems. Org. Lett. 2015, 17, 6106−
Bozio, R.; Facchetti, A.; Ferrante, C.; Pagani, G. A.; Pedron, D.;
6109. (b) Krzeszewski, M.; Dobrzycki, Ł.; Sobolewski, A. L.; Signorini, R. Novel Heterocycle-Based Two-Photon Absorbing Dyes.
Cyrański, M. K.; Gryko, D. T. Saddle-shaped aza-nanographene Org. Lett. 2002, 4 (9), 1495.
with multiple odd-membered rings. Chem. Sci. 2023, 14, 2353−2360. (35) Gaussian 16, Revision A.03 , Frisch, M. J.; Trucks, G. W.;
(25) (a) Tasior, M.; Vakuliuk, O.; Koga, D.; Koszarna, B.; Górski, Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.;
K.; Grzybowski, M.; Kielesiński, Ł.; Krzeszewski, M.; Gryko, D. T. Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.;
Method for the Large-Scale Synthesis of Multifunctional 1,4-Dihydro- Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts,
pyrrolo[3,2-b]pyrroles. J. Org. Chem. 2020, 85, 13529−13543. R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.;
(b) Tasior, M.; Koszarna, B.; Young, D. C.; Bernard, B.; Jacquemin, Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi,
D.; Gryko, D.; Gryko, D. T. Fe(III)-Catalyzed Synthesis of F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.;
Pyrrolo[3,2-b]pyrroles: Formation of New Dyes and Photophysical Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.;
Studies. Org. Chem. Front. 2019, 6, 2939−2948. Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.;
(26) (a) Neochoritis, C. G.; Zhao, T.; Dömling, A. Tetrazoles via Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Multicomponent Reactions. Chem. Rev. 2019, 119, 1970−2042. Throssell, K.; Montgomery, J. A.; Peralta, J. E., Jr.; Ogliaro, F.;
(b) Benson, F. R. The chemistry of the tetrazoles. Chem. Rev. 1947, Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov,
41, 1−61. V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.;

4671 https://doi.org/10.1021/acs.joc.3c02916
J. Org. Chem. 2024, 89, 4657−4672
The Journal of Organic Chemistry pubs.acs.org/joc Article

Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.;
Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.;
Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J.
Gaussian 16, Revision A.03; Gaussian Inc., Wallingford CT, 2016.
(36) Neese, F. Software update: the ORCA program system, version
4.0. WIREs Comput. Mol. Sci. 2018, 8, No. e1327.
(37) (a) Meth-Cohn, O.; Narine, B.; Tarnowski, B. A versatile new
synthesis of quinolines and related fused pyridines. Part II.
Tetrahedron Lett. 1979, 20, 3111−3114. (b) Meth-Cohn, O.;
Narine, B.; Tarnowski, B. A versatile new synthesis of quinolines
and related fused pyridines. Part 7. The conversion of acetamido-
thiophens into thienopyridines. J. Chem. Soc., Perkin Trans. 1981, 1,
1531−1536.
(38) Sonar, S. S.; Sadaphal, S. A.; Pokalwar, R. U.; Shingate, B. B.;
Shingare, M. S. Synthesis and antibacterial screening of new 4-((5-
(difluoromethoxy)-1H-benzo[d]imidazol-2-ylthio)methyl)tetrazolo-
[1,5-a]quinoline derivatives. J. Heterocycl. Chem. 2010, 47, 441−445.
(39) Izawa, T.; Miyazaki, E.; Takimiya, K. Solution-Processible
Organic Semiconductors Based on Selenophene-Containing Hetero-
arenes, 2,7-Dialkyl[1]benzoselenopheno[3,2-b][1]benzoselenophenes
(Cn-BSBSs): Syntheses, Properties, Molecular Arrangements, and
Field-Effect Transistor Characteristics. Chem. Mater. 2009, 21, 903−
912.
(40) De Ridder, R.; Martin, R. H. Synthèses dans le Domaine des
Composés Polycycliques Aromatiques. XVIII�1,2,3,4,5,6-Tribenzo-
fluorène (Ou Tribenzo [a,c,g] Flourène) Et 1,2,3,4,5,6,7,8-Tétraben-
zofluoréne (ou Tétrabenzo [a,c,g,i] Flourène). Bull. Soc. Chim. Belg.
1960, 69, 534−548.

4672 https://doi.org/10.1021/acs.joc.3c02916
J. Org. Chem. 2024, 89, 4657−4672