Long-Range Self-Assembly of an Electron-Deficient Hexaazatrinaphthylene with Out-of-Plane Substituents

Article abstract of DOI:10.1002/cplu.201900593

The unprecedented time-dependent long-range supramol-ecular assembly of electron-deficient hexaazatrinaphthylene (HATN) core based on peripheral crowding with three out-of-plane cyclic ketals is reported. The single-crystal X-ray structure of the diethyl derivative provided detailed information as to how four molecules in a repeating unit were packed in order to avoid steric crowding of the out-of-plane cyclic ketal side chain, providing locking and fastening for stabilizing the self-assembled structure. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) did not instantaneously show any phase transition upon the cooling process. To our surprise, POM images showed a nucleation of spherulite up to 100 μm after 24 hour later. X-ray diffraction data further confirmed that these soft crystal formed a hexagonal-like crystal. The long-range self-assembly of the new material showed a slight red shift in the UV-vis absorption spectra and further substantiated by computational method.

Full text of DOI:10.1002/cplu.201900593

Accepted Article
Title: The Long-Range Self-Assembly of Electron-Deficient
Hexaazatrinaphthylene with Out-of-Plane Substituents
Authors: Yi-Ru Chen, Yong-Yun Zhang, Ming-Che Yeh, Ying-Ting Luo,
and Chi Wi Ong
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To be cited as: ChemPlusChem 10.1002/cplu.201900593
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The Long-Range Self-Assembly of Electron-Deficient
Hexaazatrinaphthylene with Out-of-Plane Substituents
[a]
Yi-Ru Chen, Yong-Yun Zhang, Ming-Che Yeh, Ying-Ting Luo, and Chi Wi Ong*
Abstract: The unprecedented time-dependent long-range supramol-
ecular assembly of electron-deficient hexaazatrinaphthylene (HATN)
core, 2, based on peripheral crowding with three out-of-plane cyclic
ketal was reported. A single-crystal X-ray of the diethyl derivative
provided detailed structure information as to how four molecules in a
repeating unit were packed to avoid steric crowding of the out-of-
plane cyclic ketal side chain, providing locking and fastening for
stabilizing the self-assembly structure.
despite the initial belief that the steric demand disfavor
aggregation.[35]
An intriguing challenge is to realize the long-range
columnar order for electron-deficient materials. In the case of
HATN, there are, however, two major obstacles discouraging
cofacial self-assembly that have to be overcome, namely
electron-deficient core repulsion and steric interaction of the
spatial demanding side chains. It deserves to be mentioned that
the influence of steric crowding for the triangular HATN core has
not been reported and served as a comparison to the reported
hexabenzocoronene and phthalocyanine core. Herein, we
demonstrate a series of HATN analogs endowed with three out-
of-plane cyclic ketal side chains, 2, exhibit, long-range self-
organization behaviors to form spherulite textures. Further
single-crystal X-ray structure of short-chain derivative manifests
that the long-range order may contribute to the pairwise inverse
packing which effectively interlocks the molecules in the
columnar packing.
Introduction
In the last few decades there has been a growing interest
in discotic liquid crystals (DLCs) owing to their ordered
molecular assemblies that possess potential charge-transport
properties. Most of the previous studies have taken into account
of electron-rich (p-type) cores as promising organic
semiconductors.[1-5] To the authors´ knowledge, electron-
deficient (n-type) cores have been scarcely investigated from the
theoretical point of view.[6-13] Recently, Hexaazatriphenylene
(
HAT) and hexaazatrinaphthylene (HATN) have been reported
as new n-type materials exploiting in many applications,[
including light emitting diodes,[18-19] perovskite solar cells,[20-22]
field effect transistors,[23] and organogelators.[24-25] Our previous
research has established that their liquid crystalline self-
assembly enforced by π-π stacking between the molecules
modulated by the peripheral side-chains into one-dimensional
columnar supramolecular architecture despite the large
repulsive negative charge on the nitrogen atoms between
adjacent core.[26-28] In general, only short-range positional order
is attained within the columns, whereby fluctuations in columnar
orders act as structural trapping sites and suppress transport of
charge.29 As such, one of the crucial prerequisites for efficient
charge carrier transport between electrodes is the long-range
order of the columnar assembly.[30]
14-17]
Scheme 1. The structures of compound 1 and 2.
Results and Discussion
Only a few examples of discotic systems have been
utilized to induce extraordinary long-range self-ordering to form
spherulite texture; Nuckolls et al. described intermolecular
hydrogen bonding arenes,[32] Mullen et al. reported steric
crowding by dove-tailed alkyl substituents in hexa-peri-
hexabenzocoronene, and more recently, Pal et al. described
triphenylene-based discotic liquid crystals.[34] On the other hand,
the out-of-plane cyclic ketal side chains of phthalocyanine core
have been shown to form cofacial columnar self-association,
The general synthetic route of 2, having three cyclic ketal
side chains is shown in Scheme 2. The requisite ketones 5 were
prepared by Grignard addition to the aldehyde to give secondary
alcohol 4, which were subsequently oxidized under the Jones
oxidation condition. Next, condensation of ketone
5 with
[33]
catechol in benzene gave the cyclic ketal 6, and consecutive
nitration provided dinitrobenzene derivatives 7, followed by
hydrogenation to form the diaminobenzene derivatives 8. Finally,
the required compound, 2, was readily accessible by the
straightforward condensation of 8 with hexaketocyclohexane in
2 2
AcOH/CH Cl at ambient temperature. All of the compounds 2
[a]
Y.-R. Chen, Y.-Y. Zhang, Dr. M.-C. Yeh, Y.-T. Luo. Prof. C. W. Ong
Department of Chemistry
National Sun Yat-sen University
can be readily purified by column chromatography and thin layer
preparative plate chromatography on silica gel using
dichloromethane.
70 Lienhai Rd., Kaohsiung 80424 (Taiwan)
E-mail: cong@mail.nsysu.edu.tw
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Table 1. Phase transition behaviors and enthalpy changes of compound
C6,
2
C8, 2C10 and 2C12[a]
2
-1
Compound
Phase Transition ˚C (ΔH, J g )
2
C6
C8
2
2
C10
C12
2
2
Scheme 2. The synthetic approach of compound 2: (i) Aldehyde, Mg, I , ether,
2
5 ˚C, 90 %; (ii) Na
2
CrO7,
H
2
SO
4
, H
2
O, 25 ˚C, 85 %; (iii) 1,2-dihydroxybenzene,
Cl , 0 ˚C, 69 %; (v) Pd/C, N
[
a]
Determined from the DSC profiles in a second heating/cooling cycle at a
benzene, reflux, 72 %; (iv) HNO
EtOH, reflux; (vi) hexaketocyclohexane octahydrate, AcOH, CH
step 26 %.
3
, AcOH, CH
2
2
2 4
H ,
scanning rate of 10 °C/min. [b] No indication of enthalpy means that it can
2 2
Cl , 25 ˚C, two
not form crystal quickly. Cr, crystal; Iso, isotropic melt.
The short-chain (2C6 and 2C8), and long-chain (2C10 and
C12) cyclic ketals were found to display different condensed-
isotropic liquid for 80 hours at room temperature (Figure S11). It
has been found that heating thermogram recorded showed a
slightly higher melting point during the melting process,
indicating an increase in crystallinity caused by spherulite
formation. Spherulite formation had also been reported for
hexabenzocoronene having branching side chains.[33] We
observed expressive differences in the self-organization during
the solidification processes. Compounds 2C6 and 2C8 do not
exhibit spherulite texture, the nucleation of crystals is faster than
2
phase properties. The differential scanning calorimetry (DSC)
scans for compounds 2C6, 2C8, C10 and 2C12 revealed that they
melt from waxy solids into isotropic liquids at 72, 74, 82 and 81
2
˚
(
C, respectively (Table 1). The polarizing optical microscopy
POM) of 2C6 and 2C8 showed the crystal patterns on cooling to
room temperature which was confirmed from X-ray diffraction
XRD) (see the ESI†). Nevertheless, longer length 2C10 and 2C12
(
upon cooling neither formed crystals or showed any birefringent,
and small angle XRD diffractogram from cooling cycle did not
show any prominent peaks, indicating a liquid-like state. This
observation was somewhat similar to the cyclic ketal
phthalocyanine that had been reported to hamper the efficient π-
π stacking.[35] Shearing of the cool sample did not lead to the
mesophase formation.[36] The cooling rates also did not induce
2
C10 and 2C12. As expected, the bulkier the alkyl chains, the lower
[39]
the growth rate and the higher the long-range order.
The
present work is the first example showing electron-deficient core
HATN having tricyclic ketals to form spherulite texture. The
enforced packing of such a system into a highly ordered column
is astonishing. The XRD diffractogram of 2C10 collected at 25 ˚C,
one day after cooling from the isotropic liquid exhibits very sharp
peaks at 27.16 Å, and numerous small peaks in the small-angle
region as showed in Figure 1c, which were assigned as the
hexagonal-like stacking of soft crystal. The spherulites texture
showed high anisotropy and long rang order packing from the
observed Maltese cross.[39] The isogyres along the extinction of
phase transitions of 2C10 and 2C12
.
Many will conclude incorrectly that HATN endowed with
three cyclic ketal side chains cannot form self-assembly
structures. We reasoned that the cyclic ketal with long branch
length in 2C10 and 2C12 must have increased the induction time
for self-assembly of growth, similar to the phenomena of the
reported molecular dynamic simulation on branched
polyethylene having different branching chain content and chain
length.[37] To our great surprise, we observed under POM a
unique phenomenon whereby compounds 2C10 and 2C12 on
leaving the sample from isotropic cooling after 24 hours at room
temperature led to the formation of highly-ordered spherulites
texture, nucleated randomly whose columns are parallel to the
surface over the whole sample (Figure 1a, 1b). The nucleation
point for spherulite growth appeared on hours later after cooling
to room temperature from clearing temperature, which gives us
a first hint of a very slow thermal phase transition. The formation
of the spherulite growth were observed when the temperature
was kept constant at room temperature directly after nucleation
(
Video S1). In order to verify the validity of the thermal and
Figure 1. POM micrographs of (a) 2C10, x50, (b) 2C10, x100, at 25 ˚C on cooling
thermodynamic features about the spherulite, we carried out
(
c) XRD pattern of 2C10 at 25 ˚C , one day after cooling from the isotropic liquid
DSC experiments of compounds 2C10 and 2C12 after cooling from
in a glass capillary (1.5 mm φ) form hexagonal-like crystal.
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the analyzer/polarizer axes illustrated a radial alignment of
columns from the center, whereby the molecules were aligned
homogeneously (edge-on). We speculated that the cyclic ketal
locked the rigid aromatic cores together during stacking into
ordered columns, an essential characteristic of these
compounds for the mesophase to form plastic-like or waxy-soft
crystals with spherulite architecture.
In this context, knowledge about the single-crystal X-ray
diffraction of 2 could provide further understanding of the
morphology of the self-assembly molecules into spherulites.
However, the compounds of 2C6, 2C8, 2C10 and 2C12 gave only
waxy-soft crystals whatever the conditions and solvents
employed. As we failed to obtain single crystals suitable for X-
ray diffraction, we prepared the ethyl homologue 2C2 according
to Scheme 2. Crystals of sufficient quality for structure
determination had been grown from a solution of the compound
assemblies. This single X-ray diffraction provided us with the
insight into the self-assembly of the molecules in 2C10 and 2C12
for the spherulites domains (Figure 2d).[39-41] The well-ordered
packing behavior thus arose from locking of the disc to disc by
the out-of-plane cyclic ketal which reduced their rotation and
slippage within the column, and the modulation of the attractive
π-π intermolecular interaction. This was in contrast to our
previous reported HATN derivative with six long alkoxy
peripheral side chains, 1C10, whereby the electron-deficient
aromatic core had been enforced by the flexible alkoxy side-
chains to form hexagonal or rectangular columnar liquid crystal
phase.[7] The single X-ray diffraction of HATN analogues had
been reported to have an AB staggered packing, consisting of
two molecules per unit cell.[28, 42]
UV-vis optical spectroscopy can be used to study the
evolution of the single molecule absorption spectra upon
aggregation and formation of ordered states. Figure 3 showed
the UV/vis spectra of the compounds 1C10 and 2C10 in hexanes
2
C2 in dichloromethane by the slow evaporation method. The
single-crystal X-ray diffraction of 2C2 illustrated a monoclinic
lattice with space group C2/c with all the molecular planes
aligned in the same direction (Figure 2a, 2b), whereby clearly
providing insight into the columnar molecular arrangement of the
spherulites. The solid-state structure showed an A-B pairwise
assembly of the HATN cores by aryl stacking with approx. 30˚
twist (Figure 2c). The unit cell consisted of two pairwise
structures packing together in an A-B inverse B-A assembly with
an off-set alignment of an aromatic ring and as such a repeating
unit consisting of four HATNs along the stack, whereby
overcoming the steric congestion and at the same time the most
compact packing. The columnar architecture can thus be
envisaged as a zig-zag from the interaction of the two pairwise
and CH
2
Cl
2
(10-5 M) solution and thin film at room temperature.
Cl
1
C10, with linear chains, showed relatively sharp bands in CH
2
2
solution, on another hand, hexanes (apolar solvent) caused the
bands to broaden which clearly indicated the formation of
aggregates. The absorption spectrum for the thin film of 1C10
correlated well with the aggregation. Aggregation in hexanes
most likely occurred in 1C10 because of the amphiphilic nature of
HATN; whereby the hydrophilic core is poorly solubilized by the
apolar solvent and hence favored stacking to maximize
hydrophilic and π–π interactions. The UV-Vis spectrum of 2C10
2 2
displayed a sharp absorption band in CH Cl solution, but
surprisingly also displayed a similar sharp peak in hexanes,
indicating no solvent effect. More interestingly, the thin film of
2
C10 also showed the same absorption pattern. This indicated
that 2C10 aggregated to a single conformation, in line with the
interlocking of the main core by the out-of-plane cyclic ketal.
Additional increment of steric congestion as in 2c10 reduced the
disc to disc interactions with
absorption. The major two absorption band regions observed
a slight blue shift in the
[39]
Figure 2. Single-crystal XRD structure of 2C2: (a) Side view of 2C2 showing
regularly spaced four layers in the unit cell. (b) Top view of 2C2 showing the
tetrameric repeat unit that forms the stacks, with hydrogen and solvent
removed for clarity. (c) Schematic view for the pairwise stacking with twisting
Figure 3. UV-vis absorption spectrum of compound 1C10 and 2C10 at 298 K (a)
approx. 30˚ of
2
C2
.
(d) The schematic illustration of the supramolecular
-5
-5
in 10 M Hexanes (b) 10 M CH
2 2
Cl solution (c) Thin film (d) Simulated
assembly in the structure of 2C10 and 2C12
.
electronic spectrum in CH Cl and Hexanes solution.
2
2
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Table 2. Summary of the UV/vis absorption spectroscopic properties in solution and films and by TD-DFT calculations. [a]
Experimental λabs [nm]
CH Cl
(10-5 M)
Calculated λabs [nm]
CH Cl
soln.[c]
Compd.
Hexanes (10-5 M)
302,427
Thin film
348,439
Hexanes soln.[b]
324,343,414
316,354,412
Gas phase[d]
314,332,407
311,344,404
2
2
2
2
1
C10
C10
307,344,437
291,343,428
326,348,422
321,360,421
2
291,334,416
297,340,407,438
[
a]
TD-DFT calculations of optimized molecular geometries and excitation energies were performed on the level of B3LYP/6-311g(d,p). [b] The calculation was
performed in the presence of n-hexanes. [c] The calculation was performed in the presence of CH
Cl
2
. [d] The calculation was performed in the gas phase.
2
in the spectra at 416-428 nm and 334-343 nm for 2C10 and at
4
27-437 nm and 302-344 for 1C10 appeared to consist of two
intense π → π* transitions due to the increased conjugation in Conclusions
HATN system. Similar observations have been made in the case
of the HATN analogues.[43, 44]
The first electron-deficient discotic system with an
exceptional coherent long-range self-organization to form
spherulite textures is reported. We have disproved the generally
believed that steric congestion at electron-deficient HATN cores
has an adverse effect on self-assembly. On the contrary, we
have found that the incorporation of out-of-plane cyclic ketal on
the triangularly shaped core can enforce interlocking the
coherent long-range ordering of the supramolecular structure.
This newly discovered property along with good solubility and
low isotropization temperature may aid in optimizing the n-type
material as a promising candidate for the active component in
electronic devices.
Further insight into the electronic absorption spectra was
time-dependent density functional theory (TD-DFT). To simplify
the calculations, the long-chain alkyl substituents on the HATN
backbone were replaced with methoxy substituents on 1, as
were the methyl groups on the cyclic ketal HATN 2. The
geometries of these model systems were optimized by the
B3LYP functional with 6-311G(d,p) basis sets. Further support
for the assignment of electron excitations, single point TD-DFT
calculations using the B3LYP/6-31+G(d,p) level of theory were
performed (Tables 2). The calculated electron excitations for
both 1 and 2 produced a spectrum that generally matched the
experimentally observed spectrum. (Figure 3d). The calculated
electron excitations in the range λ = 310-430 nm correspond to
the main absorption region at 410-440 nm and its associated
shoulder peaks in the experimental spectrum. These transitions
represent a π → π* character and involves strongly delocalized
molecular orbitals in full agreement with transitions from the
HOMO and lower occupied MOs to the LUMO and to higher
unoccupied orbitals (Figure 4).[42]
Experimental Section
General Information, Experimental Procedures, and Analytical Data.
All reactions were conducted under an atmosphere of nitrogen in oven-
dried glassware. Dichloromethane was distilled over calcium hydride. All
other reagents were used as commercially available. Nuclear magnetic
resonance spectra were recorded on a Varian Unity- INOVA-500 MHz
spectrometer using CDCl3 as solvent. Chemical shifts are reported in
ppm relative to residual CDCl3 (δ = 7.26, 1H; 77.0, 13C). Mass spectra
were obtained on FT-MS on Bruker APEX II or MALDI-TOF on Bruker
Autoflex III TOF/TOF. Differential scanning calorimetry (DSC) was
measured on a Perkin-Elmer Pyris 1 with heating and cooling rates of 10
o
–
C min 1. Polarized Optical Micrographs (POM) were recorded on a
Nikon model ECLIPSE LV100 POL optical polarizing microscope
equipped with Mettler-Toledo FP-90 hot stage. X-Ray powder
a
diffraction (XRD) data were collected on the wiggler beamline BL17A of
the National Synchrotron Radiation Research Center (NSRRC), Taiwan,
using a triangular bent Si (111) monochromator and a wavelength of
1
5
.33367 Å. The sample in a 1 mm capillary was mounted on the Huber
020 diffractometer. An air stream heater is equipped at BL17A beamline
and the temperature controller is programmable by a PC with a PID
feedback system. Single crystal X-ray data was carried out with a Bruker
D8 venture dual X-ray single crystal diffractometer. CCDC 1872186 for
2C2 contains the supplementary crystallographic data for this paper. The
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre. UV–vis spectra were obtained on an
JASCO V-670 spectrophotometer. DFT and TD-DFT calculations were all
performed using the Gaussian 09 program with the B3LYP hybrid
functional and basis set 6-311G(d,p) for the ground state geometry
optimization. Single point TD-DFT calculation was done in medium of 1
Figure 4. Frontier Molecular Orbitals of HOMO and LUMO for 1 (left) and 2
(
right) from B3LYP/6-311G(d,p) calculations.
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and 2 at the B3LYP/6-31+G(d,p) level of theory in CH2Cl2 and n-hexane.
The solvent effect was modelled using the integral equation formalism
variant of the polarizable continuum model (IEFPCM) as implemented in
Gaussian09. The lowest 30 excited states were considered in TD-DFT
calculations. Only electron excitations with oscillator strengths greater
than 0.05 were considered in the simulation. 2,2-diethylbenzo[d][1,3]diox-
ole and 2,2-diethyl-5,6-dinitrobenzo[d][1,3]dioxole were synthesized
according to literature procedures.[45, 46]
rigorously purified by column chromatography (SiO2, CH2Cl2/Hexanes
1/10 v/v) to give pure 2 as a yellow solid.
2,2,9,9,16,16-hexaethyl-[1,3]dioxolo[4',5':6,7]quinoxalino[2,3-a]
[
(
1,3]dioxolo[4',5':6,7]quinoxalino[2,3-c][1,3]dioxolo[4,5-i]phenazine
2C2) Yellow solid (26%);
1H NMR (500 MHz, CDCl3): δ (ppm) 7.74 (s, 6H), 2.11 (q, J = 7.4 Hz,
1
1
2H), 1.07 (t, J = 7.4 Hz, 18H); 13C NMR (125 MHz, CDCl3): δ (ppm)
General procedure of 2,2-dialkyl-5,6-dinitrobenzo[d][1,3]dioxole
54.05, 142.90, 140.67, 125.01, 104.00, 31.04, 29.83, 7.13; MALDI-TOF
+
mass: calcd. for C39H36N6O6 [M+H] : m/z = 685.28; found: 685.97.
2,2-dialkylbenzo[d][1,3]dioxole (16.8 mmol) was dissolved in 15 mL
CH2Cl2 and 15 mL AcOH. The mixture was kept in ice bath to attain 0 ˚C,
then 9 mL 65% nitric acid was added dropwisely. After the addition
completed, 5 mL 100% concentrated nitric acid was added dropwisely in
cold. Then the mixture was allowed to stir at room temperature and after
2
,2,9,9,16,16-hexahexyl-[1,3]dioxolo[4',5':6,7]quinoxalino[2,3-a]
[1,3]dioxolo[4',5':6,7]quinoxalino[2,3-c][1,3]dioxolo[4,5-i]phenazine
2C6) Yellow solid (13%);
(
20
hours progress of the reaction was monitored by TLC. After
1H NMR (500 MHz, CDCl3): δ (ppm) 7.72 (s, 6H), 2.05 (t, J = 8.5 Hz,
completion of the reaction, the mixture was poured into ice-water and
CH2Cl2 and the layer was separated. The organic layer was further
washed with aqueous NaHCO3 and brine and dried over MgSO4. The
solvent was removed under reduced pressure. The resulting crude
product was crystallized from ethanol to afford the corresponding product
of 7.
1
2H), 1.52-1.45 (m, 12H), 1.40-1.20 (m, 36H), 0.84 (t, J = 7.0 Hz, 18H);
13C NMR (125 MHz, CDCl3): δ (ppm) 153.71, 142.72, 140.45, 124,49,
103.86, 38.11, 31.51, 29.06, 22.47, 22.41, 13.96; MALDI-TOF mass:
+
calcd. for C63H84N6O6 [M+H] : m/z = 1021.65; found: 1021.65.
2
,2,9,9,16,16-hexaoctyl-[1,3]dioxolo[4',5':6,7]quinoxalino[2,3-
a][1,3]dioxolo[4',5':6,7]quinoxalino[2,3-c][1,3]dioxolo[4,5-i]phenazine
2C8) Yellow solid (12%);
2,2-dihexyl-5,6-dinitrobenzo[d][1,3]dioxole (7C6) Yellow liquid (43%);
(
1H NMR (500 MHz, CDCl3): δ 7.19 (s, 2H), 1.95-1.99 (m, 4H), 1.25-1.44
m, 16H), 0.88 (t, 6H, J = 7Hz); 13C NMR (125 MHz, CDCl3): δ 151.24,
1H NMR (500 MHz, CDCl3): δ (ppm) 7.73 (s, 6H), 2.06 (t, J = 7.5 Hz,
(
1
2H), 1.53-1.45 (m, 12H), 1.40-1.15 (m, 60H), 0.85 (t, J = 7.0 Hz, 18H);
138.19, 127.49, 104.06, 37.69, 31.44, 28.93, 22.41, 22.24, 13.92.
13C NMR (125 MHz, CDCl3): δ (ppm) 153.71, 142.74, 140.48, 124.50,
1
03.91, 38.12, 31.75, 29.44, 29.31, 29.09, 22.57, 22.55, 14.04; MALDI-
TOF mass: calcd. for C75H108N6O6 [M+H]+: m/z
1189.83; found:
5,6-dinitro-2,2-dioctylbenzo[d][1,3]dioxole (7C8) Yellow liquid (69%);
=
1
189.71.
1H NMR (500 MHz, CDCl3): δ 7.18 (s, 2H), 1.94-1.97(m, 4H), 1.25-1.42
m, 24H), 0.86 (t, 6H, J = 7Hz); 13C NMR (125 MHz, CDCl3): δ 151.24,
(
2,2,9,9,16,16-hexadecyl-[1,3]dioxolo[4',5':6,7]quinoxalino[2,3-
1
1
38.20, 127.49, 104.09, 37.69, 31.72, 29.29, 29.24, 29.07, 22.56, 22.31,
4.01.
a][1,3]dioxolo[4',5':6,7]quinoxalino[2,3-c][1,3]dioxolo[4,5-i]phenazine
2C10) Yellow solid (15%);
(
2,2-didecyl-5,6-dinitrobenzo[d][1,3]dioxole (7C10) Yellow liquid (61%);
1H NMR (500 MHz, CDCl3): δ (ppm) 7.74 (s, 6H), 2.06 (t, J = 8.0 Hz,
1
2H), 1.60-1.40 (m, 12H), 1.40-1.15 (m, 84H), 0.85 (t, J = 8.0 Hz, 18H);
1H NMR (500 MHz, CDCl3): δ 7.18 (s, 2H), 1.94-1.97 (m, 4H), 1.25-1.42
m, 24H), 0.86 (t, 6H, J = 7Hz); 13C NMR (125 MHz, CDCl3): δ 151.24,
13C NMR (125 MHz, CDCl3): δ (ppm) 153.72, 142.74, 140.52, 124.52,
(
103.94, 38.14, 31.86, 29.53, 29.46, 29.39, 29.26, 22.64, 22.58, 14.08;
MALDI-TOF mass: calcd. for C87H132N6O6 [M+H] : m/z = 1358.02; found:
1358.87.
+
138.20, 127.49, 104.09, 37.69, 31.72, 29.29, 29.24, 29.07, 22.56, 22.31,
4.01.
1
2,2-didodecyl-5,6-dinitrobenzo[d][1,3]dioxole (7C12) Yellow liquid
2,2,9,9,16,16-hexadodecyl-[1,3]dioxolo[4',5':6,7]quinoxalino[2,3-
(44%);
a][1,3]dioxolo[4',5':6,7]quinoxalino[2,3-c][1,3]dioxolo[4,5-i]phenazine
(2C12) Yellow solid (12%);
1H NMR (500 MHz, CDCl3): δ 7.18 (s, 2H), 1.94-1.98 (m, 4H), 1.25-1.44
m, 40H), 0.87 (t, 6H, J = 7Hz); 13C NMR (125 MHz, CDCl3): δ 151.23,
(
1H NMR (500 MHz, CDCl3): δ (ppm) 7.74 (s, 6H), 2.06 (t, J = 8.0 Hz,
12H), 1.53-1.45 (m, 12H), 1.40-1.15 (m, 108H), 0.85 (t, J = 7.0 Hz, 18H);
13C NMR (125 MHz, CDCl3): δ (ppm) 153.73, 142.76, 140.49, 124.53,
138.22, 127.49, 104.09, 37.71, 31.88, 29.63, 29.57, 29.54, 29.43, 29.31,
2.65, 22.33, 14.07.
2
1
2
1
03.92, 38.14, 31.87, 29.68, 29.60, 29.57, 29.45, 29.38, 29.31, 22.65,
2.57, 14.08; MALDI-TOF mass: calcd. for C99H156N6O6 [M+H] : m/z =
526.21; found: 1526.98.
+
General procedure of 2,2,9,9,16,16-hexaalkyl kis-[1,3]dioxolo[4',5':6,-
]quinoxalino[2,3-a][1,3]dioxolo[4',5':6,7]quinoxalino[2,3-c][1,3]diox-
7
olo[4,5-i]phenazine
To a solution of hexaketocyclohexane (0.7 mM) and 2,2-dialkylbenzo[d]-
Acknowledgements
[
1,3]dioxole-5,6-diamine (2.3 mM) obtained after filtration of the
hydrogenation reaction in dichloromethane (40 mL) was added acetic
acid (5 mL). The reaction mixture was stirred at room temperature for 24
h. Removal of the solvent in vacuo gave crude product that had to be
This work is supported by grants from the Ministry of
Scinence and Technology (MOST106-2113-M-110-006-, MOST
1
07-2113-M-110-014- and MOST108-2113-M-110-012-). We
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are grateful to the thank of National Synchrotron Radiation
Research Center (NSRRC) for carrying out XRD experiments.
We also wish to thank Dr. Marli Ferreira for her helpful
discussions.
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The Long-Range Self-Assembly of
Electron-Deficient
Hexaazatrinaphthylene with Out-of-
Plane Substituents
Against the odd: The steric crowded cyclic ketal ring to the peripheral site of the
electron-deficient hexaazatrinaphthylene ring cunningly finds a way to interlock into
long-range self-assembly. We observed the growth of crystalline spherulites was
dependent on the aging time under the polarizing optical microscope. The single X-
ray diffraction shows hierarchical pairwise antiparallel packing for cofacial π-π
arrangement.
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