Nitrogen-rich conjugated macrocycles: Synthesis, conductivity, and

application in electrochemical CO2 capture

ABSTRACT: Here we report a series of nitrogen-rich conjugated macrocycles that mimic the structure and function of semiconduct-
ing 2D metal–organic and covalent organic frameworks while providing greater solution processability and surface tunability. Using
a new tetraaminotriphenylene building block that is compatible with both coordination chemistry and dynamic covalent chemistry
reactions, we have synthesized two distinct macrocyclic cores containing Ni–N and phenazine-based linkages, respectively. The fully
conjugated macrocycle cores support strong interlayer stacking, accessible nanochannels, and out-of-plane charge transport, with
pressed pellet conductivities of 10–3 S/cm observed for the nickel variants. Finally, using electrochemically mediated CO2 capture as
an example, we illustrate how phenazine macrocycles dramatically improve electrical contact and active site electrochemical acces-
sibility relative to bulk framework powders. Together, these results highlight how simple macrocycles can enable new synthetic
directions as well as new applications by combining the properties of crystalline porous frameworks, the processability of nano-
materials, and the precision of molecular synthesis.

Introduction. There has been rising recent interest in down- macrocycles that resemble fragments of electrically conductive
sizing crystalline porous frameworks to the nanoscale, moti- 2D metal–organic frameworks.12,19 The macrocycles self-as-
vated by the inherent processability and mass transport benefits semble into π-stacked nanotubes that preserve the porosity and
of nanomaterials.1–3 At the extreme limit of this endeavor is the out-of-plane charge transport found in the parent framework.
construction of discrete molecular cages and macrocycles Solution processability is a key property that differentiates
whose structures mimic individual pores found in bulk metal– macrocycles from bulk 2D framework materials. In the pres-
organic and covalent organic frameworks.4–8 These nanosized ence of solvent, the noncovalent interactions between macrocy-
molecules often retain the original function and porosity found cles can be partially broken to achieve short stacks of aggre-
in their parent frameworks while introducing new properties. gated macrocycles with good colloidal stability. In certain
For example, the greater processability of cages and macrocy- cases, these noncovalent interactions can even be fully replaced
cles facilitates their incorporation into gas separation mem- to achieve individual molecules dissolved in solution, though
branes,9–11 electronic devices,12 and modified electrodes for we have found such examples to be rare for metal–organic mac-
electrocatalysis.13,14 Depending on the application, the ability to rocycles with large extended π-systems.12 The improved pro-
easily deposit thin layers of active material can reduce cost, cessability provides significant advantages with respect to de-
minimize mass transport losses, and maximize active site utili- vice fabrication. For example, in our previous work, we showed
zation. From a fundamental materials discovery standpoint, sol- how fully soluble macrocycles can be leveraged to fabricate
uble porous molecules also enable the formation of new com- thin-film field-effect transistor devices.12
posite materials, such as the use of charged metal–organic cages
In this work, we expand upon our previous studies by intro-
to achieve solid porous salts with tunable compositions.15 Fi-
nally, relative to extended frameworks, porous molecules can ducing a new ditopic triphenylene-based ligand containing ni-
trogen bridging atoms (Fig. 1). Using this ligand, we illustrate
also undergo much greater structural changes in response to
stimuli, such as the reversible self-assembly and dissolution of both the broad generalizability of our synthetic approach as well
as the beneficial impact of framework truncation on electro-
aggregated architectures.16–18
chemical performance. On the synthetic front, the presence of
Our lab has been interested in truncating two-dimensional nitrogen donors dramatically expands the potential diversity of
semiconducting metal–organic frameworks (MOFs) and cova- macrocycle structures. The greater nucleophilicity of nitrogen
lent organic frameworks (COFs) into discrete macrocycles that compared to oxygen provides access to a wider range of bond-
merge the physical properties of crystalline frameworks with forming reactions. For example, o-phenylenediamine units can
the processability of soft materials.12 We recently used the di- react with 1,2-diketones, aldehydes, and ortho-difluorinated ar-
topic, tetrahydroxy ligand H4TOTP-OR (H4TOTP = 2,3,6,7-tet- omatic compounds to form phenazine,20–24 imidazole,25,26 and
rahydroxytriphenylene) to construct conjugated copper piperazine27,28 linkages, respectively (Fig. 1a). In the context of

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 Fig. 1 | (a) Schematic illustration of the different linkages that can be formed from o-phenylenediamine precursors via coordination
chemistry and dynamic covalent chemistry. (b) Construction of metal–organic macrocycles and conjugated organic macrocycles starting
from the bis(alkoxy)-tetraaminotriphenylene ligand, H4TNTP-OC4.
metal–organic materials, nitrogen donors also provide superior precursors containing tert-butyldimethylsilyl (TBDMS)-
charge transport properties relative to oxygenated analogues protected catechols, which are subsequently oxidatively cy-
due to increased metal–ligand covalency.29,30 clized and deprotected. We hypothesized that simply replacing
On the application front, we hypothesized that framework the TBDMS-protected catechols with tert-butoxycarbonyl
truncation should also improve electrochemical device perfor- (BOC)-protected o-phenylenediamine coupling partners would
mance. Colloidal nanoparticles composed of aggregated π- generate the desired nitrogen-based ligands (Fig. 2). Gratify-
stacked metal–organic macrocycles expose significantly greater ingly, the proposed synthetic route proceeded smoothly. The
external surface area relative to bulk micron-scale framework desired bis(butoxy)-tetraaminotriphenylene ligand was isolated
powders. In principle, this increased external surface area as the protonated hydrochloride salt (H4TNTP-OC4·4HCl) in
should reduce both mass transport and charge transport limita-
tions.
Here we show that the ditopic ligand H4TNTP-OC4
(H4TNTP-OC4 = 10,11-dibutoxytriphenylene-2,3,6,7-
tetraamine) can be used to construct nitrogen-rich conjugated
metal–organic and organic macrocycles that resemble semicon-
ducting 2D MOFs and COFs in both form and function (Fig.
1b). Combining H4TNTP-OC4 and nickel(II) salts produces
semiconducting nickel macrocycles with pellet conductivities
of 5(1) ×10–3 S/cm. Similarly, reacting H4TNTP-OC4 with
tetraketones forms phenazine-linked conjugated organic mac-
rocycles, which are structurally confirmed by powder X-ray dif-
fraction and solid-state 13C NMR. Finally, we show that phena-
zine-based macrocycles greatly outperform the analogous 2D
COFs as solid sorbents for electrochemically mediated CO2
capture due to their greater processability and nanoscale dimen-
sions.
Ligand design. We envisioned that bis(alkoxy)-
tetraaminotriphenylene ligands could be synthesized following Fig. 2 | Synthesis of the H4TNTP-OC4 ligand via Suzuki cou-
a similar route as the one developed by Northrop and coworkers pling followed by DDQ catalyzed ring closure and BOC pro-
for bis(alkoxy)-tetrahydroxytriphenylenes.31 Their approach re- tecting group removal.
lies on Suzuki coupling to synthesize ortho-terphenyl

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 Fig. 3 | (a) Synthesis of 1-Ni. (b) Proposed structure of 1-Ni, highlighting the partially oxidized ligand. (c) Experimental powder X-ray
diffraction pattern of 1-Ni along with modeled structure and predicted diffraction peaks. (d) High resolution Ni 2p XPS spectrum, show-
ing the absence of satellite features. (e) High resolution N 1s XPS spectrum, showing the presence of two distinct nitrogen environments.

61% overall yield over three steps (Fig. 2). We note that the dimethylformamide (DMF). We note that omitting the acetate
H4TNTP-OC4 ligand is always isolated and handled in its pro- was also not acceptable; no precipitate formed in the absence of
tonated form (H4TNTP-OC4·4HCl) to minimize oxidative deg- external base even after a reaction time of one month.
radation. While this work focuses on ligands containing n-butyl Gratifyingly, heating 1 equiv H4TNTP-OC4·4HCl, 1.5 equiv
side chains, the modular synthetic route should allow the pe- Ni(OAc)2, and 10 equiv of TBAOAc in DMSO at 65 °C for 24
ripheral side chains to be readily tuned in future studies. h produced the macrocycle NiTNTP-OC4 (1-Ni) as a highly
Synthesis and characterization of nickel macrocycles. crystalline dark blue-black powder with the expected diffrac-
Dincă and coworkers reported the first nitrogen-based conju- tion pattern (Fig. 3). Specifically, the first three peaks at 2θ =
gated 2D metal–organic framework Ni3(HITP)2 (HITP = 2.70, 4.68, and 5.40° follow the 1:1/√3:1/2 ratio in d-spacing
2,3,6,7,10,11-hexaiminotriphenylene) in 2014,30 with a subse- expected for a hexagonal unit cell (Fig. 3c). Furthermore, based
quent follow-up study on mixed-metal variants in 2020.32 Re- on the position of the first peak, an approximate a and b dimen-
cent single crystal measurements have shown that the out-of- sion of 37.8 Å was obtained. This value is nearly identical to
plane conductivity in Ni3(HITP)2 is ~100-fold higher than sim- the dimensions of a fully relaxed, geometry optimized model of
ilar 2D frameworks containing oxygen-based ligands, such as 1-Ni (a = b = 37.92 Å). Finally, a broad peak centered at 27.1°
Cu3(HHTP)2.29,33,34 Given the rich chemistry observed in this is observed, which we have assigned as the π–π stacking fea-
particular member of the conjugated 2D MOF family, we were ture. This peak corresponds to a short distance of ~3.3 Å, which
excited to explore the properties of its macrocyclic form. is consistent with both the π–π stacking metrics found in the
While the addition of external bases such as alkali acetate parent framework Ni3(HITP)2 (~3.3 Å)33 as well as our previ-
salts is critical to the synthesis of M3(HITP)2 materials,30,32 we ously reported copper-based metal–organic macrocycles (~3.2
found that the crystallinity of our materials decreased with in- Å).12
creasing equivalents of MOAc (M+ = Na+, K+). Although mod- High-resolution X-ray photoelectron spectroscopy (XPS)
erately crystalline material was obtained using 10 equiv of measurements were carried out to further probe the chemical
MOAc (Fig. S2), further increasing to 100 equiv led to amor- environment of our macrocycles and support our structural as-
phous powders (Fig. S3). We hypothesized that this was due to signment. Analysis of the Ni 2p spectrum shows a binding en-
the unusual solubility characteristics of our ligand, which con- ergy of ~855 eV for the Ni 2p3/2 peak and ~873 eV for the 2p1/2
tains highly polar ammonium groups as well as hydrophobic al- peak, consistent with a Ni(II) oxidation state (Fig. 3d).35 Im-
kyl chains. Because of the alkyl chains, the small amounts of portantly, very faint satellite features are observed, as expected
water required to dissolve the MOAc salt led to rapid precipita- for diamagnetic, square planar Ni(II) sites.35 We note that the
tion of poorly crystalline product. presence of weak satellite features associated with paramag-
We found that two important reaction conditions were neces- netic Ni(II) sites (e.g., octahedral coordination) is likely due to
sary to obtain highly crystalline macrocycle. First, we switched solvent binding at surface sites or other defects, as similar fea-
to tetrabutylammonium acetate (TBAOAc) as our acetate tures are also observed in nanocrystalline Ni3(HITP)2.32,36
source. The tetrabutylammonium cation has much greater solu- In the extended framework Ni3(HITP)2, it is proposed that
bility in organic solvents, allowing us to avoid the use of aque- each of the three o-phenylenediamine units is doubly deproto-
ous solutions. Second, we found that dimethyl sulfoxide nated and oxidized by 1 e– to generate monoanionic, o-diimino-
(DMSO) was a uniquely enabling solvent for this reaction. No benzosemiquinonate sites (Fig. 1a). Because our ligand only
precipitate was formed when N,N-dimethylacetamide (DMA) has two o-phenylenediamine units, we propose that a diamag-
was used, and an amorphous solid was obtained in N,N- netic, partially oxidized ligand containing distinct imine and

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 amine units is formed rather than a diradical species (Fig. 3b). order of magnitude higher than our previously reported
This assignment is supported by our N 1s XPS data (Fig. 3e). CuTOTP-OC4 macrocycle (6(2) × 10–4 S/cm). This increase is
The spectrum can be fit well with two distinct peaks of equal consistent with previously reported single crystal conductivity
area, one at ~400 eV and a second at ~398 eV. We assign the measurements on the analogous metal–organic frameworks,
peak at ~400 eV to the oxidized imine group (C=NH–M), and which show that the conductivity of Ni3(HITP)2 rods (~150
the lower energy peak to unoxidized amine (C–NH–M).37 S/cm) is approximately two orders of magnitude higher than
Interestingly, the structure of 1-Ni is considerably less sensi- Cu3(HHTP)2 rods (~1.5 S/cm).33
tive to solvation state than related triphenylene-based macrocy- Together, these results show that metal–organic macrocycles,
cles, such as our previously reported CuTOTP-OR macrocy- like the MOFs that inspired their synthesis, are highly tunable.
cles12 and Dichtel and coworkers’ boronate ester-linked macro- The use of alternative metals and bridging atoms can be lever-
cycles.38 Minimal changes to the unit cell dimensions (<5%) aged to achieve new families of materials with similar structures
and peak broadness (5% decrease in FWHM) are observed upon but improved charged transport properties. Finally, we note that
soaking 1-Ni in DMA and drying the material under vacuum the macrocycle periphery can also be tailored towards a specific
(Fig. S5 and Table S2). In contrast, the diffraction pattern of function. For example, while 1-Ni shows poor colloidal stability
CuTOTP-OC4 broadens significantly upon drying (28% in- in its current form (Table S5 and Fig. S12), side-chain engi-
crease in FWHM), while the a and b unit cell dimensions of neering should greatly improve the processability of these ma-
boronate ester-linked macrocycles contract by nearly 10 Å upon terials. Analogous n-butyl-functionalized copper macrocycles
desolvation (~18% decrease).38 were shown to be similarly prone to aggregation but could be
The less dynamic structure of 1-Ni suggests the material may rendered fully soluble in organic solvents with the addition of
have more robust interlayer and intercolumn interactions, which longer C18 alkyl chains.12
should promote porosity and electrical conductivity. Indeed, Synthesis and characterization of phenazine-based mac-
gas sorption measurements show that the interior channels re- rocycles. After successfully synthesizing metal–organic macro-
main accessible to guest molecules after desolvation. A BET cycles using H4TNTP-OC4, we hypothesized that the same lig-
surface area of 130 m2/g was obtained from 273 K CO2 adsorp- and could also be used to form truncated analogues of covalent
tion isotherms. We note that a lower surface area of 20 m2/g was organic frameworks. As a proof-of-concept, we targeted the
obtained using N2 at 77 K as a probe molecule. We hypothesize synthesis of phenazine-linked macrocycles, as their COF coun-
that this reduction in surface area is due to partial pore blockage terparts have become an important and widely studied class of
by frozen butoxy side-chains. Density functional theory (DFT) semiconducting crystalline frameworks.20–24
calculations of the pore size distribution, derived from 77 K N2 While some syntheses of phenazine-linked COFs employ
adsorption data, show a single narrow peak at 20 Å (Fig. S9), basic conditions,24 the vast majority use acidic modulators such
which corresponds with both the crystalline structure of 1-Ni as acetic acid and sulfuric acid. Heating H4TNTP-OC4·4HCl
and the reported pore size of Ni3(HITP)2.39 (1.2 equiv) and pyrene-4,5,9,10-tetraone (1 equiv) in 1:1 acetic
Excitingly, pressed pellet conductivity measurements pro- acid/DMF at 120 °C under an N2 atmosphere produced the mac-
vided an average conductivity of 5(1) × 10–3 S/cm, which is an rocycle PyrTNTP-OC4 (2-Pyr) as a brown crystalline solid

Fig. 4 | (a) Synthesis of two phenazine-based conjugated macrocycles, 2-Pyr and 2-tBuPyr. (b) Experimental powder X-ray diffraction
pattern alongside predicted diffraction patterns for 2-tBuPyr with eclipsed, slipped, and staggered π–π stacking motifs. (c) Solid-state
13
C NMR spectrum of 2-tBuPyr. Asterisks denote the spinning sidebands.

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 (Fig. 4a and Fig. S13). Overall, the observed experimental pow- more details). Therefore, we turned to solid-state 13C NMR to
der X-ray diffraction pattern is broadly consistent with struc- confirm the presence of phenazine linkages, as phenazine moi-
tural models optimized in a hexagonal packing arrangement eties have a diagnostic peak at ~140 ppm.20,23,24 Gratifyingly, a
(Fig. S13). The first peak is located at 2θ = 2.36°, indicating a new peak at 139.8 ppm is observed in the solid-state 13C NMR
large a and b unit cell dimension of 43.2 Å, as expected for a spectrum of both 2-Pyr and 2-tBuPyr that is not present in the
large organic macrocycle with >2 nm pore windows. Further- starting ligand (Fig. 4c and Fig. S23–24), confirming the for-
more, an intense peak is observed at 26.7°, which we have as- mation of the phenazine unit. While no evidence of dangling
signed as the π–π stacking feature. This peak corresponds to a carbonyls could be detected in the 13C NMR of 2-tBuPyr, a
distance of 3.3 Å, which is comparable to the ~3.3–3.5 Å range small residual carbonyl peak is observed at 172.8 ppm in 2-Pyr
of π–π stacking distances observed in other planar phenazine- (Fig. 4c and Fig. S23).
linked COFs.21–24 Surface area measurements using CO2 at 273 K indicate that
Excitingly, the synthesis could be extended to the di-tert-bu- 2-tBuPyr has accessible porosity with a BET surface area of
tyl functionalized pyrene-4,5,9,10-tetraone coupling partner as 134 m2/g. Preliminary pressed pellet conductivity measure-
well. Combining H4TNTP-OC4·4HCl (1.5 equiv) and 2,7-di- ments show that 2-tBuPyr has a modest electrical conductivity
tert-butylpyrene-4,5,9,10-tetraone (1 equiv) in 1:10 H2SO4/N- of 8(1) × 10–10 S/cm. This is consistent with previously reported
methyl-2-pyrolidone (NMP) at 150 °C under an N2 atmosphere conjugated 2D COFs, which generally display relatively low
produced tBu-PyrTNTP-OC4 (2-tBuPyr) as a dark reddish pellet conductivities of 10–10 to 10–5 S/cm prior to chemical dop-
brown crystalline solid (Fig. 4). The first four diffraction peaks ing.42,43
are located at 2θ = 2.74, 4.72, 5.44, and 7.22°, consistent with Finally, we tested the dispersibility of 2-tBuPyr in organic
the expected 1:1/√3:1/2:1/√7 ratio in d-spacing for a hexagonal solvents. Out of the five solvents tested (DMF, DCM, MeOH,
unit cell (Fig. 4b). A weak, broad peak around 2θ ~ 25–26° is tetrahydrofuran, and toluene), 2-tBuPyr formed the most stable
observed, corresponding to a π–π stacking distance of ~3.5 Å. colloidal dispersions in DCM (Fig. S25 and Fig. S27). Dynamic
This is slightly larger than the ~3.3 Å observed in 2-Pyr, which light scattering (DLS) measurements immediately following
is expected given the bulkier tert-butyl substituents. The π–π probe sonication showed that over 90% of the particles were
stacking distance was further confirmed by transmission elec- less than 100 nm in diameter, with a smaller population of ~500
tron microscopy (TEM), which showed an average distance of nm particles (Table S7). This particle size distribution re-
3.46(12) Å between stacked macrocycles (Fig. S14 and Table mained relatively constant over the course of 24 hours. How-
S6). ever, the population of larger ~400–500 nm particles gradually
Due to the relatively broad diffraction peaks, the exact π–π increases over the period of two weeks, indicating slow aggre-
stacking arrangements adopted by 2-Pyr and 2-tBuPyr are dif- gation over time. We note that isolating the material via centrif-
ficult to determine with absolute certainty. However, based on ugation, and not filtration, was important to maintaining good
modeling studies, we expect the second peak in the diffraction dispersibility.
pattern (specifically, the (110) peak) to increase in intensity as The relative ease by which 2-tBuPyr can be dispersed in or-
the structure deviates further from fully eclipsed (Fig. S15–17). ganic solvents highlights the processability advantages of dis-
Given the strong (110) peak in the experimental diffraction pat- crete macrocycles over structurally similar extended 2D frame-
tern and the presence of sterically bulky tert-butyl groups, we works. For comparison, we synthesized the analogous 2D COF
hypothesize that 2-tBuPyr likely adopts either a quasi-AB or from 2,3,6,7,10,11-hexaaminotriphenylene (HATP) and 2,7-
AB stacking pattern, with a significant offset between neigh- di-tert-butylpyrene-4,5,9,10-tetraone, using a slight modifica-
boring layers of macrocycles (Fig. 4b).40,41 tion of the previously reported conditions by Jiang and cowork-
The successful formation of phenazine linkages was con- ers.20 The structure and porosity of the framework, named CS-
firmed spectroscopically through a combination of infrared COF in the original report, were confirmed by PXRD and gas
spectroscopy and solid-state 13C NMR (Fig. 4c). The infrared adsorption (Fig. S31–32 and Table S12). DLS measurements
spectrum of 2-tBuPyr shows the disappearance of the amine of the framework, performed immediately after probe soni-
N–H stretches and the preservation of the alkyl C–H features, cation in DCM, show a very broad particle distribution centered
confirming that the H4TNTP-OC4 backbone is present but the ~650 nm in diameter (Fig. S33). Furthermore, unlike the mac-
free amine groups have reacted (Fig. S19). A small C=O rocycle 2-tBuPyr, the phenazine COF particles rapidly aggre-
stretching feature at 1660 cm–1 is observed, which cannot be re- gated and settled within the first hour. While colloidally stable
moved even after repeating rinsing with solvents such as DMF, imine- and boronate ester-based COF nanoparticles have been
methanol (MeOH), and dichloromethane (DCM). We attribute reported,44–46 to our knowledge similar syntheses have not been
this feature to a small number of unreacted, dangling carbonyl developed for phenazine-based COFs. This may be due to their
groups resulting from incomplete macrocyclization. Similar re- exceptionally strong π–π stacking and relatively harsh synthesis
sidual C=O stretches have been observed in related phenazine- conditions.
based COFs.24 We note that the residual C=O stretch is more Electrochemically mediated CO2 capture. Relative to
intense in 2-Pyr, likely due to the poor solubility of the pyrene- poorly processable and aggregated COF powders, we hypothe-
4,5,9,10-tetraone starting material (Fig. S20). sized that the nanoscale dimensions of 2-tBuPyr may enable
While the phenazine ring system is known to display charac- improved mass and charge transport and higher performance in
teristic stretches between 1200–1500 cm–1,20,22,23 these bands electrochemical devices. We anticipated that maximizing elec-
were difficult to definitively assign due to the large number of trical contact would be particularly important, as both our or-
peaks in this region. Vibrational frequency calculations using ganic macrocycles and previously reported 2D COFs have rel-
density functional theory show that this region of the spectra is atively low electrical conductivities (~10–10 S/cm, see Table S9
populated by a large number of skeletal vibrations involving the and S13).42,43
entirety of the macrocycle core (see Fig. S21 and the SI for

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 sorbent electrodes under specific CO2 gas feed conditions. The
electrodes were fabricated using an ink of 2-tBuPyr, Vulcan
carbon, and polyvinylidene fluoride (PVDF) binder in a 4:2:1
mass ratio. The performance of our macrocycle sorbent in a cy-
clic carbon capture and release process is shown in Fig. 5a. Us-
ing a 10% CO2 (balanced with N2) feed stream at a flow rate of
0.4 standard cm3 min–1 (sccm), the fixed bed can run stably for
more than 11 cycles (30 hours) with negligible performance de-
cay (see SI for more details).
The three key metrics commonly used for evaluating EMCC
performance are summarized in Fig. 6. To evaluate the reversi-
bility of 2-tBuPyr, we define the ratio of the total amount of
CO2 released and captured in each cycle as the release/capture
efficiency, and the ratio of the electrochemical oxidation and
reduction capacities as the Coulombic efficiency. These two
values are averaged to be 76.3% and 84.6%, respectively, illus-
trating acceptable reversibility (Fig. 6b).
The third relevant metric is the CO2 capacity utilization, or
the number of CO2 molecules captured per transferred electron.
The 2-tBuPyr device shows an average CO2 capacity utiliza-
tion of 0.45 equiv of CO2 per e– (Fig. 6c). Molecular phenazine
compounds have shown capacities closer to 1 equiv of CO2 per
e–.47–49 However, because our phenazine groups are highly sub-
Fig. 5 | Performance of (a) 2-tBuPyr and (b) the analogous
stituted, we hypothesize that CO2 is only able to bind to one of
phenazine 2D COF as solid sorbents in a fixed-bed electro-
the two reduced nitrogen centers due to steric constraints (Fig.
chemically mediated CO2 capture device. The macrocycle 2-
6a). Quinone-based sorbents show similar steric sensitivity.52,53
tBuPyr runs for stably for 11 repeated capture and release cy-
cles whereas the 2D COF shows negligible CO2 uptake under For example, the doubly reduced dianion of
the same conditions.
We identified electrochemically mediated CO2 capture as an
intriguing testing ground for comparing the performance of
phenazine-based macrocycles versus 2D covalent organic
frameworks. Recent work has shown that the Lewis basicity and
CO2 affinity of phenazine and its derivatives are redox-tunable,
allowing these molecules to be used as liquid sorbents for elec-
trochemically mediated carbon capture (EMCC).47–49 Such mol-
ecules form strong adducts with CO2 upon electrochemical re-
duction, and readily release the captured CO2 upon oxidation.
We hypothesized that phenazine-based macrocycles and COFs
could be used as solid-phase sorbents for EMCC, as the na-
nochannels should facilitate electrolyte and CO2 transport.50
To validate this assumption, we first collected cyclic voltam-
mograms (CV) of the macrocycle 2-tBuPyr in the absence and
presence of CO2 (Fig. S34). Under an inert N2 atmosphere, the
macrocycle displays a reversible redox pair corresponding to
the reduction and oxidation of the sp2-nitrogen centers in the
phenazine moiety, whose half-wave potential (E1/2) is –1.63 V
versus ferrocenium/ferrocene (Fc+/Fc). Excitingly, the CV un-
der CO2 shows a clear anodic shift of the reduction peak, con-
sistent with the formation of a CO2 adduct that decreases elec-
tron density on the reduced macrocycle. Furthermore, the oxi-
dation peak also anodically shifts and becomes electrochemi-
cally irreversible, consistent with the presence of a CO2 adduct
whose nitrogen–carbon bond requires extra energy to break
upon oxidation.
Next, infrared spectroscopy measurements were carried out
to further confirm the formation of stable CO2 adducts. Excit-
ingly, in the presence of CO2, a clear peak at ~1715 cm–1
emerges after the reduction of 2-tBuPyr, consistent with carba-
mate formation (Fig. S35).51
Fig. 6 | Overview of the (a) CO2 capture mechanism, (b) Cou-
Encouraged by the CV and IR data, we next constructed a lombic efficiency and release/capture efficiency, and (c) CO2
fixed-bed EMCC device to evaluate the performance of the capacity utilization for 2-tBuPyr.

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 tetrachlorobenzoquinone is only able to capture one molecule phenazine macrocycle nanoparticles facilitates intimate mixing
of CO2, rather than two, due to steric hindrance from the chlo- with conductive additives and good electrical contact. As a re-
ride substituents.52 In addition to these steric arguments, it is sult, phenazine macrocycles are competent sorbents for electro-
also possible that the highly conjugated structure decreases the chemically mediated CO2 capture, whereas phenazine COFs
electron density on the nitrogen center, reducing the affinity of show negligible CO2 uptake under the same conditions. To-
CO2. gether, this work illustrates how simple macrocycles preserve
We next assessed the EMCC performance of CS-COF, the key features of crystalline porous frameworks while providing
analogous phenazine-based 2D COF.20 To our surprise, the CVs distinct advantages in applications where processability and na-
of the COF under N2 and CO2 atmospheres are nearly identical, noscale dimensions are paramount.
suggesting the absence of CO2 adduct formation (Fig. S37).
Furthermore, the fixed-bed EMCC device shows no detectable ASSOCIATED CONTENT
CO2 capture or release activity (Fig. 5b). Relative to the parent Supporting Information
COF, we attribute the dramatic performance enhancement of
The Supporting Information is available free of charge on the ACS
our macrocycle nanoparticles to their greater colloidal stability Publications website.
and external surface area, which facilitates more intimate con-
tact with the conductive additives, electrolyte, and CO2. In par- Additional experimental details, synthetic procedures, and charac-
ticular, the improved electrical contact greatly increases the terization data (PDF)
number of electrochemically accessible phenazine binding
sites.
To quantify the number of electrochemically accessible AUTHOR INFORMATION
phenazine sites in 2-tBuPyr, discharge curves were performed. Corresponding Author
The capacity of 2-tBuPyr electrodes was determined to be
33.35 mAh/g, indicating that approximately 23% of the phena- * Correspondence to: [email protected].
zine sites per macrocycle could be accessed during the electro-
chemical process (see the SI for more details). While there is
ACKNOWLEDGMENT
room for improvement, this unoptimized value is already much The work described here was primarily supported by the U.S. De-
higher than those reported for several previously reported re- partment of Energy, Office of Science, Office of Basic Energy Sci-
dox-active COFs. For example, Dichtel and coworkers showed ences under Award Number DE-SC0021966. The synthesis of the
that only ~3% of the redox-active groups in an anthraquinone- phenazine macrocycles was additionally supported by the Arnold
and Mabel Beckman Foundation through a Beckman Young Inves-
based COF were accessible when electrodes were fabricated
tigator Award. Additional characterization efforts were supported
from insoluble COF powders, due to poor electrical contact.54
by the David and Lucile Packard Foundation. P.H.L. was supported
This value could be increased to 80–99% by carefully growing in part by the state of Washington through graduate fellowships
oriented thin films.54 Similarly, Yaghi, Chang, and coworkers from the University of Washington Clean Energy Institute. J.G. and
showed that only ~4–8% of the cobalt porphyrin centers in a 2D A.A.K. were supported by NSF graduate research fellowship. A.L.
COF-based electrocatalyst were electroactive, due to limited and Y.L. acknowledge financial support from the National Science
electrochemical contact between the COF powder and the elec- Foundation (award number 237096). The authors acknowledge the
trode.55 use of instrumentation at the following shared facilities: the Wash-
Together, these results establish phenazine-based macrocy- ington Research Training Testbeds, a facility operated by the Uni-
cles as competent solid sorbents for EMCC. We note that all versity of Washington Clean Energy Institute; the Molecular Anal-
prior work on EMCC with phenazine species and other sp2-ni- ysis Facility, a National Nanotechnology Coordinated Infrastruc-
trogen containing molecules were studied in flow systems, us- ture (NNCI) site at the University of Washington, which is sup-
ing liquid sorbents.47–49 This is the first demonstration of a non- ported in part by funds from the National Science Foundation
(awards NNCI-2025489, NNCI-15421010), the Molecular Engi-
quinone-based solid sorbent in a fixed-bed EMCC device.56–58
neering & Sciences Institute, and the Clean Energy Institute; and
At the same time, this work motivates further studies to improve the University of Washington Department of Chemistry. This re-
the electrochemical accessibility of phenazine binding sites, search used resources of the Advanced Photon Source, a U.S. De-
identify structure–property relationships, and further improve partment of Energy (DOE) Office of Science User Facility operated
the performance of this class of sorbents. for the DOE Office of Science by Argonne National Laboratory
Conclusion. In summary, we have developed a new nitrogen- under Contract No. DE-AC02-06CH11357. The mail-in program
based ditopic ligand, H4TNTP-OC4, which is compatible with at Beamline 17-BM contributed to the data. Finally, we gratefully
diverse coordination chemistry and dynamic covalent chemistry acknowledge Dr. Samantha Young for assistance in collecting and
reactions. Using this versatile building block, we have con- analyzing XPS data, Dr. Adrienne Roehrich for assistance in col-
structed three fully conjugated and shape-persistent macrocy- lecting and analyzing solid-state NMR data, and Rachel Tenney
clic cores with strong interlayer stacking, semiconducting be- Smith for assistance in collecting and analyzing UV-Vis data.
havior, and high chemical stability. Specifically, metalating our
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