Stack the Bowls: Tailoring the Electronic Structure of Corannulene-Integrated Crystalline Materials

Article abstract of DOI:10.1002/anie.201806202

We report the first examples of purely organic donor–acceptor materials with integrated π-bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four-orders-of-magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne–azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.

Full text of DOI:10.1002/anie.201806202

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201806202
German Edition: DOI: 10.1002/ange.201806202
Supramolecular Chemistry
Hot Paper
Stack the Bowls: Tailoring the Electronic Structure of Corannulene-
Integrated Crystalline Materials
Allison M. Rice+, Ekaterina A. Dolgopolova+, Brandon J. Yarbrough, Gabrielle A. Leith,
Corey R. Martin, Kenneth S. Stephenson, Rebecca A. Heugh, Amy J. Brandt, Donna A. Chen,
Stavros G. Karakalos, Mark D. Smith, Kelsey B. Hatzell, Perry J. Pellechia,
Sophya Garashchuk,* and Natalia B. Shustova*
Abstract: We report the first examples of purely organic
donor–acceptor materials with integrated p-bowls (pBs) that
combine not only crystallinity and high surface areas but also
exhibit tunable electronic properties, resulting in a four-orders-
of-magnitude conductivity enhancement in comparison with
the parent framework. In addition to the first report of alkyne–
azide cycloaddition utilized for corannulene immobilization in
the solid state, we also probed the charge transfer rate within
the Marcus theory as a function of mutual pB orientation for
the first time, as well as shed light on the density of states near
the Fermi edge. These studies could foreshadow new avenues
for pB utilization for the development of optoelectronic
devices or a route for highly efficient porous electrodes.
Herein, we demonstrated, for the first time, how pB
integration (in particular, corannulene [pB-C20H10]) inside
insulating porous scaffolds could tune electronic properties
resulting in circa 10000-fold conductivity enhancement.
Moreover, the porosity of the prepared crystalline hybrids
was maintained providing a pathway to re-enforce semi-
conducting behavior in typically insulating porous materials
(for example, covalent organic or metal–organic frameworks
(COFs/MOFs)).[11–21] In addition to the first report of azide–
alkyne 1,3-cycloaddition utilized for corannulene integration
in the solid state, the described corannulene material is the
first member in the family of crystalline (purely organic)
donor–acceptor (D–A) corannulene-COFs with the highest
surface area among corannulene-based extended structures
reported to date (Scheme 1). In combination with spectro-
scopic and structural analysis, we employed theoretical
calculations, which allowed us to probe charge transfer rates
within the Marcus theory as a function of pB mutual
orientation for the first time, as well as to shed light on the
density of state distribution near the Fermi edge.
T
he unique curvature of p-bowls (pBs) distinguishes them
from more traditional flat polycyclic aromatic hydrocarbons
(PAHs) and, in combination with an unusual electronic
structure, results in a number of intriguing properties includ-
ing, but not limited to, surface charge stabilization, high
reversible lithium capacity, bowl-to-bowl inversion, a signifi-
cant dipole moment, and high charge mobility.[1–8] This
combination of material properties can open a pathway for
pB utilization in applications ranging from optoelectronic
devices or electrodes to thermoresponsive materials.[4,9,10]
[*] A. M. Rice,[+] E. A. Dolgopolova,[+] B. J. Yarbrough, G. A. Leith,
C. R. Martin, R. A. Heugh, A. J. Brandt, Prof. Dr. D. A. Chen,
Dr. M. D. Smith, Dr. P. J. Pellechia, Prof. Dr. S. Garashchuk,
Prof. Dr. N. B. Shustova
Department of Chemistry and Biochemistry, University of South
Carolina (USC)
631 Sumter Street, Columbia, SC 29208 (USA)
E-mail: garashch@mailbox.sc.edu
Scheme 1. Schematic representation of pB organization inside the
crystalline framework through 1,3-cycloaddition (left). Delocalization of
pB molecular orbitals associated with ground-state charge transport
(right).
shustova@sc.edu
K. S. Stephenson
Department of Physics and Astronomy, USC
712 Main Street, Columbia, SC 29208 (USA)
For engineering corannulene-containing crystalline mate-
rials, we considered two methods based on the post-synthetic
integration of the pB through 1) utilization of azide–alkyne
1,3-cycloaddition and 2) non-coordinative pB inclusion. To
accomplish these strategies, the material used for pB integra-
tion should satisfy the following criteria: 1) Sufficient pore
apertures to accommodate pBs (for example, pB-C20H10
diameter is ca. 6.6 ꢀ), 2) structural integrity after pB
inclusion, and 3) the presence of functional groups (for
Dr. S. G. Karakalos
College of Engineering and Computing, USC
301 Main Street, Columbia, SC 29208 (USA)
Prof. Dr. K. B. Hatzell
Department of Mechanical Engineering, Vanderbilt University
2400 Highland Avenue, Nashville, TN 37212 (USA)
[+] These authors contributed equally to this work.
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201806202.
ꢀ ꢁ
example, C C) for pB integration through covalent bond
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formation. The covalent organic scaffolds, 1 ꢁ (x%) (where
x = [BPTA]/([BPTA] + [DMTA]) ꢁ 100%; Figure 1), made
from 2,5-bis(2-propynyloxy) terephthalaldehyde (BPTA),
2,5-dimethoxyterephthalaldehyde (DMTA), and tri-(4-ami-
cycloaddition (CuAAC), which involved the development of
synthetic methods using less bulky and more affordable
moieties (for example, 2-azidoethanol, Figure 1) before
pursuing the reaction with the labor-demanding pB-
C20H9N3. Therefore, we started with molecular building
blocks, such as 2-azidoethanol and BPTA, to observe reaction
progress using solution NMR spectroscopy, in contrast to the
insoluble COFs (Supporting Information, Figures S18–S20).
Based on the spectroscopic data analysis, we have
monitored the completion of a CuAAC reaction and, as
a result, formation of the desired product, 2,5-bis((1-(2-
hydroxyethyl)-1H-1,2,3-triazol-4-yl)methoxy)terephthalalde-
hyde (Figure 1 (a blue highlight) and Figures S18 and S19). As
a next step, we applied the developed conditions (N,N-
diisopropylethylamine/CuI/THF/H2O, 70 8C, 3 d) towards the
reaction of 2-azidoethanol with the COF (1 ꢁ (34%)) instead
of BPTA. To monitor the reaction progress, solid-state
techniques, including FTIR and solid-state 13C cross-polar-
ization magic angle spinning (CP-MAS) NMR spectroscopies,
were employed. In particular, we observed the disappearance
ꢀ1
of 2120 cmꢀ1 (C C) and 3300 cm (C C H) resonances in
the FTIR spectrum, indicative of reaction completion (Fig-
ure S20).[22] As a control experiment, we treated the COF
under the same reaction conditions but without the presence
ꢁ
ꢁ ꢀ
of the azide-containing precursor. As expected, we observed
ꢀ1
preservation of both 2120 cmꢀ1 (C C) and 3300 cm (H C
C) resonances in the FTIR spectrum (Supporting Informa-
tion, Figure S26). Interestingly, in the case of the CuAAC
reaction with bis(2-azidoethyl) malonate (that is, containing
two azide groups, Figure S21), the disappearance of the
ꢁ
ꢀ ꢁ
stretch at 3300 cmꢀ1 (H C C) is evidence of the reaction
ꢀ ꢁ
progress, while the persistence of the stretch at 2100 cmꢀ1 (N
ꢀ
=
N N) is indicative of the preservation of the second azide
group.[27]
After 2-azidoethanol and bis(2-azidoethyl) malonate,
bulkier precursors such as dimethyl 5-azidoisophthalate and
1-azidopyrene (Figure 1) were probed for the CuAAC
reaction under the developed experimental conditions. In
both cases, the complete disappearance of the resonances at
2120 cmꢀ1 and 3300 cmꢀ1 was confirmed by FTIR spectros-
copy (Supporting Information, Figures S22 and S23). In
addition, presence of the characteristic carbonyl stretch at
circa 1716 cmꢀ1 in the case of dimethyl 5-azidoisophthalate
after an extensive several-day washing procedure also sup-
ports successful reaction completion. After the development
of the synthetic method for successful solid-state CuAAC
reactions, we finally focused on integration of pBs, in
particular, an azide-containing building block (pB-C20H9N3,
Figure 1). Based on the combination of solid-state 13C CP-
MAS NMR and FTIR spectroscopic data, incorporation of
the corannulene-based unit led to pB-C20H9N3[1 ꢁ (50%)]
formation (Figures 2 and Supporting Information, Fig-
ures S24 and S25). Even after pB incorporation, the
Brunauer–Emmett–Teller (BET) surface area was found to be
865 m2 gꢀ1 according to the gas sorption analysis, which is the
highest surface area reported for any corannulene-containing
structure to date (Supporting Information, Figure S25).
Notably, the observed surface area is in line with corannulene
integration since the measured surface area of the parent
Figure 1. Synthesis of 1ꢁ(50%) including the reaction conditions
utilized for azide–alkyne cycloaddition reaction in the solid state. Blue
color highlights the moieties participating in CuAAC reaction on
molecular species (top). Building blocks utilized in a stepwise
approach for the development of the CuAAC synthetic conditions
applicable for the COF (bottom).
nophenyl)benzene (TAPB) and 1-OMe consisting of DMTA
and TAPB, were utilized for coordinative and non-coordina-
tive pB integration, respectively (Supporting Information,
Schemes S1–S4 and Figures S1–S17).[22] Both selected frame-
works, possessing layered structures with a pore aperture of
33 ꢀ, maintain structural integrity under a wide pH range[22]
making it possible to explore a number of synthetic conditions
for pB immobilization without material degradation. How-
ever, several challenges still had to be addressed for not only
reaction condition development but also synthesis of coran-
nulene-based building blocks on a gram scale. The latter
challenge has been overcome owing to recent advances in pB
chemistry,[3,23–26] allowing for the preparation of azide-con-
taining corannulene (pB-C20H9N3, Figure 1, Scheme S5) using
a 12-step procedure[26] as well as pristine corannulene (pB-
C20H10) by a 9-step approach (Scheme S5).[25]
A stepwise approach was devised for the investigation of
reaction conditions for a copper-catalyzed azide–alkyne
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Figure 2. FTIR spectra of 1ꢁ(50%) (black) and pB-C20H9N3[1ꢁ(50%)]
ꢀ ꢁ
ꢁ
(blue). Grey areas show H C C and C C stretches, present in
1ꢁ(50%) and absent in pB-C20H9N3[1ꢁ(50%)] (left). 13C CP-MAS
NMR spectra of 1ꢁ(50%), a control experiment with 1ꢁ(50%), and
pB-C20H9N3[1ꢁ(50%)], shown in black, orange, and blue, respectively
(right).
COF was found to be 1452 m2 gꢀ1. The synthesized material
also maintains its crystallinity, resulting in the first example of
a crystalline, porous corannulene-based COF.
Figure 3. a) Normalized diffuse reflectance spectra of pB-C20H10@1-
For a comparison, we performed non-coordinative immo-
bilization of the pB inside 1-OMe. For that, we used a simpler
9-step synthetic route required for pB-C20H10 preparation
rather than the 12-step procedure necessary for pB-C20H9N3
preparation (Supporting Information, Figures S27–S29).[25,26]
An additional simplification is also found in pB-
C20H10@1-OMe synthesis. This was achieved through soaking
1-OMe in a pB-C20H10 solution for 5 days, followed by
a thorough washing procedure to remove pB-C20H10 from
the COF surface. Based on 1H NMR spectroscopic analysis of
the digested COF, non-coordinative immobilization led to
inclusion of one corannulene molecule per six -OMe units.
The crystallinity of pB-C20H10@1-OMe after corannulene
incorporation was confirmed by PXRD (Supporting Infor-
mation, Figure S28). The measured BET surface area of pB-
C20H10@1-OMe was found to be 898 m2 gꢀ1 (Supporting
Information, Figure S29).
To probe the electronic structures of pB-containing
materials, we employed diffuse reflectance (DR), steady-
state and time-resolved photoluminescence (PL), and X-ray
photoelectron (XPS) spectroscopies, conductivity measure-
ments, and theoretical calculations. Integration of corannu-
lene moieties inside the COFs through CuAAC or non-
coordinative integration resulted in a significant color change
from pale-yellow to dark red (Figure 3). Indeed, DR spec-
troscopic analysis revealed that corannulene integration
resulted in appearance of an additional absorption band
(550–650 nm) leading to a bathochromic shift of the absorp-
tion profile of over 100 nm in comparison with both the
pristine COF and corannulene units. Such a drastic change
could be attributed to charge transfer (CT) between the
covalent organic host and pB moieties, especially taking into
account the electron donating character of the framework
functional groups (for example, -OMe) and electron-accept-
ing behavior of corannulene moieties.[22] This fact is in line
with the results observed in the case of naphthalene (C10H8)
and pyrene (C16H10) integration, both possessing higher-lying
LUMOs than that of pB-C20H10 (ꢀ2.27 eV in contrast to
OMe (red), 1-OMe (black), pB-C20H9N3[1ꢁ(50%)] (blue), and pB-
C20H10 (grey) with corresponding conductivity values. b) XPS data for
the valence band region for pB-C20H10@1-OMe (red), 1-OMe (black),
pB-C20H9N3[1ꢁ(50%)] (blue), and pB-C20H10 (grey). c) Fluorescent
decay plots of pB-C20H10@1-OMe (red), pB-C20H9N3[1ꢁ(50%)] (blue),
and 1-OMe (grey). d) Photographs of 1-OMe, pB-C20H10, and pB-
C20H10@1-OMe. The table shows the amplitude-weighted average
lifetimes for 1-OMe, pB-C20H10@1-OMe, and PAHs@1-OMe.
ꢀ1.20 eV (C10H8)[28] and ꢀ1.48 eV (C16H10)[29]), which did not
result in CT band formation. Integration of 1,4-dimethox-
ybenzene and 1,5-dimethoxynaphthalene exhibiting electron-
donating behavior also did not result in CT band formation.
To further study the behavior of the prepared materials, we
employed time-resolved PL spectroscopy. With the assump-
tion that the PL decay rate consists of radiative, nonradiative,
and CT components, analysis should reveal shortening of PL
lifetimes of the host owing to integration of corannulene
moieties.[30,31] Indeed, the amplitude-averaged lifetimes esti-
mated by fitting the time-resolved PL decay curves were
474 ps (1-OMe) while pB-C20H10@1-OMe and pB-C20H9N3-
[1 ꢁ (50%)] exhibited much shorter lifetimes of 192 ps and
167 ps, respectively, which is in line with the possibility of CT.
Similar behavior was previously reported for fullerene–
porphyrin dyads in which the decrease in lifetime was
attributed to an electron transfer from porphyrin moieties
(D) to fullerene units (A).[30] Immobilization of planar PAHs
(that is, naphthalene or pyrene) did not result in significant
CT, and estimated lifetimes were similar to that of 1-OMe
(Figure 3).
As a next step, we employed XPS to probe the electronic
structure of the pB-based materials by monitoring the density
of states (DOS) near the Fermi level (EF, binding energy =
0 eV) as a fast and nondestructive pre-screening technique.
This capability is especially crucial in the case of the multi-
step preparation of corannulene derivatives.[32] The valence-
band spectrum of pB-C20H10 itself exhibits behavior associ-
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ated with insulating materials, given that there is zero
intensity within 3 eV of the Fermi level. The spectrum of 1-
OMe itself also shows nearly zero intensity at 2 eV. In
contrast, the XPS valence-band spectra for pB-C20H10@1-
OMe and pB-C20H9N3[1 ꢁ (50%)] have much higher inten-
sities within 2 eVof EF; and this indicates a greater DOS near
EF, which is associated with higher conductivity (see more
details in the Supporting Information). The DOS curves
obtained from the 4-unit computational models are quite
similar for the “stack” and “pinwheel” orientations (see
below) and show overall agreement with the DOS of pristine
corannulene (see more details in the Supporting Information,
Figure S33). To further shed light on the changes of electronic
structure near EF, we have performed pressed-pellet con-
ductivity measurements as well as estimated the optical band
gap values based on DR spectroscopic data. The bulk
conductivity values for 1-OMe, pB-C20H10@1-OMe, and pB-
C20H9N3[1 ꢁ (50%)] were found to be 2.32 ꢁ 10ꢀ12, 6.67 ꢁ 10ꢀ8,
and 2.25 ꢁ 10ꢀ5 Scmꢀ1, respectively, highlighting that conduc-
tivity of corannulene-integrated materials is circa 10000-fold
higher in comparison to the parent framework.
This fact is consistent with the appearance of DOS in the
XPS spectra as well as the trend observed for the optical band
gap values derived from the Tauc plot.[33,34] The estimated
band gaps for COF (1-OMe), pB-C20H10@1-OMe, and pB-
C20H9N3[1 ꢁ (50%)] were found to be 2.24 eV, 1.94 eV, and
1.93 eV, respectively. Thus, pB incorporation resulted in
a conductivity enhancement of four orders of magnitude
while preserving material crystallinity and porosity, thus
providing a pathway to enhance semiconducting behavior in
typically insulating porous COFs. To elucidate how pB
packing (in addition to D–A interactions) could potentially
promote charge transport, we explored the dependence of
electronic properties as a function of possible pB arrange-
ments inside the crystalline host. The pB organization could
be defined by the interplay of electrostatic (dipole–dipole
attractions, repulsions between electron clouds of p-surfaces,
and attractions between the edges and bowl centers),
Figure 4. Interlayer distance in 1-OMe (top).[22] Selected LUMOs,
associated with the ground CT for the three pB-C20H10 units in “stack”
and “pinwheel” orientations (bottom). Theory level, LRC-wPBEh/6-
31G*.
(MOs) associated with the charge transport (see the Support-
ing Information for more details).[41,42] Figure 4 illustrates the
variation of frontier MOs associated with ground state CT. In
the case of convex-to-concave corannulene stacks, frontier
MOs form one p-column through all units, suggesting long-
range p-interactions promoting charge transport. Our calcu-
lations do not show significant orbital delocalization for the
cases of corannulene packing with disordered arrangements
of units (for example, “pinwheel”, Figure 4 and the Support-
ing Information, Figures S32 and S34). The latter fact is in
agreement with previous studies that showed a strong corre-
lation of molecular packing with charge transport.[41,43]
To apply a more generalized approach and establish the
correlation of our suggested model to experimental conduc-
tivity data, we estimated CT constants according to the
Marcus theory [Equation (1)]:
ꢀ
dispersive (surface interactions), and interstack C H···p
interactions with distance between pBs ranging from 3.3 ꢀ
to 3.7 ꢀ.[35,36] In addition, the open nature of the one-
dimensional COF channels provides a structural basis for
accommodation of guest molecules and their efficient con-
finement and packing. Furthermore, molecular dynamics and
intermolecular distances of anchoring corannulene moieties
are restricted by the COF interlayer distance of 3.8 ꢀ
(Figure 4).[22]
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ꢀ
ꢁ
k ¼ 2pjVc j expðꢀ l þ DG0 2=ð4lkBTÞÞ=ꢀh= 4plkBT
2
ð1Þ
where k = charge transfer rate, Vc = direct effective electron
coupling, and l = reorganization energy of the system, see the
Supporting Information for more details.[44,45] By applying the
Einstein relation (m = eD/kB T, D = kL2/2, where m = mobility
of charge transfer carriers, D = diffusion constant, L = mean
length of particle movement) and assuming an equal number
of charge carriers in different packing motifs, we estimated
the conductivity value ratio as a ratio of the corresponding k
values. Within this model, we found that a shift from
noncolumnar organization to a one-dimensional corannulene
stack could result in a circa 42-fold increase in conductivity
values (see the Supporting Information for a detailed descrip-
tion). Therefore, the experimentally observed conductivity
enhancement could be attributed not only to the pB
integration and/or D–A corannulene–host communication
We employed theoretical calculations for a series of pB
motifs by considering three main packing scenarios, convex-
to-concave “stack” (Figure 4), concave-to-concave/convex-
to-convex “clam”, and “pinwheel” observed for the pristine
corannulene in the solid state (Figures 4 and the Supporting
Information, Figure S30).[5,36]
We evaluated the ground state CT in the chosen geo-
metrical arrangements assuming a charge hopping mecha-
nism, which involves transfer of charge through its relocation
from charged to neutral species.[37–40] The approach, based on
the Hartree–Fock theory paired with 6–31 + G* basis, yielded
the electronic couplings and the frontier molecular orbitals
4
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[11] H. Wang, X. Dong, J. Lin, S. J. Teat, S. Jensen, J. Cure, E. V.
inside the crystalline COF but also to the mutual orientation
of the corannulene moieties as shown in Figure 4.
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The preceding results describe the properties of the first
examples of corannulene-based (purely organic) crystalline
and porous scaffolds with embedded pBs. Corannulene
integration resulted in significant changes in the valence
band structure and, thus, a four-orders-of-magnitude con-
ductivity enhancement. Moreover, 1,3-cycloaddition, utilized
for the first time for corannulene integration in the solid state,
led to the formation of materials with the highest surface area
reported for any corannulene-containing materials to date.
Our theoretical analysis paves the way toward simulation of
the electronic coupling constants as a function of corannulene
mutual orientation. Overall, this work demonstrates the high
potential of pBs for the development of materials with
tunability of electronic structures preserving material poros-
ity and crystallinity; and this combination could be crucial for
future technological advances in the fields of optoelectronic
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Acknowledgements
This work was supported by the NSF CAREER Award
(DMR-1553634). N.B.S. thanks the Cottrell Scholar Award
from the Research Corporation for Science Advancement
and Sloan Research Fellowship provided by Alfred P. Sloan
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Keywords: conductivity · corannulene ·
covalent organic frameworks · photophysics ·
theoretical calculations
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Chemie
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Version of record online: && &&, &&&&
6
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ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2018, 57, 1 – 7
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Supramolecular Chemistry
Supra-bowls: A p-bowl is ready to expe-
rience the outside world as it peers into
the window of potential that could exist
with its immobilization inside the scaf-
fold. Corannulene integration resulted in
the first examples of purely organic
crystalline porous materials with tunable
electronic profiles and four-orders-of-
magnitude conductivity enhancement in
comparison with the parent framework.
A. M. Rice, E. A. Dolgopolova,
B. J. Yarbrough, G. A. Leith, C. R. Martin,
K. S. Stephenson, R. A. Heugh,
A. J. Brandt, D. A. Chen, S. G. Karakalos,
M. D. Smith, K. B. Hatzell, P. J. Pellechia,
S. Garashchuk,*
N. B. Shustova*
&&&& — &&&&
Stack the Bowls: Tailoring the Electronic
Structure of Corannulene-Integrated
Crystalline Materials
Angew. Chem. Int. Ed. 2018, 57, 1 – 7
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7
These are not the final page numbers!