Job/Unit: O20161
/KAP1
Date: 04-04-12 16:25:11
Pages: 11
Tuning Wavefunction Mixing in Push–Pull Molecules
1
CCDC-823205 (for 1), -823206 (for 2) and -823207 (for 3) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
7.72 (m, 2 H), 7.86 (m, 1 H), 8.66 (s, 1 H), 8.82 (m, 1 H) ppm. H
NMR (400 MHz, [D6]DMSO, 2.62 ppm vs. CDCl3): δ = 1.80 (m,
2 H), 1.85 (m, 4 H), 3.90 (m, 4 H), 7.23 (d, 3J = 5.2 Hz, 1 H), 7.92–
3
3
7.94 (m, 2 H), 7.97 (d, J = 5.2 Hz, 1 H), 8.08 (d, J = 7.3 Hz, 1
H), 8.44 (br. s, 1 H), 8.69 (d, 3J = 7.9 Hz, 1 H) ppm. C21H17N3O2S2
(407.50): calcd. C 61.89, H 4.20, N 10.31, S 15.74; found C 61.57,
H 4.22, N 10.09, S 15.66.
Computational Details: DFT and time dependent DFT (TDDFT)
calculations were carried out by using the Gaussian 09 package.[28]
The M05-2X/6-31+G(d,p) level of computation was used. The
M05-2X functional was chosen as it holds a high percentage of
Hartree–Fock exchange and it is known to give more accurate re-
sults than standard hybrid functionals for systems experiencing
long-range charge transfer.[29] Effects due to polarization of solvent
were included by using the polarizable continuum model (PCM) as
implemented in the Gaussian software.[30] Second-order Møller–
Plesset perturbation theory (MP2) and approximate coupled cluster
theory computations including single and double excitations (CC2)
were carried out by using the Turbomole suite of programs.[31] The
def2-TZVPP basis set was used in MP2 computations whereas the
smaller SV(P) basis set was employed for the more demanding CC2
computations. The frozen core and the resolution of identity (RI)
approximations were used in the MP2 and CC2 computations.
Wiberg bond orders were computed by using the natural bond or-
bital (NBO) method[32] through the NBO3 facility implemented in
the Gaussian software. For chromophores 1 and 2 the piperidinyl
substituent was replaced by a dimethylamino group in all the com-
putations.
1,3-Bis(dicyanomethylidene)-2-(4-dimethylaminobenzylidene)indane
(3): M.p. 245 °C (ref.[12a] 246–248 °C). IR: ν = 3078 (w), 2925 (w),
˜
2859 (w), 2810 (w), 2215 (m), 2202 (m), 1607 (m), 1506 (s), 1438
(m), 1374 (m), 1196 (m), 1165 (m) cm–1. 1H NMR (400 MHz,
CDCl3, 7.26 ppm): δ = 3.21 (s, 6 H), 6.74 (d, 3J = 9.2 Hz, 2 H),
7.56 (d, J = 9.2 Hz, 2 H), 7.73 (dd, J = 8.9, J = 3.1 Hz, 2 H),
8.58 (dd, J = 8.9, J = 3.1 Hz, 2 H), 8.70 (s, 1 H) ppm. H NMR
(400 MHz, [D6]DMSO, 2.62 ppm vs. CDCl3): δ = 3.34 (s, 6 H),
7.03 (d, J = 9.2 Hz, 1 H), 7.76 (d, J = 9.0 Hz, 2 H), 7.97 (m, 2
H), 8.51 (m, 2 H), 8.57 (s, 1 H) ppm. C24H15N5 (373.42): calcd. C
77.20, H 4.05, N 18.76; found C 76.98, H 3.99, N 18.59.
3
3
4
3
4
1
3
3
Supporting Information (see footnote on the first page of this arti-
cle): 1H NMR spectra for all final products, Table of calculated
transition wavelengths and oscillator strengths for 1–3 and Tables
of Wiberg bond orders for 1–3.
Acknowledgments
Synthesis: Chromophores 1–3 were prepared by the condensation
of 5-piperidinylthiophene-2-carbaldehyde[33] or commercial 4-(di-
methylamino)benzaldehyde with 1,3-bis(dicyanomethylidene)-
indane or 3-dicyanomethylidene-1-thiaindane-1,1-dione[12a] accord-
ing to the procedure described in ref.[34] Equimolar amounts of the
aldehyde and substituted indane were suspended in acetic anhy-
dride. The mixture was heated at reflux for 3 min and then cooled
to room temperature. The solid obtained was filtered, washed with
acetic anhydride and recrystallized from hot acetic anhydride.
The Ministero Italiano dell’Università e della Ricerca Scientifica e
Tecnologica (MIUR) and the University of Salerno and University
of Naples “Federico II” are acknowledged for financial support
within the PRIN 2008 and PRIN 2009 projects. Thanks are also
due to the CIMCF of University of Naples “Federico II” for the
X-ray facility.
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2-[1,3-Bis(dicyanomethylideneindan-2-ylidene)methyl]-5-(piperidin-
1-yl)thiophene (1): M.p. 274 °C. IR: ν = 3094 (w), 2945 (w), 2859
˜
(w), 2197 (s), 1567 (m), 1525 (m), 1470 (s), 1454 (m), 1250 (m),
1095 (m) cm–1. 1H NMR (400 MHz, CDCl3, 7.26 ppm): δ = 1.87
3
3
(m, 6 H), 3.74 (m, 4 H), 6.50 (d, J = 5.3 Hz, 1 H), 7.51 (dd, J =
4
3
3
9.4, J = 3.4 Hz, 2 H), 7.79 (d, J = 5.3 Hz, 1 H), 8.43 (dd, J =
9.2, 4J = 3.4 Hz, 2 H), 8.62 (s, 1 H) ppm. 13C NMR and HSQC
(400 MHz, CDCl3, 77.00 ppm): δ = 176.4 (C-13), 158.8 (C-7, C-
14), 153.3 (C-11), 138.1 (C-5, C-6), 137.7 (C-9), 132.1 (C-2, C-3),
130.6 (C-10), 124.0 (C-1, C-4), 116.6 (2 CN), 116.5 (CN), 116.1
(CN), 113.6 (C-12), 112.9 (C-8), 61.5 [C(CN)2], 53.9 (C-21, C-25),
25.7 (C-22, C-24), 23.1 (C-23) ppm. 1H NMR (400 MHz, [D6]-
DMSO, 2.62 ppm vs. CDCl3): δ = 1.80 (m, 2 H), 1.89 (m, 4 H),
3
4.00 (br. s, 2 H), 4.17 (br. s, 2 H), 7.68 (d, J = 6.0 Hz, 1 H), 7.69
(m, 2 H), 8.21 (s, 1 H), 8.29 (m, 2 H), 8.35 (d, 3J = 6.0 Hz, 1
H) ppm. 13C NMR and HSQC (400 MHz, [D6]DMSO, 40.76 ppm
vs. CDCl3): δ = 180.1 (C-13), 156.5 (C-7, C-14), 153.2 (C-11), 140.4
(C-10), 138.3 (C-5, C-6), 135.2 (C-9), 132.5 (C-2, C-3), 124.4 (C-
12), 123.7 (C-1, C-4), 119.0 (2 CN), 118.3 (2 CN), 110.8 (C-8),
56.2 [C(CN)2], 55.1–54.7 (C-21, C-25), 27.0 (C-22, C-24), 23.6 (C-
23) ppm. C25H17N5S (419.50): calcd. C 71.58, H 4.08, N 16.69, S
7.65; found C 71.23, H 4.05, N 16.64, S 7.71.
2-(1,1-Dioxo-3-dicyanomethylidene-1-thiaindan-2-ylidenemethyl)-5-
(piperidin-1-yl)thiophene (2): M.p. 280 °C (ref.[13a] 276–278 °C). IR:
ν = 3098 (w), 2962 (w), 2924 (w), 2853 (w), 2205 (s), 1527 (s), 1482
˜
(s), 1463 (s), 1434 (s), 1407 (s), 1357 (s), 1250 (s), 1203 (m), 1177 (s),
1152 (s), 1016 (m) cm–1. 1H NMR (400 MHz, CDCl3, 7.26 ppm): δ
= 1.80 (m, 6 H), 3.67 (m, 4 H), 6.40 (br. s, 1 H), 7.61 (br. s, 1 H),
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