Escolar Documentos
Profissional Documentos
Cultura Documentos
201500431
Full Paper
Carbazole Chromophores
eties. All of the products feature intramolecular charge-transfer bands in the visible region. TCBD substitution at the 1position of the carbazole gave rise to small HOMOLUMO
gaps compared to that at the 2- and 3-positions. The relationship between the TCBD substitution pattern of the carbazole moiety and the effectiveness of donoracceptor pconjugation was evaluated, and it was established that the
p-conjugation was effective in order of positions 1 < 2 < 3.
Introduction
The rational design of novel donoracceptor (DA) compounds, so-called pushpull chromophores,[1] featuring intense
intramolecular charge-transfer (ICT) interactions, has received
an impressive amount of attention because of their potential
application in nonlinear optics (NLOs),[2] organic photovoltaics
(OPVs),[3] dye-sensitized solar cells (DSSCs),[4] and ambipolar organic field-effect transistors (OFETs).[5] Variation of the donor
and acceptor moieties has been widely recognized as a useful
approach for tuning the HOMOLUMO gaps in pushpull systems. From the geometrical point of view, a large number of
fully planar pushpull chromophores have been extensively investigated over the past decades, for which efficient electronic
communication between the donor and acceptor is expected.
Nonplanar molecules have several advantagesthey are generally more soluble, less aggregating, and more readily sublimable than planar ones; these features favor the formation of
the thin films that are used in optoelectronic devices. Diederichs group and others have recently shown that alkynes activated appropriately by electron-donating groups undergo
formal [2+
+2] cycloadditions with electron-withdrawing olefins,[68] such as tetracyanoethylene (TCNE), 7,7,8,8-tetracyanop-quinodimethane (TCNQ), and related powerful electron acceptors, followed by retro-electrocyclization, to afford a class
[a] Dr. S.-i. Kato, H. Noguchi, S. Jin, Prof. Dr. Y. Nakamura
Division of Molecular Science
Faculty of Science and Technology
Gunma University
1-5-1 Tenjin-cho, Kiryu, Gunma 376-8515 (Japan)
Fax: (+ 81) 277-30-1314
E-mail: nakamura@gunma-u.ac.jp
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ajoc.201500431.
Asian J. Org. Chem. 2016, 5, 246 256
246
Full Paper
www.AsianJOC.org
(83 8C) led to complete consumption of 11, and 2 was obtained in 85 % yield.
In contrast to 1012, the reaction of bicarbazoles 1318
with TCNE did not proceed at room temperature. Heating a solution of 1318 and TCNE was required for this transformation
to occur; 1,1,2,2-tetrachloroethane, with a boiling point of
147 8C, was used as a reaction solvent (Schemes 2 and 3).
Moreover, an excess amount of TCNE was used for the transformation of bicarbazoles except for 18; we added 1 equivalent of TCNE at a time up to 10 equivalents, while monitoring
247
Full Paper
www.AsianJOC.org
Full Paper
conjugation between the carbazole donor and TCBD acceptor
moieties in 1 is less effective than that in 2 and 3 (see below).
The longest lmax values of 46 are blue-shifted relative to
those of 13, respectively, by 3487 nm (4: 650 nm, 5: 412 nm,
6: 455 nm; Figure 2 b). The increase of the optical HOMO
LUMO gaps (DEopt) observed by electronic absorption spectroscopy results from an increase of the LUMO levels relative to
the HOMO levels, as confirmed by CV (see below). Incorporation of the second carbazole chromophore increases the
e values in the ICT bands. The e values in the ICT absorption
band of 4 are significantly low compared to 5 and 6, indicating
that the DA conjugation in 4 is ineffective for the same steric
reason as in the case of 1.
The substantial redshifts of the longest lmax in 8 and 9 as
compared to 5 and 6, respectively, by approximately 40 nm,
are attributed to the extension of p-conjugation (8: 451 nm, 9:
491 nm; Figure 2 c). In sharp contrast, the longest lmax of 7 is
blue-shifted relative to that of 4 by 7 nm (7: 643 nm), suggesting that the large twist between the carbazole and TCBD moieties is present in 7 as in 1 and 4 (see below).
In any of the series 13, 46, and 79, TCBD substitution at
the 1-position of the carbazole leads to the most-redshifted
absorption spectra, and TCBD at the 2-position gives rise to
the least. Thus there is a clear relationship between the TCBDsubstitution pattern of the carbazole moiety and the DEopt
values; the optical gaps generally decrease in order of position
2 > 3 > 1, although we cannot entirely rule out the effect of
the tBu groups in 1, 4, and 7. Consequently, the DEopt value of
1.81 eV for 1 is the lowest in the compounds in this study.
Electrochemistry
We performed CV for 19 as well as 9-ethyl-9H-carbazole (19)
and 3,6-di-tert-butyl-9-ethyl-9H-carbazole (20) in CH2Cl2 containing nBu4NPF6 (0.1 mol L1) as the supporting electrolyte.
Compounds 19 are amphoteric within the available potential
window (Figure 3), and the oxidation potentials (Epa) and reduction potentials (Epc) versus ferrocenium/ferrocene (Fc + /Fc)
are summarized in Table 2.
All TCBD-substituted carbazoles showed oxidation steps centered on the electron-donating carbazole moiety. The oxidation
processes for 1, 4, and 7 bearing the tBu groups at the 3,6-positions of the carbazole moiety are reversible or quasi-reversible, while those for 2, 3, 5, 6, 8, and 9 are irreversible. The tBu
groups at the 3- and 6-positions in 1, 4, and 7 sufficiently increase the kinetic stability of cationic species formed upon
electron release.[10b, 11b,c] The somewhat lower reversibility in 7
than 1 and 4 is attributed to the electron-accepting ethynylene
unit in 7. Irreversible oxidation processes for 2, 3, 5, 6, 8, and 9
indicate the formation of an unstable radical cation, which can
be involved in electrochemical dimerization or polymerization.
Compounds 19 has two reversible, well-resolved reduction
steps characteristic of TCBD-substituted derivatives; each dicyanovinyl moiety is responsible for a 1 e reduction.
As summarized in Table 2, compounds 19 are oxidized at
higher potentials than the corresponding 19 or 20, attributable
to p-conjugation between the carbazole donor and TCBD ac-
www.AsianJOC.org
249
Full Paper
Table 1. Electronic absorption spectral data and calculated lowest excitation energies of 19.
Compd
e [L mol1 cm1][a]
f[c]
Composition of band[c]
684 (1.81)
800
2
3
480 (2.53)
542 (2.29)
5300
5300
650 (1.90)
2500
412 (3.00)
27 100
745 (1.66)
616 (2.01)
574 (2.16)
649 (1.90)
571 (2.16)
683 (1.81)
650 (1.90)
411 (3.01)
0.036
0.032
0.141
0.088
0.026
0.074
0.065
0.078
455 (2.72)
34 300
406 (3.04)
426 (2.90)
0.087
0.045
416 (2.97)
0.064
610 (2.03)
592 (2.09)
466 (2.65)
0.020
0.216
0.267
450 (2.74)
0.204
481 (2.57)
459 (2.69)
0.083
0.406
H-1!L, 3 %; H!L, 96 %
H-1!L, 96 %; H!L, 3 %
H-1!L, 98 %
H!L, 98 %
H-1!L, 97 %
H!L, 98 %
H-1!L, 97 %;
H-3!L, 3 %; H-3!L + 1, 10 %;
H-2!L, 81 %; H-2!L + 1, 2 %
H-3!L, 21 %; H-3!L + 1, 8 %; H-2!L, 2 %; H-2!L + 1, 65 %
H-1!L, 6 %; H-1!L + 1, 5 %;
H!L, 85 %
H-1!L, 21 %; H-1!L + 1, 12 %;
H!L + 1, 60 %
H-1!L, 93 %; H!L, 4 %
H-1!L, 4 %; H!L, 93 %
H-3!L, 29 %; H-3!L + 1, 2 %;
H-2!L, 66 %
H-3!L, 65 %; H-2!L, 27 %;
H-2!L + 1, 2 %
H-1!L, 62 %; H!L, 34 %
H-1!L, 35 %; H!L, 59 %
643 (1.92)
7900
451 (2.74)
26 300
491 (2.52)
31 900
[a] In CH2Cl2. [b] Only the longest absorption maxima are shown. [c] TD-DFT [TD-PBE0/6-31G(d)] calculations were performed with the use of optimized
structures at the PBE0/6-31G(d) level of theory, and only energies with f > 0.02 are shown; f = oscillator strength; H = HOMO, L = LUMO.
www.AsianJOC.org
Full Paper
Table 2. Oxidation (Epa) and reduction (Epc) potentials of 19 determined
by CV in CH2Cl2 (0.1 mol L1 nBu4NPF6),[a] theoretically calculated HOMO
and LUMO levels and their gaps (DEHOMOLUMO),[b] and electrochemical
(DEredox)[c] and optical energy gaps (DEopt)[d] .
Compd
Epa
[V]
+ 0.97[e] 0.56[e]
1.32[e]
+ 1.03[f] 0.62[e]
1.27[e]
[g]
+ 1.07
0.67[e]
1.30[e]
+ 1.06[e] 0.60[e]
1.29[e]
+ 1.04[f] 0.85[e]
1.23[e]
+ 1.10[f] 0.96[e]
1.29[e]
+ 0.98[g] 0.61[e]
1.17[e]
[f]
+ 1.02
0.70[e]
1.12[e]
+ 1.05[f] 0.80[e]
1.17[e]
+ 0.89[f] [h]
+ 0.71[e] [h]
2
3
4
5
6
7
8
9
19
20
Epc
[V]
4.06
2.34
1.53
1.81
6.49
4.16
2.33
1.65
2.53
6.54
4.08
2.46
1.74
2.29
6.21
3.75
2.46
1.66
1.90
6.35
3.04
3.31
1.89
3.00
6.35
2.80
3.55
2.06
2.72
6.12
3.56
2.56
1.59
1.92
6.40
3.46
2.94
1.72
2.74
6.34
3.23
3.11
1.85
2.52
5.76
5.53
0.81
0.77
4.95
4.76
[h]
[h]
[a] All potentials are given versus the Fc + /Fc couple used as external
standard. Scan rate: 100 mV s1. [b] PBE0/6-311G(d,p)//PBE0/6-31G(d).
[c] Electrochemical gap, DEredox, is defined as the potential difference between Epa and Epc. [d] Optical gap, DEopt, is defined as the energy corresponding to the lmax. [e] Reversible wave. [f] Irreversible wave. [g] Quasireversible. [h] No reduction peak within the available potential window.
www.AsianJOC.org
251
Full Paper
Figure 4. Molecular orbital plots [PBE0/6-311G(d,p)//PBE0/6-31G(d)] of a) 1, b) 2, c) 3, d) 4, e) 5, f) 6, g) 7, h) 8, and i) 9. The lower plots represent the HOMOs,
and the upper plots represent LUMOs. The optimized structures are shown in Figure S5.
ized in Table 1. The absorption maxima in the low-energy regions of 1, 3, 4, 6, 7, and 9 are essentially ascribed to transitions from the HOMOs and/or HOMO-1s, mainly localized on
the carbazole moiety, to the LUMOs, mainly localized on the
TCBD moiety, judging from their moderate-to-high oscillator
strengths f, which are 0.0200.406. Compounds 2, 5, and 8
have significantly low f values of 0.0012, 0.0091, and 0.0159, respectively, for the HOMOLUMO transitions. This suggests that
the HOMOLUMO transitions for 2, 5, and 8 are almost forbidden, unlike those of 1, 3, 4, 6, 7, and 9. The absorption
maxima in the low-energy region of 2, 5, and 8 are ascribed to
the transitions from the HOMO-1s, HOMO-2s, and/or HOMO-3s,
mostly localized on the carbazole moiety, to the LUMOs (Figures S6S8). The calculated lmax values of 2, 5, and 8 are blueshifted relative to those of 1 and 3, 4 and 6, and 7 and 9, reAsian J. Org. Chem. 2016, 5, 246 256
www.AsianJOC.org
spectively (Table 1), which is in good agreement with the electronic absorption spectroscopy results. The forbidden HOMO
LUMO transitions in 2, 5, and 8 are explained by the almost no
overlap between the HOMOs and LUMOs in the TCBD moiety,
which should lead to a lack of the transition dipole moment
from the carbazole moiety to the TCBD moiety. In other words,
the small but distinctive overlap between the HOMOs and
LUMOs in both the carbazole and TCBD moieties in 1, 3, 4, 6,
7, and 9 are essential for their allowed HOMOLUMO transitions. Therefore, it can be concluded that the difference in
trend of the TCBD-substitution pattern for the optical gaps
and that for the electrochemical gaps is attributed to the forbidden HOMOLUMO transitions that result from the TCBD
substituent at the 2-position of the carbazole.
252
Full Paper
Conclusions
Quantum chemical calculations were performed using the Gaussian 09 program package.[27] Molecular properties in the electronic
ground state were computed using the hybrid PBE0 DFT
method.[30] Geometry optimization of 19 was performed with no
symmetry constraints with the 6-31G(d) basis set.[31] Frequency calculations on these optimized geometries revealed no imaginary
frequencies. Further single-point calculations were performed with
the 6-311G(d,p) basis set[32] to obtain molecular orbital energies
with use of optimized structures at the PBE0/6-31G(d) level of
theory. TD calculations for 19 were performed at the PBE0/631G(d) level of theory with use of optimized structures at the
PBE0/6-31G(d) level of theory. The calculated electronic transitions
are vertical.
[2+
+2] Cycloaddition/Retro-Electrocyclization Reactions
General procedure: One equivalent of TCNE was added to a solution of acetylenic carbazole derivative (1 equiv) in 1,2-dichloroethane or 1,1,2,2-tetrachloroethane, and the resulting mixture was
stirred at 25147 8C under an argon atmosphere. To fully react the
precursor carbazole, 1 equivalent of TCNE was added at a time to
the mixture up to 10 equivalents, while being monitored by TLC.
After the mixture was stirred for 15 min48 h, the solvent was removed under reduced pressure. The residue was purified by washing with hexane, recrystallization, and/or column chromatography.
An analytically pure material was obtained by using recycling GPC,
eluting with CHCl3.
2-(3,6-Di-tert-butyl-9-ethyl-9H-carbazol-1-yl)buta-1,3-diene1,1,4,4-tetracarbonitrile (1): Compound 10 (40 mg, 0.12 mmol)
was allowed to react with TCNE (15 mg, 0.12 mmol) in 1,2-dichloroethane (5 mL) at room temperature for 2 h. The crude material was
dissolved in hexane, and insoluble material was removed by filtration. The filtrate was evaporated under reduced pressure to give
1 as a blue solid (55 mg, quant); m.p. 190193 8C; 1H NMR
(300 MHz, CDCl3): d = 1.25 (t, J = 7.2 Hz, 3 H), 1.45 (s, 9 H), 1.47 (s,
9 H), 3.914.02 (m, 1 H), 4.174.29 (m, 1 H), 7.18 (d, J = 1.8 Hz, 1 H),
7.36 (d, J = 8.7 Hz, 1 H), 7.60 (dd, J = 1.8, 8.7 Hz, 1 H), 8.11 (d, J =
1.8 Hz, 1 H), 8.13 (s, 1 H), 8.37 ppm (d, J = 1.8 Hz, 1 H); 13C NMR
(125 MHz, CDCl3): d = 14.1, 31.8, 32.0, 34.9, 35.0, 40.5, 93.2, 98.2,
107.7, 109.3, 110.8, 110.9, 111.0, 112.2, 116.9, 122.7, 123.0, 124.9,
125.3, 126.8, 135.7, 139.7, 143.6, 144.0, 149.5, 162.2 ppm; UV/vis/
NIR (CH2Cl2): lmax (relative intensity) = 275 (sh, 0.65), 301 (1.00), 360
(sh, 0.18), 684 nm (0.02); HRMS (FAB): m/z: calcd for C30H29N5 :
459.2423 [M] + ; found 459.2422. Elemental analysis calcd (%) for
C30H29N50.05 CHCl3 : C 77.53, H 6.29, N 15.04; found: C 77.68, H
6.55, N 14.82.
Experimental Section
General
Column chromatography and plug filtrations were carried out with
SiO2 60. TLC was conducted on aluminum sheets coated with SiO2
60 F254 ; visualization was performed with a lamp (254 or 365 nm).
Melting points (m.p.) are uncorrected. Residual and deuterated solvent signals in the 1H and 13C NMR spectra were used as internal
references, respectively (CDCl3, 1H: d = 7.26 ppm, 13C: d =
77.16 ppm; 1,1,2,2-[D2]tetrachloroethane, 1H: d = 6.00 ppm; 13C: d =
74.00 ppm). Chemical shifts (d) are given as values in ppm. The
coupling constants (J) are given in Hz. The apparent resonance
multiplicity is described as s (singlet), d (doublet), t (triplet), q
(quartet), or m (multiplet). FAB-MS spectra were recorded in the
positive-ion mode with m-nitrobenzyl alcohol as the matrix.
MALDI-TOF MS spectra were recorded in the positive-ion mode
with dithranol as the matrix. The most important signals are reported in m/z units with M as the molecular ion. The UV/vis spectra
were measured in a 1 cm cuvette at 298 K. The absorption maxima
(lmax) are reported in nm with relative intensities. Shoulders are indicated as sh. Gel permeation chromatography (GPC) was performed with CHCl3 ; an analytically pure material was obtained by
recycling GPC. Compounds 1018 were prepared according to literature procedures.[11b]
CV was performed by using a cell equipped with a platinum working electrode, a platinum wire counter electrode, and Ag/AgNO3 as
Asian J. Org. Chem. 2016, 5, 246 256
www.AsianJOC.org
2-(9-Ethyl-9H-carbazol-2-yl)buta-1,3-diene-1,1,4,4-tetracarbonitrile (2): Compound 11 (30 mg, 0.13 mmol) was allowed to react
with TCNE (17 mg, 0.13 mmol) in 1,2-dichloroethane (10 mL) at
reflux (84 8C) for 3 h. The crude material was purified by column
chromatography (SiO2, CH2Cl2) and recrystallization from CH2Cl2/
hexane to give 2 as a purple solid (40 mg, 85 %); m.p. 97100 8C;
1
H NMR (500 MHz, CDCl3): d = 1.48 (t, J = 7.2 Hz, 3 H), 4.43 (q, J =
7.2 Hz, 2 H), 7.18 (dd, J = 1.8, 8.1 Hz, 1 H), 7.307.34 (m, 1 H), 7.48 (d,
J = 8.1 Hz, 1 H), 7.587.62 (m, 2 H), 8.13 (s, 1 H), 8.16 (d, J = 7.8 Hz,
1 H), 8.27 ppm (d, J = 8.1 Hz, 1 H); 13C NMR (125 MHz, CDCl3): d =
14.1, 38.1, 90.1, 98.3, 108.5, 109.3, 109.6, 111.4, 111.9, 112.1, 119.4,
120.3, 121.9, 121.9, 122.1, 126.5, 128.1, 128.5, 139.6, 141.9, 153.4,
163.1 ppm; UV/vis/NIR (CH2Cl2): lmax (relative intensity) = 267 (1.00),
253
Full Paper
304 (0.79), 360 (sh, 0.15), 480 nm (0.16); HRMS (FAB): m/z: calcd for
C22H13N5 : 347.1171 [M] + ; found 347.1176. Elemental analysis calcd
(%) for C22H13N50.23 CHCl3 : C 71.23, H 3.56, N 18.68; found: C
71.28, H 3.89, N 18.44.
2-(9-Ethyl-9H-carbazol-3-yl)buta-1,3-diene-1,1,4,4-tetracarbonitrile (3): Compound 12 (170 mg, 0.77 mmol) was allowed to react
with TCNE (102 mg, 0.80 mmol) in 1,2-dichloroethane (8 mL) at
room temperature for 15 min. The crude material was purified by
recrystallization from CH2Cl2/hexane to give 3 as a purple solid
(241 mg, 90 %); m.p. 233236 8C; 1H NMR (500 MHz, CDCl3): d = 1.50
(t, J = 7.2 Hz, 3 H), 4.43 (q, J = 7.2 Hz, 2 H), 7.357.38 (m, 1 H), 7.49
(d, J = 8.1 Hz, 1 H), 7.557.60 (m, 3 H), 8.15 (d, J = 8.1 Hz, 1 H), 8.16
(s, 1 H), 8.24 ppm (d, J = 1.8 Hz, 1 H); 13C NMR (125 MHz, CDCl3): d =
14.0, 38.3, 86.4, 98.3, 108.7, 109.7, 110.1, 111.8, 112.0, 112.7, 120.9,
121.2, 121.3, 122.6, 122.8, 124.4, 126.9, 127.8, 141.0, 143.3, 154.9,
162.3 ppm; UV/vis/NIR (CH2Cl2): lmax (relative intensity) = 288 (1.00),
330 (sh, 0.50), 350 (sh, 0.29), 450 (sh, 0.12), 542 nm (0.16); HRMS
(FAB): m/z: calcd for C22H13N5 : 347.1171 [M] + ; found: 347.1143. Elemental analysis calcd (%) for C22H13N50.03 CHCl3 : C 75.39, H 3.74, N
19.96; found: C 75.37, H 3.85, N 19.65.
Bis(9-ethyl-9H-carbazol-2-yl)buta-1,3-diene-1,1,4,4-tetracarbonitrile (5): Compound 14 (42 mg, 0.102 mmol) was allowed to react
with TCNE (36 mg, 0.282 mmol) in 1,1,2,2-tetrachloroethane
(10 mL) at reflux (147 8C) for 40 h. The crude material was purified
by column chromatography (SiO2, CH2Cl2) to give 5 as a purple
solid (24 mg, 43 %); m.p. 181183 8C; 1H NMR (300 MHz, CDCl3): d =
1.48 (t, J = 7.2 Hz, 6 H), 4.42 (q, J = 7.2 Hz, 4 H), 7.277.32 (m, 2 H),
7.42 (dd, J = 1.8, 8.4 Hz, 2 H), 7.47 (d, J = 8.4 Hz, 2 H), 7.577.63 (m,
2 H), 8.12 (d, J = 8.4 Hz, 2 H), 8.13 (s, 2 H), 8.20 ppm (d, J = 8.4 Hz,
2 H); 13C NMR (125 MHz, CDCl3): d = 14.1, 38.1, 84.8, 109.4, 110.1,
111.9, 113.1, 120.4, 120.5, 121.8, 121.8, 121.9, 128.1, 128.6, 128.8,
139.4, 142.4, 168.8 ppm; UV/vis/NIR (CH2Cl2): lmax (relative intensity) = 262 (1.00), 306 (0.44), 412 nm (0.63); MS (MALDI-TOF): m/z:
541.18 [M+
+H] + ; HRMS (FAB): m/z: calcd for C36H24N6 : 540.2062 [M] +
; found: 540.2063. Elemental analysis calcd (%) for
C36H24N60.03 CHCl3 : C 79.52, H 4.45, N 15.44; found: C 79.73, H
4.79, N 15.51.
Bis(9-ethyl-9H-carbazol-3-yl)buta-1,3-diene-1,1,4,4-tetracarbonitrile (6): Compound 15 (40 mg, 0.096 mmol) was allowed to react
with TCNE (24 mg, 0.192 mmol) in 1,1,2,2-tetrachloroethane
(10 mL) at 100 8C for 6 h. The crude material was purified by
column chromatography (SiO2, CH2Cl2) to give 6 as a purple solid
(42 mg, 80 %); m.p. 223226 8C; 1H NMR (300 MHz, CDCl3): d = 1.49
(t, J = 7.2 Hz, 6 H), 4.40 (q, J = 7.2 Hz, 4 H), 7.307.36 (m, 2 H), 7.46
7.59 (m, 6 H), 8.03 (dd, J = 2.1, 8.7 Hz, 2 H), 8.11 (d, J = 7.8 Hz, 2 H),
8.64 ppm (d, J = 1.8 Hz, 2 H); 13C NMR (125 MHz, CDCl3): d = 14.0,
38.3, 80.9, 109.6, 109.9, 112.6, 113.9, 121.4, 121.4, 122.6, 122.7,
Asian J. Org. Chem. 2016, 5, 246 256
www.AsianJOC.org
254
Full Paper
127.8, 131.6, 140.6, 140.9, 142.4, 143.5, 150.0, 164.2 ppm; UV/vis/
NIR (CH2Cl2): lmax (relative intensity) = 289 (1.00), 331 (0.63), 345 (sh,
0.57), 389 (0.46), 491 nm (0.85); MS (MALDI-TOF): m/z: 565.18
[M+
+H] + ; HRMS (FAB): m/z: calcd for C38H24N6 : 564.2062 [M] + ;
found:
564.2062.
Elemental
analysis
calcd
(%)
for
C38H24N60.05 CHCl3 : C 80.09, H 4.25, N 14.73; found: C 80.37, H
4.43, N 14.35.
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science
and Technology of Japan (No. 24550040, 15K05416). This work
was performed under the Cooperative Research Program of
Network Joint Research Center for Materials and Devices
(Kyushu University: no. 2015474). We thank Prof. Takayuki
Miyazaki (Gunma University) for generous permission to use
the UV/vis/NIR spectrometer. Quantum chemical calculations
were performed in the Research Center for Computational Science, Japan.
[7]
[8]
[9]
[10]
www.AsianJOC.org
[11]
[12]
[13]
[14]
[15]
[16]
255
Angew. Chem. Int. Ed. 2007, 46, 6357; Angew. Chem. 2007, 119, 6473;
e) T. Shoji, S. Ito, K. Toyota, M. Yasunami, N. Morita, Chem. Eur. J. 2008,
14, 8398; f) T. Shoji, J. Higashi, S. Ito, T. Okujima, M. Yasunami, N. Morita,
Chem. Eur. J. 2011, 17, 5116; g) T. M. Pappenfus, D. K. Schneiderman, J.
Casado, J. T. L. Navarrete, C. R. Delgado, G. Zotti, B. Vercelli, M. D. Lovander, L. M. Hinkle, J. N. Bohnsack, K. R. Mann, Chem. Mater. 2011, 23,
823; h) A. Lelige, P. Blanchard, T. Rousseau, J. Roncali, Org. Lett. 2011,
13, 3098; i) S. Niu, G. Ulrich, P. Retailleau, R. Ziessel, Org. Lett. 2011, 13,
4996; j) R. Garca, M. . Herranz, M. R. Torres, P.-A. Bouit, J. L. Delgado, J.
Calbo, P. M. Viruela, E. Ort, N. Martn, J. Org. Chem. 2012, 77, 10707;
k) Y.-L. Wu, M. C. Stuparu, C. Boudon, J.-P. Gisselbrecht, W. B. Schweizer,
K. K. Baldridge, J. S. Siegel, F. Diederich, J. Org. Chem. 2012, 77, 11014;
l) T. Michinobu, N. Satoh, J. Cai, Y. Li, L. Han, J. Mater. Chem. C 2014, 2,
3367.
Donoracceptor-type aromatic polymers were also synthesized: a) T.
Michinobu, J. Am. Chem. Soc. 2008, 130, 14074; see also a review: b) T.
Michinobu, Chem. Soc. Rev. 2011, 40, 2306.
For a review on nonplanar push pull chromophores, see: S.-i. Kato, F.
Diederich, Chem. Commun. 2010, 46, 1994.
Thermal [2+
+2] cycloaddition of TCNE with electron-rich ruthenium
acetylide complexes, followed by ring opening of the initially formed
cyclobutenes to form organometallic TCBD derivatives, was first reported by Bruce and co-workers: M. I. Bruce, J. R. Rodgers, M. R. Snow, A. G.
Swincer, J. Chem. Soc. Chem. Commun. 1981, 271.
For reviews, see: a) J. V. Grazulevicius, P. Strohriegl, J. Pielichowski, K.
Pielichowski, Prog. Polym. Sci. 2003, 28, 1297; b) J.-F. Morin, M. Leclerc,
D. Ads, A. Siove, Macromol. Rapid Commun. 2005, 26, 761; c) N. Blouin,
M. Leclerc, Acc. Chem. Res. 2008, 41, 1110; d) P.-L. T. Boudreault, J.-F.
Morin, M. Leclerc in Design and Synthesis of Conjugated Polymers (Eds.:
M. Leclerc, J.-F. Morin), Wiley-VCH, Weinheim, 2010, pp. 205.
a) S.-i. Kato, S. Shimizu, H. Taguchi, A. Kobayashi, S. Tobita, Y. Nakamura,
J. Org. Chem. 2012, 77, 3222; b) S.-i. Kato, H. Noguchi, A. Kobayashi, T.
Yoshihara, S. Tobita, Y. Nakamura, J. Org. Chem. 2012, 77, 9120; c) S.-i.
Kato, S. Shimizu, A. Kobayashi, T. Yoshihara, S. Tobita, Y. Nakamura, J.
Org. Chem. 2014, 79, 618; d) S.-i. Kato, Y. Yamada, H. Hiyoshi, K. Umezu,
Y. Nakamura, J. Org. Chem. 2015, 80, 9076.
For photorefractive materials, see: a) Y. Zhang, T. Wada, L. Wang, H.
Sasabe, Chem. Mater. 1997, 9, 2798; see also a review: b) Y. Zhang, T.
Wada, H. Sasabe, J. Mater. Chem. 1998, 8, 809.
For selected examples of NLO materials, see: a) J. L. Daz, A. Dobarro, B.
Villacampa, D. Velasco, Chem. Mater. 2001, 13, 2528; b) S. Lee, K. R. J.
Thomas, S. Thayumanavan, C. J. Bardeen, J. Phys. Chem. A 2005, 109,
9767; c) E. De Meulenaere, W.-Q. Chen, S. Van Cleuvenbergen, M.-L.
Zheng, S. Psilodimitrakopoulos, R. Paesen, J.-M. Taymans, M. Ameloot, J.
Vanderleyden, P. Loza-Alvarez, X.-M. Duan, K. Clays, Chem. Sci. 2012, 3,
984.
For selected examples of fluorophores, see: a) X. Sun, Y. Liu, X. Xu, C.
Yang, G. Yu, S. Chen, Z. Zhao, W. Qiu, Y. Li, D. Zhu, J. Phys. Chem. B
2005, 109, 10786; b) C.-H. Zhao, A. Wakamiya, Y. Inukai, S. Yamaguchi, J.
Am. Chem. Soc. 2006, 128, 15934; c) A. P. Kulkarni, X. Kong, S. A. Jenekhe, Adv. Funct. Mater. 2006, 16, 1057; d) R. M. Adhikari, D. C. Neckers,
B. K. Shah, J. Org. Chem. 2009, 74, 3341; e) P. Kotchapradist, N. Prachumrak, R. Tarsang, S. Jungsuttiwong, T. Keawin, T. Sudyoadsuk, V. Promarak,
J. Mater. Chem. C 2013, 1, 4916.
For selected examples of dye-sensitized solar cells, see: a) N. Koumura,
Z.-S. Wang, S. Mori, M. Miyashita, E. Suzuki, K. Hara, J. Am. Chem. Soc.
2006, 128, 14256; b) Z.-S. Wang, N. Koumura, Y. Cui, M. Takahashi, H. Sekiguchi, A. Mori, T. Kubo, A. Furube, K. Hara, Chem. Mater. 2008, 20,
3993; c) N. Koumura, Z.-S. Wang, M. Miyashita, Y. Uemura, H. Sekiguchi,
Y. Cui, A. Mori, S. Mori, K. Hara, J. Mater. Chem. 2009, 19, 4829; d) Y.
Ooyama, Y. Shimada, S. Inoue, T. Nagano, Y. Fujikawa, K. Komaguchi, I.
Imae, Y. Harima, New J. Chem. 2011, 35, 111; e) W. Lee, N. Cho, J. Kwon,
J. Ko, J.-I. Hong, Chem. Asian J. 2012, 7, 343; f) C. Chen, J.-Y. Liao, Z. Chi,
B. Xu, X. Zhang, D.-B. Kuang, Y. Zhang, S. Liu, J. Xu, J. Mater. Chem.
2012, 22, 8994; g) P. Thongkasee, A. Thangthong, N. Janthasing, T. Sudyoadsuk, S. Namuangruk, T. Keawin, S. Jungsuttiwong, V. Promarak,
ACS Appl. Mater. Interfaces 2014, 6, 8212; see also a review: h) N. Koumura, K. Hara, Heterocycles 2013, 87, 275.
T. Michinobu, H. Fujita, Materials 2010, 3, 4773.
2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Full Paper
[17] Increasing the number of the electron-donating carbazole units from
one in 1012 to two in 1315, is considered to be electronically favorable for the reactions with TCNE.
[18] Compounds 16 and 18 should be electronically less favorable for the
cycloaddition reaction with TCNE than 13 and 15, respectively, reflecting the more electron-withdrawing butadiynylene unit than the ethynylene unit: J.-P. Gisselbrecht, N. N. P. Moonen, C. Boudon, M. B. Nielsen, F.
Diederich, M. Gross, Eur. J. Org. Chem. 2004, 2959.
[19] Compound 17 was not entirely consumed on the basis of a TLC analysis of the reaction mixture.
[20] Double [2+
+2] cycloaddition/retro-electrocyclization reactions between
TCNE and aniline-capped buta-1,3-diynes were reported: B. Breiten, Y.-L.
Wu, P. Jarowski, J.-P. Gisselbrecht, C. Boudon, M. Griesser, C. Onitsch, G.
Gescheidt, W. B. Schweizer, N. Langer, C. Lennartz, F. Diederich, Chem.
Sci. 2011, 2, 88.
[21] The close proximity of the Et groups to the ethynylene moiety in 13 in
the solid state was revealed by X-ray diffraction analysis. See Ref. [11b].
[22] Compound 4 gave broad and complex 1H NMR signals in 1,1,2,2[D2]tetrachloroethane at room temperature. Upon heating to 120 8C,
well-resolved peaks appeared and could be clearly assigned to the proposed structure (Figure S15). This indicates that the rotation of the CC
single bond connecting the carbazole moiety to the TCBD moiety is restricted at room temperature, which should be attributable to the
severe steric hindrance between the Et groups and the dicyanovinyl
moieties.
[23] Compounds 19 are nonfluorescent.
[24] Similar significant effects of the structural variations on the Epc values
compared to the Epa values were also observed in other tetracyanobutadiene-donor systems. For details, see Ref. [6c].
[25] N. N. P. Moonen, F. Diederich, Org. Biomol. Chem. 2004, 2, 2263.
[26] We note that the conformational difference of the TCBD moiety in 19
might also affect their Epc values.
[27] All calculations were performed using Gaussian 09, Revision D.01, M. J.
Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R.
Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G.
Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven,
J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E.
www.AsianJOC.org
[28]
[29]
[30]
[31]
[32]
Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi,
M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V.
Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,
A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski,
D. J. Fox, Gaussian, Inc., Wallingford CT, 2013.
We note that the optimized structures are strongly affected by the initial structures in general; we did not perform the conformation search
for 19. We note that 2,3-diarylated buta-1,3-dienes often adopt an scis conformation with a torsion angle of approximately 65 8; see
refs. [6l] and [29]. Based on this finding, the conformations of 49 are
considered to be s-cis conformation in the TCBD unit, although the optimized structures of 49 with an s-trans conformation can be also obtained. Judging from the reported X-ray crystal structures of 2-arylated
buta-1,3-dienes, such as TCBD-N,N-dimethylaniline conjugates, which
adopt an s-trans conformation, 2 and 3 are considered to have an strans conformation in the TCBD unit; see Ref. [6b]. However, the conformation of 1 should be s-cis-type. 1 cannot adopt an s-trans conformation due to the significant steric clash between the Et group and the dicyanovinyl moieties. The optimized structures of 19 are shown in Figure S5.
a) C. A. van Walree, B. C. van der Wiel, L. W. Jenneskens, M. Lutz, A. L.
Spek, R. W. A. Havenith, J. H. van Lenthe, Eur. J. Org. Chem. 2007, 4746;
b) P. A. Limacher, H. P. Luethi, J. Phys. Chem. A 2008, 112, 2913.
a) J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865;
b) J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1997, 78, 1396;
c) C. Adamo, V. Barone, J. Chem. Phys. 1999, 110, 6158.
J. S. Binkley, J. A. Pople, W. J. Hehre, J. Am. Chem. Soc. 1980, 102, 939.
a) G. A. Petersson, M. A. Al-Laham, J. Chem. Phys. 1991, 94, 6081; b) G. A.
Petersson, A. Bennett, T. G. Tensfeldt, M. A. Al-Laham, W. A. Shirley, J.
Mangzaris, J. Chem. Phys. 1988, 89, 2193.
256