<br>二氰基乙烯基取代的三苯胺和三氰基乙烯基取代的三苯胺：结构和计算研究,ACS Omega

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二氰基乙烯基取代的三苯胺和三氰基乙烯基取代的三苯胺：结构和计算研究
ACS Omega ( IF 3.7 ) Pub Date : 2024-02-28 , DOI: 10.1021/acsomega.3c05312
Phuong-Truc T Pham ₁ , Mamoun M Bader ₂

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我们在此报告了三种密切相关的具有三氰基乙烯基（TCV）和二氰基乙烯基（DCV）基团的三苯胺衍生物的固态结构。所描述的分子包含功能有机材料设计中常见的结构特征，特别是供体-受体分子和聚合物结构。这些结构中值得注意的共同特征是这些异常强的电子接受基团的影响，迫使带有这些基团的分子部分部分平面化，并引导分子堆积在固态，从而形成π-堆叠每个晶胞内的二聚体。堆叠在两个相邻分子上带有电子接受基团的苯基之间形成。观察到 π-π 堆叠距离范围为 3.283 至 3.671 Å。这种图案被认为有利于有机半导体中更好的电荷传输和增强的器件性能。从所有三种化合物中观察到的实验键长的缩短来看，分子内电荷转移是明显的。（氰基的）氮原子已被证明广泛参与所有三种结构中的短接触，主要是通过距离短至 2.462 Å 的 C-H·NC 相互作用。这里报道的化合物是(3,3-二氰基-2-(4-(二苯基氨基)苯基)-1λ ³ -烯丙基)酰胺或三氰基乙烯基三苯胺，Ph ₃ NTCV ( 1 )； 2-(4-(二苯氨基)亚苄基)-丙二腈或二氰基乙烯基三苯胺，Ph ₃ NDCV( 2 )； (3,3-二氰基-2-(4-(二对甲苯氨基)苯基)-1λ ³ -烯丙基)酰胺或二甲基三氰基乙烯基三苯胺，Me ₂ Ph ₃ NTCV ( 3 )。使用 DFT-B3LYP/6-31G(d,p) 的密度泛函理论计算结果表明，由于引入这些化合物1 – 3的带隙为 3.13、2.61 和 2.55 eV 的基团，LUMO 能级降低分别与三苯胺的计算值 4.65 eV 相比。这些分子的电子光谱和荧光光谱证实了这一点，化合物1、2和3的吸收λ _max分别为483、515和545 nm。

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Di- and Tricyanovinyl-Substituted Triphenylamines: Structural and Computational Studies

We report herein on the solid-state structures of three closely related triphenylamine derivatives endowed with tricyanovinyl (TCV) and dicyanovinyl (DCV) groups. The molecules described contain structural features commonly found in the design of functional organic materials, especially donor–acceptor molecular and polymeric architectures. The common feature noticeable in these structures is the impact of these exceptionally strong electron-accepting groups in forcing partial planarity of the portion of the molecule carrying these groups and directing the molecular packing in the solid state, resulting in the formation of π-stacks of dimers within the unit cell of each. Stacks are formed between phenyl groups bearing electron-accepting groups on two adjacent molecules. Short π–π stack distances ranging from 3.283 to 3.671 Å were observed. Such motif patterns are thought to be conducive for better charge transport in organic semiconductors and enhanced device performance. Intramolecular charge transfer is evident from the shortening of the observed experimental bond lengths in all three compounds. The nitrogen atoms (of the cyano groups) have been shown to be extensively involved in short contacts in all three structures, primarily through C–H···NC interactions with distances as short as 2.462 Å. The compounds reported here are (3,3-dicyano-2-(4-(diphenylamino)phenyl)-1λ³-allylidene)amide or tricyanovinyltriphenylamine, Ph₃NTCV (1); 2-(4-(diphenylamino)benzylidene)-malononitrile or dicyanovinyltriphenylamine, Ph₃NDCV (2); and (3,3-dicyano-2-(4-(di-p-tolylamino)phenyl)-1λ³-allylidene)amide or dimethyltricyanovinyltriphenylamine, Me₂Ph₃NTCV (3). Results of density functional theory calculations using DFT-B3LYP/6-31G(d,p) indicate the lowering of LUMO levels as a result of the introduction of these groups with band gaps of 3.13, 2.61, and 2.55 eV for compounds 1–3, respectively, compared with 4.65 eV calculated for triphenylamine. This is supported by the electronic and fluorescence spectra of these molecules with absorption λ_max of 483, 515, and 545 nm for compounds 1, 2, and 3, respectively.

更新日期：2024-02-28

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