A comprehensive study of tetracyanobutadiene push-pull chromophores derived from γ-pyranylidene

Tetrahedron chem Pub Date : 2023-03-01 DOI:10.1016/j.tchem.2023.100036

Clotilde Philippe , Johann Melan , Alberto Barsella , Thomas Vives , Yann R. Leroux , Françoise Robin-Le Guen , Loïc Lemiègre , Denis Jacquemin , Sébastien Gauthier , Yann Trolez

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引用次数: 3

Abstract

A new class of push-pull 1,1,4,4-tetracyanobutadienes (TCBDs) chromophores bearing a γ-pyranylidene as a pro-aromatic donor group have been developed, characterized and studied for their electrochemical, photophysical and second-order nonlinear optical (NLO) properties. [2 + 2] Cycloaddition-retroelectrocyclizations (CA-RE) with tetracyanoethylene (TCNE) allowed the formation of new TCBDs by taking advantage of the electron-donating ability of γ-pyranylidene functional groups. The limits of the reaction between TCNE and the corresponding alkynes have been investigated, both in terms of reactivity and solubility. Electrochemical studies of pyranylidene-TCBD 1a-1j revealed two reversible reduction waves typical of TCBDs, and two oxidation waves originating from the γ-pyranylidene moiety. More complex electrochemical signals have been recorded when studying chromophores bearing multiple TCBD and/or γ-pyranylidene units. All pyranylidene-TCBDs showed panchromatic absorption properties, extending to the NIR in some cases. Changes made around the electron-withdrawing TCBD units significantly affected the ICT performance of the push-pull chromophores. Computational studies have been performed on this series of compounds to rationalize the origin of their optical properties. TD-DFT calculations confirmed that the synthesized pyranylidene-TCBDs are potential NLOphores. The second-order NLO properties of all chromophores were determined by the Electric Field-Induced Second Harmonic generation (EFISH) technique, and all systems exhibited valuable NLO properties with large μβ_EFISH values for purely organic compounds, up to 5700 10⁻⁴⁸ esu.

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γ-吡喃亚基四氰基丁二烯推挽发色团的综合研究

以γ-吡喃二烯为亲芳给基的一类新型推拉式1,1,4,4-四氰丁二烯(TCBDs)发色团，对其电化学、光物理和二阶非线性光学(NLO)性质进行了表征和研究。[2 + 2]与四氰乙烯(TCNE)的环加成-反电环化反应(CA-RE)利用了γ-芘官能团的给电子能力，形成了新的TCBDs。从反应活性和溶解度两方面考察了TCNE与相应炔之间反应的极限。对pyranylide - tcbd 1a-1j的电化学研究发现，TCBDs具有两种典型的可逆还原波和两种源自γ-pyranylide部分的氧化波。当研究含有多个TCBD和/或γ-pyranylidene单元的发色团时，记录了更复杂的电化学信号。所有的pypyylide - tcbds都表现出全色吸收特性，在某些情况下延伸到近红外光谱。吸电子TCBD单元周围的变化显著影响了推拉发色团的ICT性能。对这一系列化合物进行了计算研究，以使其光学性质的起源合理化。TD-DFT计算证实了所合成的pypyylide - tcbds是潜在的nlophode。用电场诱导二次谐波产生(EFISH)技术测定了所有发色团的二阶NLO性质，结果表明，所有体系都具有良好的NLO性质，纯有机化合物的μβEFISH值高达5700 10−48 esu。

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