2-(4-(1-cyano-2-(1,3,3-trimethylindolin-2-ylidene)ethylidene)cyclohexa-2,5-dienylidene)malononitrile | 475661-65-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 2-(4-(1-cyano-2-(1,3,3-trimethylindolin-2-ylidene)ethylidene)cyclohexa-2,5-dienylidene)malononitrile
• 英文别名: 2-[4-[1-Cyano-2-(1,3,3-trimethylindol-2-ylidene)ethylidene]cyclohexa-2,5-dien-1-ylidene]propanedinitrile；2-[4-[1-cyano-2-(1,3,3-trimethylindol-2-ylidene)ethylidene]cyclohexa-2,5-dien-1-ylidene]propanedinitrile
• CAS: 475661-65-5
• 化学式: C₂₃H₁₈N₄
• 分子量: 350.423
• InChiKey: NXTIXXDIDZOMSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  27
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  74.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(4-(1-cyano-2-(1,3,3-trimethylindolin-2-ylidene)ethylidene)cyclohexa-2,5-dienylidene)malononitrile 、 7,7,8,8-四氰基对苯二醌二甲烷 以 乙腈 为溶剂， 以50%的产率得到
  参考文献：
  名称：

  Charge-Transfer Complexes between Indoline–Tricyanoquinodimethane Compounds and 7,7,8,8-Tetracyanoquinodimethane

  摘要：

  由 1-烷基-3,3-二甲基-2-亚甲基吲哚啉（In，供体，n = 烷基链长度；1或6）和 7,8,8-三氰基二甲烷（=2-(4′-氰基亚甲基-2′,5′-环己二烯亚基)丙二腈，3CNQ，受体）分子组成的分子内电荷转移化合物与 7,7,8,8-四氰基二甲烷（TCNQ）形成了电荷转移复合物：(I1-3CNQ)2(TCNQ) 和 (I6-3CNQ)(TCNQ) 的电荷转移配合物。(I1-3CNQ)2(TCNQ) 包括两种不同分子构象的 I1-3CNQ 分子。(I1-3CNQ)2(TCNQ)和(I6-3CNQ)(TCNQ)分别由3CNQ--TCNQ--3CNQ三元组和3CNQ--TCNQ二元组的一维柱构建而成。除了 In-3CNQ 复合物特有的 600-900 纳米波长的分子内电荷转移带之外，这些复合物还显示出延伸到近红外区域（1000-1500 纳米波长）的分子间电荷转移带。根据分子轨道计算、键长和振动光谱对电荷转移程度的估计，这些化合物被定性为弱电荷转移固体。分子间电荷转移导致分子内电荷转移程度略有增加。

  DOI：

  10.1246/bcsj.81.1492
• 作为产物：
  描述：

  1,3,3-三甲基-2-亚甲基吲哚啉 、 7,7,8,8-四氰基对苯二醌二甲烷 以 氯苯 为溶剂， 生成 2-(4-(1-cyano-2-(1,3,3-trimethylindolin-2-ylidene)ethylidene)cyclohexa-2,5-dienylidene)malononitrile
  参考文献：
  名称：

  Crystal Structures, Degree of Charge Transfer, and Non-Linear Optical Characteristics of Intramolecular Charge-Transfer Compounds: Indoline-Substituted Tricyanoquinodimethanes

  摘要：

  取代基对由1,3,3-三甲基-2-亚甲基吲哚啉(I1)和取代的7,8,8-三氰基喹诺二甲烷(=2-(4-氰基亚甲基-2,5-环己二烯亚基)丙二腈，3CNQ-R，R=取代基基团)组成的供体-π-受体化合物的分子内电荷转移程度(δ)和光学性质的影响(I1-3CNQ-R)。在晶体结构中，I1-3CNQ-R分子以头对尾的方式堆积在吲哚啉和/或3CNQ-R基团上以消除其偶极矩，并建立了分离或混合的堆叠柱型图案。使用晶体结构中的键长比、分子轨道计算和分子内电荷转移吸收的溶剂化色移分别估计了I1-3CNQ-R分子在固体和溶液状态下的δ值，并显示出对3CNQ基团的取代基的显著和合理的依赖关系。结构分析表明，分子构象和平面性影响I1-3CNQ-R分子的δ值。分子轨道计算表明，通过调节δ可以调节分子的(超)极化率。I1-3CNQ-R表现出溶剂化色移，基态从较低极性溶剂中的中性态(δ≤0.5)变为极性溶剂中的离子态(δ≥0.5)。I1-3CNQ-R的双光子吸收性质显示出显著的取代基效应，表明δ是调节非线性光学性质的基本参数。

  DOI：

  10.1246/bcsj.81.1131

文献信息

• Structural Properties and Degree of Intramolecular Charge Transfer of an<i>N</i>-Alkyl Indoline–Tricyanoquinodimethane System
  作者：Tsuyoshi Murata、Kazukuni Nishimura、Yuichiro Enomoto、Genki Honda、Yasuhito Shimizu、Akihiro Otsuka、Gunzi Saito

  DOI：10.1246/bcsj.81.869

  日期：2008.7.15

  A series of intramolecular charge-transfer compounds comprised of 1-alkyl-3,3-dimethyl-2-methyleneindoline (In, donor, n = alkyl chain length; 1–8, 10, 14, 16, 18, 20, and 22) and 7,8,8-tricyanoquinodimethane (=2-(4′-cyanomethylene-2′,5′-cyclohexadienylidene)malononitrile (3CNQ), acceptor) moieties linked through a π-bond, In–3CNQ were prepared, and their structures are discussed. The melting points of the In–3CNQ solids decreased with increasing alkyl chain length until reaching a minimum point (95 °C) at n=18, and then began to gradually increase, indicating self-aggregation of the alkyl chains. The In–3CNQ derivatives with long alkyl chains (n≥6) produced supercooled liquids displaying conspicuous color changes after melting. Diverse molecular packing patterns were observed in the crystal structures. Most In–3CNQ derivatives formed face-to-face and/or side-by-side dimeric motifs to cancel net dipole moments. I20–3CNQ formed a two-dimensional bilayer structure by π-stacking and self-assembly of the alkyl chains. Two types of molecular conformation, which significantly affect the electronic structures, were observed to be dependent on the alkyl chain length. A parameter to evaluate the degree of intramolecular charge transfer, namely bond length ratio, was proposed; it exhibited good agreement with solvatochromic shifts and molecular orbital calculations.

  一系列分子内电荷转移化合物由 1-烷基-3,3-二甲基-2-亚甲基吲哚啉（In，供体，n = 烷基链长度；1-8、10、14、16、18、20 和 22）和 7,8,8-三氰基二甲烷（=2-(4′-氰基亚甲基-2′,5′-环己二烯亚基)丙二腈 (3CNQ)，受体）分子通过 π 键连接而成的分子内电荷转移化合物，即 In-3CNQ，并讨论了它们的结构。In-3CNQ 固体的熔点随着烷基链长度的增加而降低，直到 n=18 时达到最低点（95 °C），然后开始逐渐升高，表明烷基链发生了自聚集。具有长烷基链（n≥6）的 In-3CNQ 衍生物产生过冷液体，熔化后显示出明显的颜色变化。在晶体结构中观察到了不同的分子堆积模式。大多数 In-3CNQ 衍生物形成面对面和/或并排的二聚体图案，以抵消净偶极矩。I20-3CNQ 通过烷基链的π堆积和自组装形成了二维双层结构。观察到两种对电子结构有重大影响的分子构象取决于烷基链的长度。提出了一个评估分子内电荷转移程度的参数，即键长比值；该参数与溶解色移和分子轨道计算结果十分吻合。
• Crystal Structures, Degree of Charge Transfer, and Non-Linear Optical Characteristics of Intramolecular Charge-Transfer Compounds: Indoline-Substituted Tricyanoquinodimethanes
  作者：Tsuyoshi Murata、Gunzi Saito、Kazukuni Nishimura、Chin-Hong Chong、Masaru Makihara、Genki Honda、Yuichiro Enomoto、Salavat Khasanov、Hideki Yamochi、Akihiro Otsuka、Kenji Kamada、Koji Ohta、Jun Kawamata

  DOI：10.1246/bcsj.81.1131

  日期：2008.9.15

  The substituent effect on the degree of intramolecular charge transfer (δ) and optical properties of donor–π–acceptor compounds comprised of 1,3,3-trimethyl-2-methyleneindoline (I1) and substituted 7,8,8-tricyanoquinodimethane (=2-(4-cyanomethylene-2,5-cyclohexadienylidene)malononitrile, 3CNQ-R, R = substituent groups) moieties were investigated (I1–3CNQ-R). In the crystal structures, I1–3CNQ-R molecules stacked on indoline and/or 3CNQ-R moieties in a head-to-tail manner to cancel their dipole moments and established segregated or mixed stack columnar motifs. The δ values of I1–3CNQ-R molecules in solid and solution states were estimated using the bond length ratio in the crystal structures, molecular orbital calculation, and the solvatochromic shift of intramolecular charge-transfer absorption, respectively, and showed significant and reasonable dependences on substituents of the 3CNQ moiety. Structural analysis revealed that molecular conformation and planarity affect the δ values of I1–3CNQ-R molecules. Molecular orbital calculations revealed that molecular (hyper)polarizabilities can be modulated by tuning δ. I1–3CNQ-R exhibited a solvatochromic shift, and the ground state changed from neutral (δ≤0.5) in less-polar solvents to ionic (δ≥0.5) in polar solvents. Two-photon absorption properties of I1–3CNQ-R showed a significant substituent effect and indicated that δ is a fundamental parameter for modulating non-linear optical properties.

  取代基对由1,3,3-三甲基-2-亚甲基吲哚啉(I1)和取代的7,8,8-三氰基喹诺二甲烷(=2-(4-氰基亚甲基-2,5-环己二烯亚基)丙二腈，3CNQ-R，R=取代基基团)组成的供体-π-受体化合物的分子内电荷转移程度(δ)和光学性质的影响(I1-3CNQ-R)。在晶体结构中，I1-3CNQ-R分子以头对尾的方式堆积在吲哚啉和/或3CNQ-R基团上以消除其偶极矩，并建立了分离或混合的堆叠柱型图案。使用晶体结构中的键长比、分子轨道计算和分子内电荷转移吸收的溶剂化色移分别估计了I1-3CNQ-R分子在固体和溶液状态下的δ值，并显示出对3CNQ基团的取代基的显著和合理的依赖关系。结构分析表明，分子构象和平面性影响I1-3CNQ-R分子的δ值。分子轨道计算表明，通过调节δ可以调节分子的(超)极化率。I1-3CNQ-R表现出溶剂化色移，基态从较低极性溶剂中的中性态(δ≤0.5)变为极性溶剂中的离子态(δ≥0.5)。I1-3CNQ-R的双光子吸收性质显示出显著的取代基效应，表明δ是调节非线性光学性质的基本参数。
• Charge-Transfer Complexes between Indoline–Tricyanoquinodimethane Compounds and 7,7,8,8-Tetracyanoquinodimethane
  作者：Tsuyoshi Murata、Genki Honda、Chin-Hong Chong、Masaru Makihara、Kazukuni Nishimura、Salavat Khasanov、Akihiro Otsuka、Gunzi Saito

  DOI：10.1246/bcsj.81.1492

  日期：2008.11.15

  Intramolecular charge-transfer compounds composed of 1-alkyl-3,3-dimethyl-2-methyleneindoline (In, donor, n = alkyl chain length; 1 or 6) and 7,8,8-tricyanoquinodimethane (=2-(4′-cyanomethylene-2′,5′-cyclohexadienylidene)malononitrile, 3CNQ, acceptor) moieties afforded charge-transfer complexes with 7,7,8,8-tetracyanoquinodimethane (TCNQ): (I1–3CNQ)2(TCNQ) and (I6–3CNQ)(TCNQ). (I1–3CNQ)2(TCNQ) included two kinds of I1–3CNQ molecules of different molecular conformations. (I1–3CNQ)2(TCNQ) and (I6–3CNQ)(TCNQ) were constructed from one-dimensional columns of 3CNQ···TCNQ···3CNQ triads and 3CNQ···TCNQ dyads, respectively. These complexes exhibited intermolecular charge-transfer bands extending to the near IR region (1000–1500 nm) in addition to intramolecular charge-transfer bands around 600–900 nm characteristic of In–3CNQ compounds. They were characterized as weak charge-transfer solids from estimations of the degree of charge transfer using molecular orbital calculations, bond lengths, and vibration spectra. Intermolecular charge transfer caused a slight increase in the degree of intramolecular charge transfer.

  由 1-烷基-3,3-二甲基-2-亚甲基吲哚啉（In，供体，n = 烷基链长度；1或6）和 7,8,8-三氰基二甲烷（=2-(4′-氰基亚甲基-2′,5′-环己二烯亚基)丙二腈，3CNQ，受体）分子组成的分子内电荷转移化合物与 7,7,8,8-四氰基二甲烷（TCNQ）形成了电荷转移复合物：(I1-3CNQ)2(TCNQ) 和 (I6-3CNQ)(TCNQ) 的电荷转移配合物。(I1-3CNQ)2(TCNQ) 包括两种不同分子构象的 I1-3CNQ 分子。(I1-3CNQ)2(TCNQ)和(I6-3CNQ)(TCNQ)分别由3CNQ--TCNQ--3CNQ三元组和3CNQ--TCNQ二元组的一维柱构建而成。除了 In-3CNQ 复合物特有的 600-900 纳米波长的分子内电荷转移带之外，这些复合物还显示出延伸到近红外区域（1000-1500 纳米波长）的分子间电荷转移带。根据分子轨道计算、键长和振动光谱对电荷转移程度的估计，这些化合物被定性为弱电荷转移固体。分子间电荷转移导致分子内电荷转移程度略有增加。