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How to cite: Angew. Chem. Int. Ed. 2021, 60, 1082 – 1097
Synthetic Photochemistry International Edition: doi.org/10.1002/anie.202006416
German Edition: doi.org/10.1002/ange.202006416

A Rational Approach to Organo-Photocatalysis: Novel

Designs and Structure-Property Relationships
Alberto Vega-PeÇaloza, Javier Mateos, Xavier Companyl,
Margarita Escudero-Casao, and Luca Dell’Amico*

Keywords:
catalyst design ·
organocatalysis ·
photocatalysis ·
photoredox
catalysis ·
synthetic
photo-
chemistry

Angewandte
Chemie
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Organic photocatalysts are emerging as viable and more sustainable singlet state (S1) is defined by its E0,0
tools than metal complexes. Recently, the field of organo-photo- separation (Jablonski diagram). This
energy is reflected in the excited state
catalysis has experienced an explosion in terms of applications, rede- reduction (E* ) and oxidation poten-
red
sign of well-established systems, and identification of novel scaffolds. tials (E*ox), which can be tuned by
A rational approach to the structural modification of the different rational structural modifications. In
photocatalysts is key to accessing unprecedented reactivity, while organic PCs, the excited species in-
improving their catalytic performances. We herein discuss the concepts volved in the photocatalytic cycle is
usually the singlet (S1) state, but in
underpinning the scaffold modification of some of the most recently some cases (see below) this species
used photocatalysts and analyze how specific structural changes alter rapidly decays to the triplet state (T1)
their physicochemical and redox properties. by intersystem crossing (ISC).[5] In
these cases, the energy of the T1 state
(3E0,0) determines the reduction
(3E*red) and oxidation potential
1. Introduction 3
( E*ox). In general, we can assume that when the T1 state is
the reactive photocatalytic species; the lifetime (t) of the S1
Over the past several years synthetic photochemistry has state is shorter, its emission prevented, and its fluorescence
undergone a renaissance.[1] This trend was boosted by the quantum yield (Ff) lowered. Another property that should be
tremendous developments in photocatalysis.[2] Pioneering mentioned is the charge-transfer (CT) character of the
contributions have involved the use of metal-based photo- excited state. Similar to the metal to ligand CT (MLCT) in
catalysts,[2a,b] which have clearly demonstrated the synthetic metal complexes, some organic PCs are able to access excited
potential of photoredox catalysis for novel reactivity that is states when the electron density is transferred from an
inaccessible by means of conventional polar reactions.[1, 2] As electron-rich portion to an electron-deficient moiety. This
a result,[3] photocatalysis, previously only mastered by a few charge movement is dictated by the electron-accepting and
specialized research groups, has rapidly become a widely used electron-donating ability, as well as the structural surround-
method in synthetic chemistry. Over the last decade, major ings. It is possible to roughly estimate the CT experimentally
efforts have been devoted to the development of new light- by looking at the Stokes shift and the Ff value. The higher the
driven synthetic methods, often at the expense of an accurate Stokes shift, the stronger the CT.[5b] In most cases, when CT is
study of the photocatalytic system. More recently, with the effective, a new S1-CT or T1-CT excited state is generated. In
consolidated knowledge acquired,[1c] the field has moved some cases, this phenomenon is desired to generate a long-
towards a more conscious approach, which relies on tuning lived CT excited species; in other cases, it is detrimental to the
the physicochemical properties of the photocatalysts (PCs).[2d] reactivity, by reducing the reductive/oxidative power of the
Apart from being a cheaper and more sustainable option than excited state. Together with the above excited-state proper-
metal-based PCs, organic PCs offer an increasing number of ties, we will also consider the key ground-state parameters of
modular scaffolds that are characterized by peculiar and the PCs. Importantly, structural changes also alter the
tunable physicochemical features. In fact, different organic absorption spectra, such as the maximum absorption (l),
PCs have proved the synthetic potential and versatility of the and the molar extinction coefficient at a certain wavelength
most used Ru and Ir complexes.[2d] In this Minireview we (e). Particularly relevant are also the ground-state potential
summarize recent progress in organo-photocatalysis. We Ered, which represents the tendency of a PC to acquire one
report the structure–activity relationships of diverse organic electron from an electrode, and the ground-state potential
PCs, along with the synthesis that enables the rational Eox, which represents the tendency to lose one electron to an
modulation of their properties. electrode. Although the excited-state potentials are generally
responsible for the initiation of the photocatalytic cycle, a Ered
or Eox potential is essential to close the cycle, thereby
1.1. Objective, Methods, and Acronyms restoring the ground state of the PC.[2] All the redox
properties reported in this Minireview are in volts (V) versus
The aim of this Minireview is to provide an overview of the saturated calomel electrode (SCE).
the rational design and structural evolution of the different
classes of organic PCs. This task will be addressed by
analysing how diverse structural changes alter the key
physicochemical properties and affect the synthetic perform-
ances. The organic PCs discussed herein are summarized in [*] Dr. A. Vega-PeÇaloza, J. Mateos, Dr. X. Companyk,
Dr. M. Escudero-Casao, Dr. L. Dell’Amico
Figure 1, along with their main physicochemical properties.
Department of Chemical Sciences
We do not include organic dyes previously discussed in more University of Padova
[4]
extended and comprehensive reviews. Via Marzolo 1, 35131 Padova (Italy)
A summary of the main PC properties that we will E-mail: [email protected]
consider in this Minireview are shown in Figure 1 (left). The ORCID identification numbers for the authors of this article can
Considering the excited state of a PC, the energy of the first be found under: https://doi.org/10.1002/anie.202006416.

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Figure 1. PCs discussed in this Minireview. The reported properties refer to the maximum value registered. Abbreviations and main properties are
explained in the gray box (left).

2. Strongly Reducing Organic Photocatalysts 2.1. Phenoxazine, Phenothiazine, Dihydrophenazine, and

Dihydroacridine Photocatalysts
Strongly reducing organic PCs are particularly suitable for
thermodynamically challenging C@C bond-forming synthetic The electron-rich scaffolds 1 (Figure 2) represent the most
transformations,[2d, 6] including light-driven polymerization used families of PCs that operate through an oxidative
reactions.[6b] The key step under these processes is generally quenching mechanism.[6] The fused tricyclic core is structur-
a single-electron reduction of the starting substrate (e.g. a- ally versatile and can include different atoms, thereby giving
halocarbonyl, fluoroalkyl iodides) by the light-excited PC.[2d] rise to the four different variants 1 a–d.
Interestingly, structural variations have a specific impact on
the diverse physicochemical parameters which govern the
catalytic performances.

Figure 2. Commonly used methods for the arylation of 1.

Luca Dell’Amico completed his MSc in
medicinal chemistry in 2010 at Parma
University (Italy). He completed his PhD 2.2. Synthetic Strategies for the Preparation of Photocatalysts 2
with Prof. F. Zanardi in 2014, which
included a spell at the Center for Catalysis, The prototypical modification at the PC scaffold 1 involves
brhus Univesity (Denmark), with Prof. K. A.
arylation of the secondary amine. Although the Buchwald–
Jørgensen. He then joined the group of Prof.
P. Melchiorre at ICIQ, Tarragona (Spain), Hartwig cross-coupling reaction is commonly used for all the
as a Marie-Curie cofound fellow. In 2017 he structural variants, the Ullmann coupling reaction is preferred
started his independent career as an assis- for accessing phenothiazines (Figure 2).[6] On the other hand,
tant professor at Padova University (Italy). core modifications at positions 3 and 7 of phenoxazine (1 a),
He was awarded the G. Ciamician Medal phenothiazine (1 b), and dihydroacridine (1 d) are generally
2019 and the Thieme Chemistry Journals accomplished by a two-step procedure involving a bromina-
Award 2020. His research focuses on the development of photochemical
tion followed by a Suzuki cross-coupling reaction (Fig-
methods and the use of renewables in synthesis.
ure 3).[6a] Conversely, dihydrophenazine (1 c) is usually modi-

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Table 1: Impact of extended conjugation at positions 3 and 7 of the

photocatalyst core.

Figure 3. Core modifications of 1 a at positions 3 and 7. NBS = N-

bromosuccinimide.

fied only at the N atom.[6b] Structure-property relationships

have been reported for all the different heterotricyclic
scaffolds 1 a–d, with an emphasis on the phenoxazine core Table 2: Impact of substitution with EDGs or EWGs at positions 3 and
(1 a).[6c] Miyake and co-workers evaluated the impact of the 7.[6c]
structural modifications in depth by a mixed experimental
and computational approach.[7–10]
Three main structural features impact the physicochem-
ical properties of this class of PCs (Figure 4): a) the substi-
tution at positions 3 and 7 of the core (Table 1, 2), b) the
heteroatom in the heterocyclic core (Table 3), and c) the aryl
group placed on the N atom (Tables 4 and 5). In the following,
we will mainly refer to the redox properties of the charge-
transfer triplet excited state (T1-CT) of the PC, as it is
responsible for the initial key reductive step in diverse
synthetic applications.[6, 7]
Table 3: Heteroatom exchange and alteration of the PC properties.[7, 9]

Figure 4. Structural modification sites and impact on the PC proper-

ties.

2.2.1. Modification at the Heterocyclic Core

When the H atoms at positions 3 and 7 of phenoxazine

PCs 3 are replaced by a phenyl group, the absorption red-
shifts from l = 318 nm to 367 nm (Table 1).[6c] Importantly,
core modifications resulting in an increased conjugation also
enhance the CT excited-state character of the PC.[8]
As mentioned above, core modifications also have an
impact on the photoredox properties. When 4 (Table 2) is
substituted with diverse electron-donating groups (EDGs), heterocycles have labs = ca. 320 nm, the nitrogenated counter-
the calculated 3E*ox value increases from @1.75 V to @1.83 V. part reaches labs = 369 nm. The calculated 3E*ox potential
Conversely, the E*red value significantly decreases from increases with the introduction of the N-Ar group, approach-
0.62 V to 0.30 V.[6c] ing @2.25 V (7), at the expenses of the 3E*red potential, which
From looking at PCs 5–7 (Table 3, top), it is possible to drops from 0.58 V for 5 to 0.08 V for 7.[7–9] A similar trend is
discern a positive trend with respect to the absorption when observed for the corresponding 1-naphthyl derivatives 8–10,
passing from O or S to N. Indeed, while the O- and S- which are characterized by an increased CT character.

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2.2.2. Modification of the Exocyclic Aryl Group centred radical, which is then trapped by an acrylate, thereby
generating a new radical. This radical chain is later terminated
Taking dihydroacridine PCs as an example (Table 4) and by the PCC+, which regenerates the PC ground state.[6b]
altering the aryl group on the N atom, it is possible to increase In 2016, Miyake and co-workers reported a remarkable
the emission wavelength (lem) from 443 nm for 11 to 487 nm example of a photo-organocatalyzed polymerization process
for 13, while maintaining a constant absorption wavelength involving a-bromoester 15 and vinyl acrylate 16 (Figure 5).[6b]
(labs).This indicates in an enhanced Stokes shift.[6d] A reduced Importantly, the dihydrophenazines 14 used in this study
Ff value is observed, which decreases from 27 % for 11 to outcompete commonly used Ir-based PCs in terms of both
0.3 % for 13, thus indicating a superior T1-CT excited-state initiator efficiency (I) and polymer dispersity (Y). The best
character for 13. The different substituents on the exocyclic performances were registered for PCs 14 b and 10, which were
aryl rings also affect the redox potentials of the PC. The more characterized by less-reducing T1 excited-state properties and
reductive dihydrophenazine 14 PCs (Table 5) bear EDGs an increased Ered value.[6b] Importantly, PC 14 b and 10
(3E*[email protected] V). delivered polymers with controlled sizes (up to 1.17 Y) and
high conversion (up to 98.4 %). The CT character also
increased over the series. Interestingly, dihydrophenazine
Table 4: Impact of exocyclic aryl substituents on the PC properties. PCs have also been used for the synthesis of fine-chemicals
and biorelevant molecules. In 2017, Miyake and co-workers
reported a mild visible-light-driven method for the trifluoro-
methylation of indoles (Figure 6).[10] An initial screening of
PCs revealed that the CT character was key to reach long-
lived T1 excited states, thus ensuring an increased reactivity.
Photocatalysts 10 and 14 e—characterized by a higher Stokes
shift, which indicates a strong CT character—delivered the
trifluoromethylated product 20 in yields of 40 % and 49 %,
respectively. Reaction optimization led to a 65 % yield of the
isolated product. The synthetic procedure was effectively
extended to diverse aromatic systems (e.g. pyrroles, ben-
zenes) and substituted olefins (42 %–98 % yield).[10]

Table 5: Impact of substitution with EDGs or EWGs on the PC proper-

ties.[7, 8]

2.3. Impact of Structural Changes on the Synthetic Performance

The strongly reducing PCs mentioned above have been Figure 5. Effect of different substitutions on the visible-light-driven
atom transfer radical polymerization. LED = light-emitting diode.
widely used for diverse synthetic purposes.[6, 10] They were
particularly effective for replacing more-expensive Ir com-
plexes in polymer synthesis. In this sense, organic PCs
represent a cheaper and sustainable option, and avoid issues
of metal contamination. In these processes the T1-CT excited
state of the PC—generated upon irradiation with light—
reduces a carbon–halogen bond, with the generation of a C-

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3. Strongly Oxidizing Organic Photocatalysts

3.1. Acridinium Photocatalysts

A stronger oxidative or reducing power can be obtained

with ionic PCs than with neutral ones. Cationic PCs, show
faster electron-transfer kinetics, because of charge exchange
when the radical cation of the donor is formed upon
photoinduced electron transfer (PET).[2f] Among the cationic
organic PCs, acridiniums are the most used class of mole-
cules.[2e] First introduced by Fukuzimi et al. in 2001,[12a] they
are characterized by a high excited-state oxidative power
E*red = up to 2.32 V, E*ox = up to @0.57 V,[12b,c] and long
lifetimes (t) up to 31 ns.[13] Acridinium-based PCs are soluble
in numerous organic solvents, while showing high stability to
electron-rich species. This feature was achieved by structural
refinement over the years by various research groups. Finally,
their high structural modularity allows easy tuning of their
properties.

Figure 6. Effect of the use of differently substituted PCs on the visible- 3.1.1. Structural Optimization for Increased Chemical Stability
light-driven trifluoromethylation of indoles.[9, 10] Value in parenthesis
refer to the yield of the isolated product after optimization.
The acridinium precursor 24 suffers from low stability in
the presence of nucleophilic species. In particular, the C9-
position is highly electrophilic (Figure 8). Additionally, PC 24
2.4. Other Strongly Reducing Photocatalysts can undergo light-promoted radical coupling side reactions
that lead to undesired functionalizations. The introduction of
In 2018, Gualandi, Cozzi et al. investigated the use of a phenyl group at position 9 (25) only reduces the radical
coumarin dyes 21 as photoredox catalysts.[11] These photo- coupling reactions, while switching to a more hindered
catalysts can be easily synthesized from available materials. mesityl group reduces the two types of photobleaching (26–
As a consequence of the highly reducing nature of the excited 28).[14] Despite the improved chemical stability, N-Me-pro-
state of the photocatalysts, they efficiently catalyze the tected acridinium salts 26 can undergo demethylation reac-
reductive homocoupling of aldehydes and ketones (Figure 7). tions. Hence, the use of PCs 27 and 28, first reported by
Substitution at position 3 with different aromatic groups red- Nicewicz and co-workers, was the decisive step to an
shifted the absorption, while maintaining a high E*ox value. improved stability.[15–17]
PC 21 c, with E*ox = @1.89 V, provided the best synthetic
performance (66 % yield).

Figure 7. Impact of the use of differently substituted coumarin PCs for Figure 8. Structural evolution of acridinium derivatives towards in-
the pinacol-type homocoupling of aldehydes. creased stability. Mes = mesityl.

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3.2. Synthetic Strategies for the Preparation of Acridinium 3.2.1. Structure-Property Relationships of Acridinium Photocatalysts
Photocatalysts
Three main structural features affect the PC properties:[22]
Sparr and co-workers reported three useful strategies for 1) the donor moiety at C9, 2) the acridinium core, and 3) the
the construction of acridinium libraries. The first method N substituent (Figure 11). The electron-rich aromatic ring at
involves the use of 1,5-bifunctional nucleophile 29 to access, C9 (red) is approximately perpendicular to the acceptor
in the presence of an ester, the PC core 30 with different aryl acridinium core (blue), which hinders p-conjugation across
groups at C9 (Figure 9 a).[18] An analogous strategy is the the planar system.[12] The HOMO and LUMO are localized
double directed ortho-metalation of 31 to afford the 1,8- on the aryl group and acridinium core, respectively. Depend-
dimethoxy substitution pattern of 32 (Figure 9 b).[18b] By ing on the electron-donating ability of the group at C9 and the
combining these strategies, it is also possible to access the substituents on the acridinium core, two distinct types of
unsymmetrical PC 34 (Figure 9 c).[19] In 2016, Nicewicz and singlet excited states can be populated: a) the singlet state
co-workers reported the direct conversion of the xanthylium (S1) or b) the charge-transfer singlet state (S1-CT). Upon the
salt 35 into the corresponding acridinium PC 36 (Fig- absorption of light, the PC reaches the excited S1 state. With
ure 10).[20] This is a cost- and step-efficient method that a pronounced donor–acceptor effect, the S1 state can undergo
allows the rapid modification of: 1) the aryl ring at C9, 2) the internal charge transfer to form the S1-CT state, in which the
acridinium core, and 3) the N substituent. Recently, Manche- positive charge is localized on the mesityl ring.[23] However, in
Ço, Alem#n, and co-workers also developed a method for the acridinium-based PCs, the S1-CT state can be counterproduc-
introduction of imide units at C9.[21] tive, because of its fast nonradiative decay, its lower oxidative
power, and its higher decomposition in the presence of
dioxygen.[24]

Figure 11. Structural modifications and impact on the properties of the

acridinium-based PCs.

In general, the initial acridinium scaffolds 24–26 possess

an unbalanced distribution of E0,0 between the reduction and
oxidation potentials. The high reduction potentials in the
excited state (E*red) can lead to unselective substrate oxida-
tion.[25f] Additionally, the weak Ered potential make acridi-
nium radical anions very challenging to oxidize, and in some
cases this precludes PC turnover. Therefore, modulation of
the properties of acridinium-based PCs is generally directed
Figure 9. 1,5-Bifunctional nucleophiles for the synthesis of acridinium- at 1) attenuating the E*red potential in favor of a more
based PCs. balanced potential, and 2) inhibiting the CT-S1 character of
the excited state to increase the lifetime (t).

3.2.2. Modifications of the Ring at C9

One of the main strategies to increase the lifetime (t) of

the S1 state is based on lowering the CT-S1 character. This
strategy relies on altering the donor ability of the aryl
substituent (Table 6).[24] The removal of a methyl group from
the mesityl ring in 28 lowers the CT-S1 character, thereby
extending the lifetime from 14.4 ns in 28 to 16.4 ns in 37. This
Figure 10. Conversion of xanthylium salts into acridinium-based PCs.
trend is also observed for 38, which contains a dihalogenated
aryl substituent.

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Table 6: Impact of C9 modifications of the acridinium-based PCs. redox and absorption properties. The presence of ortho
substituents on the ring reduces the nonradiative decay,
thereby increasing the lifetime t. This is attributed to
restricted rotation about the C@N bond.

3.3. Impact of Structural Changes on the Synthetic Performance

Their high visible-light absorption, together with the

superior E*red potential, render acridinium-based PCs excel-
lent alternatives to metal-based PCs that operate through
a reductive quenching mechanism.[25] DiRocco, Nicewicz, and
co-workers achieved the decarboxylative conjugate addition
3.2.3. Modifications of the Acridinium Core of Cbz-proline (45) to dimethyl maleate (46) by using
acridinium derivative 40 (Figure 12).[17] The excited-state
The LUMO is generally delocalized over the electron- reduction potential of 40 (E*red = 1.62 V) is thermodynami-
poor acridinium core of the PC.[17–20] The presence of cally suitable to promote the single-electron oxidation of the
a methoxy or a dimethylamino group lowers the E*red Cbz-proline carboxylate group (Eox = 1.16 V vs. SCE), where-
potential from 0.2 V to 0.4 V, respectively. The smaller as its ground-state redox potential (Ered = @0.84 V vs. SCE)
HOMO–LUMO gap lowers the E*red potential and increases enables reduction of the a-acyl radical intermediate (Ered =
the Ered potential (Table 7). @0.61 V vs. SCE), thereby regenerating the PC.
In contrast, the Fukuzumi catalyst 25 resulted in poor
conversion because of its low radical anion reductive power
Table 7: Structural modification of the acridinium core to modulate the
redox properties. (Ered = @0.55 V), thus highlighting the importance of bal-
anced operating redox margins. More recently, Sparr, Weng-
er, and co-workers thoroughly investigated the photophysical
properties of several aminoacridinium PCs. The authors
observed that 48 efficiently promotes the dual catalytic
photoredox/nickel decarboxylative C@C cross-coupling reac-
tion between Boc-l-proline (49) and methyl 4-iodobenzoate
(50; Figure 13).[19]
In contrast, a large number of organic PCs (e.g. 53)
promote energy transfer from nickel(II) species and deliver
the C@O coupling product 52 or a mixture of products. The
lower T1 quantum yield of 48 (7 %) and the high kinetic
reactivity of its S1 state with the carboxylate anion for electron
transfer give rise to this divergent pathway. Again, the more
3.2.4. Modifications of the N Substituent balanced redox properties are instrumental to obtaining high
conversions (86 %).
The emergence of new synthetic strategies for the
construction of acridinium-based PCs allowed the study of
different N substitutions (Table 8).[20] In general, the intro-
duction of EWGs significantly increases the S1 lifetimes (t) up
to 22.8 ns. However, minimal changes are observed in the

Table 8: Modification of the N-substituent of the acridinium core.

Figure 12. Performance of PCs in the decarboxylative conjugate addi-

tion of Cbz-proline (45) to dimethyl maleate (46).

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Figure 14. Triphenylpyrylium-based PC optimization for the [3+

+2] dipo-
lar cycloaddition of epoxides.

4.1. Carbazolyldicyanobenzene Photocatalysts

Figure 13. Acridinium photoredox/nickel dual catalytic decarboxylative
C@C cross-coupling reaction. Carbazolyldicyanobenzenes (CDCBs) are structural de-
rivatives of cyanoarenes such as 1,4-dicyanobenzene and 9,10-
dicyanoanthrecene.[2e] These electron-poor scaffolds are char-
3.4. Other Strongly Oxidizing Photocatalysts acterized by a high singlet energy, which allows the oxidation
of several substrates. Their structural evolution to obtain a PC
Among the other classes of strongly oxidative PCs, able to access both reductive and oxidative quenching
triphenylpyrylium derivatives have found extensive applica- mechanisms indicated a red-shift in the absorption. Working
tions.[2d] Similar to the initial acridinium scaffolds, they can on the aromatic core, Adachi and co-workers described in
undergo a deactivation pathway through dimerization or 2012 the rational design of simple aromatic compounds that
nucleophilic addition.[2d] Interestingly, the introduction of exhibit efficient thermally activated delayed fluorescence
a mesityl group at C4 generates a more stable PC. Recently, (TADF).[28] In 2016 Luo and Zhang reported the first
Beeler and co-workers showed how the electronic properties application of a CDCB as a photoredox catalyst.[32]
of the catalyst can be rationally tuned through different
structural modifications.[26] PCs 57 and 58 were prepared and
tested in a [3+ +2] dipolar cycloaddition of epoxides 54 with 4.2. Synthetic Strategies for the Preparation of CDCB
acetylenedicarboxylate (55) to give 56 (Figure 14). 58 cata- Photocatalysts
lyzed the reaction in excellent yield (93 %), with no photo-
bleaching observed over 24 h. However, 59, bearing two The preparation of CDCBs involves the incorporation of
EDGs at positions 1 and 5, furnished the product in higher different donor units through nucleophilic aromatic substitu-
yield in one hour (95 %). This is due to its increased e value tion of 61 (Figure 15).[32, 33] The use of sodium hydride or
and a more balanced distribution of the excited-state sodium bis(trimethylsilyl)amide permits the incorporation of
oxidative/reductive power. Remarkably, 59 was also used carbazolyl (Cz) or diphenylamino (DPA) groups in excellent
for the synthesis of intermediates for lignan-based deriva- yields on a multigram scale (from 10 to 90 % yield). This
tives.[26] simple synthetic approach enabled the study of different
CDCB variants.

4. Bimodal Organic Photocatalysts 4.2.1. Structure-Property Relationships of the CDCB Photocatalysts

Bimodal PCs can undergo both reductive and oxidative The high activity and generality of 60 in photocatalysis
quenching mechanisms. In this scenario, carbazolyl dicyano- relies on the donor–acceptor character of the molecule.[32] The
benzenes (CDCBs) have played a central role amongst the carbazole unit acts as a modulable electron-donor moiety
organic sensitizers.[27–29] Dicyanopyrazines (DPZs)[30] and while the core behaves as an electron acceptor. This marked
naphthochromenones (NTCs)[31] demonstrated similar prop- differentiation is also reflected in the strong delocalization of
erties, catalyzing several thermodynamically opposite mech- the natural bonding orbitals.[28] The HOMO is mainly
anisms. delocalized over the four carbazolyl moieties (red in Table 9),

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Table 10: Impact of the modification of the EDGs on the PC properties.

Figure 15. Straightfoward one-step synthetic procedure for the syn-

thesis of 4CzIPN derivatives. Table 11: Impact of the substitution of the carbazole moiety with
halogens.

Table 9: Main properties and relevant features of the CDCB PCs.

potential, which increases along the series from 1.49 (for 60)
to 1.89 V (for 63). The structural optimization was key for the
development of an oxidative ring fragmentation reaction.

while the LUMO is centred on the dicyanobenzene ring (blue 4.2.3. Modification at the Acceptor Core
in Table 9).
Hence, the CDCBs have a strong CT-S1 character. In The acceptor properties of the core can also be tuned and
addition, the steric hindrance between the carbazolyl and have a major impact on the Eox potential. This feature was
nitrile units causes a large dihedral angle (about 6088), which initially studied by Zeitler and co-workers.[34] The substitution
limits torsional flexibility and reduces the nonradiative of just one carbazole moiety at position 3 by a chlorine atom
decay.[34] PC 60 exhibits bimodal redox properties both in its (69) increases the Eox potential from 1.49 to 1.79 V (Table 12).
ground and excited states (Table 1). Interestingly, these Additionally, the position of the cyano groups can be
properties can be tuned by: 1) modification of the EDGs or changed, further altering the ground-state redox properties
2) structural alteration of the acceptor core.[32, 34, 35] (PCs 67 and 68). Unfortunately, these structural isomers have

4.2.2. Modification of the EDGs

Table 12: Impact of core alterations on the PC properties.
The introduction of EDGs such as 4,6-dimethyoxycarba-
zole (64) or diphenylamino groups (65) increases the E*ox
potential up to @1.52 V (@1.18 for 60),[32] while the E0,0
separation showed the opposite trend (Table 10). In a remark-
able contribution, Waser and co-workers determined how 4,6-
disubstitution of the carbazole moieties by halogens impact
the redox properties.[35] The calculated Ered potential increases
along the halogen series (Br < Cl < F < H), from @0.83 to
@1.24 V (Table 11). The opposite trend is observed for the Eox

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found less applications in photocatalysis, because they have

a large number of decomposition pathways.[32] For example,
67 and 68 show a strong quenching of their absorption after
short irradiation periods in DMF (10 minutes),[32] with up to
89 % decomposition.

4.2.4. Impact of Structural Changes on Synthetic Performances

Thanks to the high versatility and scalable synthesis,

CDCB PCs have been extensively used for electron-transfer
reactions.[28] Zeitler and co-workers elegantly used the newly
designed PC 69 in a decarboxylative Giese-type conjugate
addition (Figure 16).[34] The utilization of PC 64 with an
inferior E*red potential furnished only traces of product 71.
On the other hand, PCs 69 and 60 furnished the product 71 in
high yield (up to 80 %).[17]

Figure 17. Application of the CDCB PCs in the alternative EnT/reduc-

tive synthetic process.

4.3. Dicyanopyrazines

Over the last decade the Bureš group has developed

a number of push-pull chromophores.[38] In particular, 2,3-
dicyanopyrazines (DPZs) have received attention from the
synthetic community.[39] Such X-shaped PCs are characterized
by a donor-p-acceptor system, which allows modular struc-
tural modifications.

4.3.1. Synthetic Strategies for the Preparation of 2,3-Dicyanopyrazine

Photocatalysts

The synthesis of DPZ PCs can be accomplished by

Figure 16. Synthetic application of the CDCB PCs in the Giese decar- a simple condensation reaction between the benzil derivative
boxylative addition. 77 a–c and diaminomaleonitrile (78; Figure 18). This synthetic
strategy furnishes 79 a and 79 b in excellent yields.[40] On the

Recently, Zhang and co-workers studied the ability of

these PCs to undergo energy-transfer (EnT) mechanisms
(Figure 17).[36] The 3E0,0 values of CDCB span from 69.9 to
53.9 kcal mol@1.[37] The authors predicted that a CDCB with
a 3E0,0 value larger than that of Ir(ppy)3 (53.7 kcal mol@1)
should provide a similar sensitization efficiency as a nickel-
(II)-based complex.[19] From the reaction between benzoic
acid 72 and 73, is possible to discern a trend, with the E*red
potential playing a crucial role. When 60 was used, only the
dehalogenation product 75 was observed (97 %). Compound
75 is obtained after a single-electron reduction of 73 by
the PCC@ , generated upon reduction of the PC* by the amine.
In fact, incorporation of stronger EDGs together with the
use of a less electron-withdrawing core (76) switched the
reaction selectivity in favour of the esterification (EnT)
product 74.[19]

Figure 18. Synthetic procedures for the synthesis of 2,3-dicyanopyra-

zine PCs. Bpin = Boron pinacol ester.

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other hand, a Suzuki cross-coupling between boronic acid 80

and 81 delivers 79 c in 83 % yield.

4.3.2. Structure-Property Relationships of the DPZ Photocatalysts

The 2,3-dicyanopyrazine core plays a prominent role in

many organic photocatalysis. The electron-withdrawing het-
eroaromatic ring permits differentiation of the natural bond-
ing orbitals (NBOs). The LUMO is mainly localized in the
pyrazine core, while the HOMO is centered on the donor
groups at positions 5 and 6.[30] This polarized system shows an
effective CT character (Figure 19). In strong contrast to
CDCB PCs, their weak fluorescence indicates a short S1
lifetime (< 1 ns).[41] Hence, DPZ PCs exclusively react in
their T1 state. Bureš and co-workers suggested that this fast
decay may be due to the heavy sulfur atom effect increasing
the intersystem crossing rate from S1 to T1. Two structural
features can be tuned to optimize the lifetime of the CT state
of DPZ PCs: 1) the EDGs at positions 5 and 6, and 2) the
electron-withdrawing heterocyclic core, with the second Figure 20. Synthetic application of DPZ PCs in the Povarov-type
reaction.
possibility having an inferior impact.

character also increases along the series. Core modification

has less impact on the photoredox properties, but generates
unstable PCs (Figure 20).

4.3.3. Impact of Structural Changes on the Synthetic Performance

The Bureš group has investigated the synthetic abilities of

DPZ PCs.[30, 41] A comparison of the synthetic performances of
the different scaffolds was performed for the Povarov
Figure 19. Main structure-property relationships of the DPZ PCs. cyclization (Figure 20). The initial key step in this reaction
is the oxidation of amine 82 by PC*. The utilization of the 2,6-
dicyanopyrazine isomer 85 with the methoxy-substituted
The main strategy to modulate the reduction potential thienyl ring was unsuccessful because of its low chemical
relies on modification of the donor groups.[41] The furyl group stability. On the other hand, the use of the 2,3-dicyanopyr-
(79 a) decreases the energy of the HOMO. 79 a is a PC with azine PCs 79 b and 79 c afforded 84 in good to excellent yields
a balanced distribution of the oxidative and reductive power, (73 % and 95 %, respectively). The authors attributed these
which mainly relies on the absorption of UV light (Table 13). results to the increased absorption by 79 c generating a higher
The substitution of the furyl group by its sulfur analogue in amount of the PC excited state in solution.
79 b reduces its E0,0 value, while red-shifting its absorption.
Additionally, the presence of more EDGs renders 79 c an
excellent visible-light PC, with an lmax centered at 448 nm and 4.4. Naphthochromenone Photocatalysts
maintains the Ered and Eox potentials sufficiently high. The CT
In 2020, Dell’Amico and co-workers described a novel
Table 13: Impact of EDGs at positions 5 and 6. class of purely organic naphthochromenone (NTC) PCs.[31]
The distinctive absorption of these new PCs across the UV-
and the visible-light spectrum allows a high E0,0 separation to
be reached, up to 3.22 eV. An additional advantage of the
NTCs is their well-balanced excited-state redox potentials
spanning from E*red = 1.77 to E*ox = @1.84 V as well as their
recyclability.[31]

4.4.1. Synthetic Strategies for the Preparation of NTC Photocatalysts

The synthesis of NTCs[42a–b] can be accomplished starting

from readily available 2-methylbenzophenones 86 and cou-
marins 87. The synthesis consists of a photoenolization/[4+
+2]

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contrast, substitutions at position 3 cause major alterations in

the absorption and emission spectra of the PC (see below).
With EDGs, the absorption red-shifts, the Ff increases, and
the S1 lifetime increases up to 8.50 ns. Furthermore, the
extended p-conjugation at position 3 has two general effects:
a) the e value significantly increases and b) the absorption
spectrum red-shifts. The latter is ascribed to the increased
HOMO energy, as a result of the presence of the appended
group. This observation can be easily explained looking at PC
88 a (Figure 22). This carbazole-containing PC has the most
red-shifted absorption, where the HOMO is located predom-
inantly on the carbazole moiety and the LUMO on the NTC
core. The spatial separation between the orbitals indicates
a strong CT character in the excited state.
Figure 21. Selected synthetic strategies to NTC PCs.
4.4.3. Modification of the NTC Core

cycloaddition sequence followed by an elimination/aromati- The modularity of the NTC core allows modification of
zation process, with overall yields up to 82 % yield (Fig- the redox properties for diverse synthetic applications. The
ure 21 a). The light-driven [4+
+2] cycloaddition reaction allows introduction of EDGs at position 3 gives access to higher
the straightforward introduction of various groups at posi- values of E*ox up to @1.77 V (Table 14 a). On the other hand,
tions 3 and 7 of the NTC core. Interestingly, position 3 can be the incorporation of EWGs stabilizes the HOMO. This is
subsequently functionalized to extend the conjugation with reflected in the increased E*red potential of PCs 88 f and 88 g
EDGs or EWGs (see Table 14), while tuning their properties. of up to 1.65 V (Table 14 b). In particular, 88 f demonstrated
The construction of the NTC core can also be accomplished high chemical stability and an excellent E0,0 separation
by other methods. Wang and co-workers developed a method (3.12 eV), thereby resulting in a strong E*red potential of
for the one-pot synthesis of NTCs 90 by Pd-catalyzed 1.56 V and an equally strong reductive E*ox potential of
oxidative lactonization, with yields up to 80 % (Fig- @1.45 V.
ure 21 b).[42c] The procedure allows the introduction of EDGs
and EWGs at R1 and different patterns of fused aromatic
Table 14: Introduction of EDGs and EWGs on the NTC core.
rings.

4.4.2. Structure-Property Relationships of the NTC PCs

The NBOs in this class of PCs are localized over the NTC
core. The phenyl group at position 7, perpendicular to the
planar core, can affect the E0,0 and t values, while having only
a small influence on the other properties (Figure 22). By

4.4.4. Impact of Structural Changes on the Synthetic Performance

The NTC PCs can work under both thermodynamically

challenging reductive and oxidative quenching. Their syn-
Figure 22. Structural modifications and impact on the photophysical thetic potential was demonstrated by extending the Povarov-
and redox properties of the PCs. type addition to electron-poor anilines, such as 91, with an

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Figure 23. Application of NTC PCs in the Povarov-type addition of

anilines to N-phenylmaleimide.

Eox = 1.33 V vs. SCE (Figure 23). This multistep transforma-

tion was inefficient when using PCs 88 c and 88 f, which
furnished 92 in poor yields. The utilization of the highly
oxidizing PC 88 f (E*red = 1.56 V vs. SCE) was instrumental to
produce 92 in 70 % yield. Importantly, Ru(bpy)3 and Eosin Y
(53) were completely unproductive PCs for this type of
substrate. The versatility of the NTCs was also proved for the
reductions of benzyl chlorides.
Figure 24. DTC as a nucleophilic PC for the activation of redox-inert
substrates. [a] Data related to the corresponding catalytic intermedi-
ates 95 a, R = Ph. Yield at 60 8C is given in parenthesis.
5. Dithiocarbamate (DTC) Anions as Nucleophilic
Photocatalysts
heterocycles in the presence of t-BuOK and CS2, the authors
Most organic PCs rely on the match between the redox synthesized a range of photocatalysts bearing different light-
properties of the (excited) PC and the substrate to effectively absorbing nitrogenated heteroaromatic scaffolds. For exam-
promote the SET event and ensure the subsequent formation ple, the introduction of a carbazole (93 b) or a 5-bromoindole
of the reactive radical species. In 2019, Melchiorre and co- (93 c) chromophore dramatically enhanced the optical prop-
workers disclosed a conceptually alternative strategy towards erties of the DTC catalysts (93 b and 93 c). The corresponding
the formation of carbon-centered radicals. The authors catalytic intermediates 95 b and 95 c experienced a red-shifted
developed a DTC[43, 44] anionic catalyst 93, bearing a light- absorbance up to l = 650 nm, thereby enabling their excita-
absorbing chromophore that is able to covalently engage with tion at l = 465 nm. Thus, 10 mol % of catalyst 93 c together
a variety of redox-inert electrophilic substrates 94 through an with a stoichiometric amount of g-terpinene afforded the final
SN2 mechanism. Upon absorption, the covalent catalytic product in 90 % of yield. g-Terpinene acts both as a hydrogen
intermediate 95 undergoes homolysis of the weak C@S bond atom transfer donor to form the product after the radical
to generate the target radical 96 (Figure 24).[44] Subsequently, coupling as well as a terminal reductant of the radical catalyst
to close the catalytic cycle, the radical PC derivative 97 is intermediate. Finally, the reaction can be easily scaled up to
reduced to its anionic active form (93), either by a stoichio- a multigram scale without erosion of the catalytic perform-
metric reagent or by the substrate. This innovative nucleo- ances. Subsequently, the authors implemented the DTC
philic PC was firstly implemented in the Giese-type addition catalysis to other types of transformations.[45]
of the photogenerated radicals 96 to electron-deficient
alkenes, such as fumarate (98). As radical precursors, the
authors selected alkyl halides such as benzyl chloride 94 a, an 6. Conclusions and Future Directions
abundant bulk chemical generally inert to most metal and
organic PCs because of its low reduction potential (Ered = In this Minireview we have summarized the main
@2.13 V vs. SCE). Exploiting the straightforward formation structure-property relationships of some of the recently
of DTC salts, by simple treatment with diverse N-containing (re)designed organic PCs. The understanding of how struc-

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tural changes impact the PC properties allows the rational Acknowledgements

selection of one or more PC classes. The choice of the scaffold
is dictated by the synthetic purpose and the corresponding We thank the University of Padova, the CariParo Foundation
reaction mechanism (Figure 25). In particular, the under- Synergy—Progetti di Eccellenza 2018 (L.D.), the GREEN
standing of the key mechanistic steps involving E*ox or E*red is C-C STARS starting grant (X.C.), and the Seal of Excellence
instrumental in selecting the proper PC scaffold. Other @unipd PLACARD (A.V.) for funding. Prof. Marcella
parameters also impact this choice, such as the availability, Bonchio and Prof. Andrea Sartorel are acknowledged for
namely, if the PC is available at a reasonable price or easy to proofreading the manuscript. This Minireview is dedicated to
make in a large amount. In this last case, the synthesis should all the doctors, nurses and researchers fighting the covid-19
ideally be accomplished from simple substrates in a few steps. pandemic.
After the selection of one or more PCs for screening, the
preliminary results obtained can be further improved by
rational structural optimization, dedicated to the fine-tuning Conflict of interest
of specific properties.
The authors declare no conflict of interest.

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