Synthesis, structure, linear and nonlinear properties of tricyanofuran–terminated merocyanine dyes

Tillotson, John P.; Bogdanov, Georgii; Jucov, Evgheni V.; Khrustalev, Victor N.; Rigin, Sergei; Hales, Joel M.; Perry, Joseph W.; Timofeeva, Tatiana V.

doi:10.1016/j.molstruc.2019.04.001

Cited by 14 publications

(14 citation statements)

References 23 publications

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“…Comparing DTB to TMI, it is observed that DTB possesses a more planar and rigid structure, consistent with previously reported results for studies of push-pull chromophores with different -bridge lengths (Tillotson et al, 2019). The dihedral angles between the three fragments are smaller, 3.21 14between the donor group and the bridge and 1.04 14between the bridge and the acceptor group.…”

Section: Structural Commentarysupporting

confidence: 89%

Synthesis and structure of push–pull merocyanines based on barbituric and thiobarbituric acid

Bogdanov¹,

Tillotson²,

Bustos³

et al. 2019

Acta Cryst E

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Two compounds, 1,3-diethyl-5-{(2E,4E)-6-[(E)-1,3,3-trimethylindolin-2-ylidene]hexa-2,4-dien-1-ylidene}pyrimidine-2,4,6(1H,3H,5H)-trione or TMI, C25H29N3O3, and 1,3-diethyl-2-sulfanylidene-5-[2-(1,3,3-trimethylindolin-2-ylidene)ethylidene]dihydropyrimidine-4,6(1H,5H)-dione or DTB, C21H25N3O2S, have been crystallized and studied. These compounds contain the same indole derivative donor group and differ in their acceptor groups (in TMI it contains oxygen in the para position, and in DTB sulfur) and the length of the π-bridge. In both materials, molecules are packed in a herringbone manner with differences in the twist and fold angles. In both structures, the molecules are connected by weak C—H...O and/or C—H...S bonds.

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Section: Structural Commentarysupporting

confidence: 89%

Synthesis and structure of push–pull merocyanines based on barbituric and thiobarbituric acid

Bogdanov¹,

Tillotson²,

Bustos³

et al. 2019

Acta Cryst E

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“…Both molecules have acceptor--bridge-donor structures. It was found, as in our previous studies (Tillotson et al, 2019), that with an increase of the length of the -conjugated bridge the molecule becomes less planar, and the angles between the different planar fragments (acceptor-bridge, bridge-donor) become larger (Table 1).…”

Section: Structural Commentarysupporting

confidence: 81%

“…For the synthesis of the title compounds, two aldehydes were used: 4-(dimethylamino)benzaldehyde (A1; purchased from Aldrich) and 4-(dimethylamino)cinnamaldehyde (A2), which was synthesized as described previously (Tillotson, et al, 2019). 2,3-Indanedione was purchased from Aldrich and used without further purification.…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

Crystal structures, syntheses, and spectroscopic and electrochemical measurements of two push–pull chromophores: 2-[4-(dimethylamino)benzylidene]-1H-indene-1,3(2H)-dione and (E)-2-{3-[4-(dimethylamino)phenyl]allylidene}-1H-indene-1,3(2H)-dione

2019

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“…There has been considerable interest in the study of intermolecular interactions between near-infrared (NIR) push–pull chromophores containing a strong electron acceptor of 2-dicyanomethylidene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF), which influences most properties of the derived organic second-order nonlinear optical (NLO) materials in thin films and devices. − From crystal structural analyses, various antiparallel molecular packing structures have been found for essentially all the reported TCF-based dipolar polyenes and merocyanines. ,,− In particular, the role of non-classic C–H···N(cyano) hydrogen bonding interactions in affecting the π–π stacking of TCF-based chromophores is being increasingly recognized, which cooperatively stabilize the centrosymmetric packing of dipolar molecules (Figure ). Due to the strong intramolecular charge transfer (ICT) of chromophores, the negative electrostatic potential (ESP) of three cyano groups in a TCF acceptor can attract to the protons of nonpolar C–H bonds to form hydrogen bonding.…”

Section: Introductionmentioning

confidence: 99%

Critical Role of Non-classical Intermolecular Hydrogen Bonding in Affecting the π–π Stacking and Nonlinear Optical Properties of Tricyanofuran-Based Push–Pull Heptamethines

Zhang

Zou

et al. 2021

Chem. Mater.

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Currently, there is immense interest in the chemistry of push–pull heptamethines containing a strong acceptor of 2-dicyanomethylidene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF). This class of compounds is important as second-order nonlinear optical (NLO) chromophores for electro-optic (EO) applications. The crystal packing of TCF-based NLO chromophores is generally dominated by intermolecular π–π stacking and non-classical C–H···N(cyano) hydrogen bonding interactions, considerably limiting the bulk NLO properties of chromophores in solid films. In this paper, we report a series of TCF-based push–pull heptamethines bearing the substituent of 4,5-diphenyl-oxazol-2-ylsulfanyl group at the central position of the π-conjugated bridge. Crystallographic studies show a very uncommon crystal packing mode of one-dimensional chain structure with vanished C–H···N(cyano) contacts and negligible π–π stacking. Such reduced intermolecular interactions and fine-tuned bond length alternation lead to NLO performance breakthrough of these chromophores in poled polymeric films, including much better EO coefficients up to 465% in improvement, higher polar order, and larger molecular hyperpolarizabilities (up to 4,135 × 10–30 esu at 1304 nm), over the results from the simple chloro-substituted heptamethines. Our study indicates that the interplay of steric effect, non-classical C–H···N hydrogen bonding, and intermolecular π–π stacking is critically important in optimizing the supramolecular assembly and NLO properties of TCF-based heptamethines for photonic applications.

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Synthesis, structure, linear and nonlinear properties of tricyanofuran–terminated merocyanine dyes

Cited by 14 publications

References 23 publications

Synthesis and structure of push–pull merocyanines based on barbituric and thiobarbituric acid

Synthesis and structure of push–pull merocyanines based on barbituric and thiobarbituric acid

Crystal structures, syntheses, and spectroscopic and electrochemical measurements of two push–pull chromophores: 2-[4-(dimethylamino)benzylidene]-1H-indene-1,3(2H)-dione and (E)-2-{3-[4-(dimethylamino)phenyl]allylidene}-1H-indene-1,3(2H)-dione

Critical Role of Non-classical Intermolecular Hydrogen Bonding in Affecting the π–π Stacking and Nonlinear Optical Properties of Tricyanofuran-Based Push–Pull Heptamethines

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