Abstract:The crystal and molecular structures of five 2,5-bis(aryl-2-vinyl)-l,4-dimethoxybenzene derivatives la-le were determined by X-ray diffraction with respect to topochemical aspects. We found three types of packing arrangements: (1) a-type packing with 7 A. stacking axes, (2) /3-type packing with 4 A, stacking axes and (3) a third intermediate packing type. The intermolecular distances between the vinylic double bonds of all derivatives exceed the limits of 4 A. in the crystals. Therefore photochemical [2 +2]cyc… Show more
“…A, 1.414(2) A) and single (1.386 A) C-C bonds in the thiophene ring are very similar in length, in contrast to the strongly alternating pattern found in the absence of strong donor and acceptor substitution. [50][51][52] The patterns of bond lengths in 1 are similar to those seen in the structure of other related donor-acceptor chromophores with strong p-acceptors, such as IV (Fig. 4c).…”
Section: Crystal Structuresupporting
confidence: 73%
“…0.1 A are found in fully quinoidal structures 49 ); the vinylene portion of the bridge shows a bond-length alternation (BLA) between formally double and single bonds of ca. 0.079 (6) A, a little lower than the >0.1 A found for -CH]CH-groups (including those linking aryl and thienyl groups) in the absence of significant zwitterionic contributions; [50][51][52] and the formally double (1.384(2)…”
Section: Crystal Structurementioning
confidence: 74%
“…0.079 (6) A, a little lower than the >0.1 A found for -CH]CH-groups (including those linking aryl and thienyl groups) in the absence of significant zwitterionic contributions; [50][51][52] and the formally double (1.384 (2) A, 1.414(2) A) and single (1.386 A) C-C bonds in the thiophene ring are very similar in length, in contrast to the strongly alternating pattern found in the absence of strong donor and acceptor substitution. [50][51][52] The patterns of bond lengths in 1 are similar to those seen in the structure of other related donor-acceptor chromophores with strong p-acceptors, such as IV (Fig. 4c).…”
E-2-Tricyanovinyl-3-n-hexyl-5-[4-{bis(4-n-butylphenyl)amino}-2-methoxystyryl]-thiophene, 1, has previously been used to demonstrate applications relying on frequency tripling of 1.55 mm light. Here we report the synthesis and chemical characterisation of 1, along with quantum-chemical calculations and additional experimental investigations of its third-order nonlinear properties that give more insight into its frequency tripling properties. Although 1 can be processed into amorphous films, crystals can also be grown by slow evaporation of solutions; the crystal structure determined by X-ray diffraction shows evidence of significant contributions from zwitterionic resonance forms to the ground-state structure, and reveals centrosymmetric packing exhibiting p-p and C-H/N^C interactions. Both solutions and films of 1 exhibit near-infrared two-photon absorption into the low-lying one-photon-allowed state with a peak two-photon cross-section of ca. 290 GM (measured using the white-light continuum method with a pump wavelength of 1800 nm) at a transition energy equivalent to degenerate two-photon absorption at ca. 1360 nm; two related chromophores are also found to show comparable near-IR two-photon crosssections. Closed-aperture Z-scan measurements and quantum-chemical calculations indicate that the nonlinear refractive index and third-harmonic generation properties of 1 are strongly dependent on frequency in the telecommunications range, due the aforementioned two-photon resonance.
“…A, 1.414(2) A) and single (1.386 A) C-C bonds in the thiophene ring are very similar in length, in contrast to the strongly alternating pattern found in the absence of strong donor and acceptor substitution. [50][51][52] The patterns of bond lengths in 1 are similar to those seen in the structure of other related donor-acceptor chromophores with strong p-acceptors, such as IV (Fig. 4c).…”
Section: Crystal Structuresupporting
confidence: 73%
“…0.1 A are found in fully quinoidal structures 49 ); the vinylene portion of the bridge shows a bond-length alternation (BLA) between formally double and single bonds of ca. 0.079 (6) A, a little lower than the >0.1 A found for -CH]CH-groups (including those linking aryl and thienyl groups) in the absence of significant zwitterionic contributions; [50][51][52] and the formally double (1.384(2)…”
Section: Crystal Structurementioning
confidence: 74%
“…0.079 (6) A, a little lower than the >0.1 A found for -CH]CH-groups (including those linking aryl and thienyl groups) in the absence of significant zwitterionic contributions; [50][51][52] and the formally double (1.384 (2) A, 1.414(2) A) and single (1.386 A) C-C bonds in the thiophene ring are very similar in length, in contrast to the strongly alternating pattern found in the absence of strong donor and acceptor substitution. [50][51][52] The patterns of bond lengths in 1 are similar to those seen in the structure of other related donor-acceptor chromophores with strong p-acceptors, such as IV (Fig. 4c).…”
E-2-Tricyanovinyl-3-n-hexyl-5-[4-{bis(4-n-butylphenyl)amino}-2-methoxystyryl]-thiophene, 1, has previously been used to demonstrate applications relying on frequency tripling of 1.55 mm light. Here we report the synthesis and chemical characterisation of 1, along with quantum-chemical calculations and additional experimental investigations of its third-order nonlinear properties that give more insight into its frequency tripling properties. Although 1 can be processed into amorphous films, crystals can also be grown by slow evaporation of solutions; the crystal structure determined by X-ray diffraction shows evidence of significant contributions from zwitterionic resonance forms to the ground-state structure, and reveals centrosymmetric packing exhibiting p-p and C-H/N^C interactions. Both solutions and films of 1 exhibit near-infrared two-photon absorption into the low-lying one-photon-allowed state with a peak two-photon cross-section of ca. 290 GM (measured using the white-light continuum method with a pump wavelength of 1800 nm) at a transition energy equivalent to degenerate two-photon absorption at ca. 1360 nm; two related chromophores are also found to show comparable near-IR two-photon crosssections. Closed-aperture Z-scan measurements and quantum-chemical calculations indicate that the nonlinear refractive index and third-harmonic generation properties of 1 are strongly dependent on frequency in the telecommunications range, due the aforementioned two-photon resonance.
“…The “ortho” methoxy (O(1)) does not interact strongly with neighboring molecules but points the lone pairs on O toward the olefin on the same molecule (O(1)···H(9)C, 2.46 Å). The intermolecular O···H interaction in 4 is not present in the lattice of 1,4-distyryl 2,5-dimethoxybenzene ( HESMUN ) or any of the chlorinated derivatives of 1,4-distryl-2,5-dimethoxybenzene. , 6 A layer of the structure of 1,4-bis(2,5-dimethoxystyryl)benzene ( 4 ) roughly in the bc plane. Annotated close contacts are of a distance of 2.56(4) Å.…”
A range of 1,4-distyrylbenzene derivatives were synthesized and characterized by single-crystal X-ray diffraction to investigate the effects of substitution on the resulting crystal
lattices. Molecules in this report include 1,4-bis(2,2-diphenylethenyl)benzene (1), 1,4-bis(1-cyano-2,2-diphenylethenyl)benzene (2), 1,4-bis(1-cyano-2-phenylethenyl)benzene (3) 1,4-bis(2,5-dimethoxystyryl)benzene (4), 1,4-bis(3,5-dimethoxystyryl)benzene (5), 2,5-difluoro-1-(pentafluorostyryl)-4-(4-tert-butylstyryl)benzene (6), and 1,4-bis(4-nitrostyryl)benzene·2DMF
(7). The lattice of each is described and contrasted in light of distyrylbenzene derivatives
previously reported. The results of thermal analysis by differential scanning calorimetry
are included to further examine the effect of substitution on crystal properties.
“…The solid-state structures and electronic properties of one particular class of these oligomeric organic semiconductors, viz. distyrylbenzenes, oligomeric derivatives of PPV [poly(pphenylene vinylene)], have already been extensively studied and the influence of substituents on the properties of the carbon backbone have been investigated (Baeke et al, 2007;Vande Velde et al, 2004;Vande Velde, Baeke et al 2005;Vande Velde, De Borger et al, 2005;Vande Velde et al, 2006;Irngartinger et al, 1994;Hakansson et al, 1992;Bartholomew et al, 2000a,b;Coates et al, 1998;Nohra et al, 2006;Renak et al, 1999;Sancho-Garcia et al, 2005;Zeller et al, 2005). However, keeping in mind the tunability of these materials, it is equally interesting to determine the effects of the replacement of the ethenylic -CH CH-link by other spacers such as -CH N-…”
Three substituted triphenyl(phenylimino)phosphoranes, namely (4-cyanophenylimino)triphenylphosphorane, C(25)H(19)N(2)P, (I), (4-nitrophenylimino)triphenylphosphorane, C(24)H(19)N(2)O(2)P, (II), and (3-nitrophenylimino)triphenylphosphorane, C(24)H(19)N(2)O(2)P, (III), were synthesized as precursors for the preparation of substituted diphenylcarbodiimides. All three compounds display a supramolecular arrangement in which the substituted benzene rings are organized in an antiparallel fashion. The nitro group on the ring participates in C-H...O and O...pi interactions, forming intermolecular dimers. Compound (III) shows disorder which involves the rotation of one of the phenyl rings of the triphenylphosphine group.
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