2,5-diethoxy-7,7,8,8-tetracyanoquinodimethane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2,5-diethoxy-7,7,8,8-tetracyanoquinodimethane
• 英文别名: 2,5-Diethoxy-7,7,8,8-tetracyanoquinodimethane；2-[4-(dicyanomethylidene)-2,5-diethoxycyclohexa-2,5-dien-1-ylidene]propanedinitrile
• 化学式: C₁₆H₁₂N₄O₂
• 分子量: 292.297
• InChiKey: AGTDHKSOXHOZNP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,3,3-三甲基-2-亚甲基吲哚啉 、 2,5-diethoxy-7,7,8,8-tetracyanoquinodimethane 以 氯苯 为溶剂， 以40%的产率得到C₂₇H₂₆N₄O₂
  参考文献：
  名称：

  Ionicity of Intramolecular Charge-Transfer Molecule D^δ+−π−A^δ- Based on 1,3,3-Trimethyl-2-methyleneindoline and 7,7,8,8-Tetracyanoquinodimethane

  摘要：

  We report a simple and convenient method to evaluate the relative ionicity delta of the typical intramolecular charge-transfer (CT) molecules linked by pi-bond Ddelta+-pi-Adelta- (D, donor; A, acceptor; delta, degree of CT) derived from 1,3,3-trimethyl-2-methylene indoline and TCNQ derivatives on the basis of the solvatochromic effects of the CT band in various solvents and their redox properties. The functionality of the intramolecular CT molecules as dyes, photovoltaic materials, nonlinear optics, rectifiers, and conductors is discussed in terms of delta.

  DOI：

  10.1021/ja027749p

文献信息

• 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。
• Ionicity Diagrams for Electron-Donor and -Acceptor Metal–Organic Frameworks: DA Chains and D₂A Layers Obtained from Paddlewheel-Type Diruthenium(II,II) Complexes and Polycyano-Organic Acceptors
  作者：Yoshihiro Sekine、Masaki Nishio、Tomoka Shimada、Wataru Kosaka、Hitoshi Miyasaka

  DOI：10.1021/acs.inorgchem.0c03335

  日期：2021.3.1

  two-dimensional D2A layers. The series were obtained by reacting paddlewheel-type diruthenium(II,II) complexes ([Ru2II,II]), which served as D units, with the polycyano-organic acceptors N,N′-dicyanoquinodiimine (DCNQI) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), which served as A units. Fifteen novel members of neutral charged DA chains were fabricated in this study to characterize the ionicity diagrams

  有关金属有机骨架和配位聚合物的研究的最新进展为电荷可变分子骨架的成功设计提供了条件。但是，很少有全面的研究来研究诸如此类的一系列分子框架中电荷状态的控制。在这里，我们讨论包含电子供体（D）和受体（A）单元的两个系列的电离图：一维DA链和二维D 2 A层。该系列是通过将用作D单元的轮式二钌（II，II）配合物（[Ru 2 II，II ]）与多氰基有机受体N，N'-二氰基喹二亚胺（DCNQI）和7反应制得的。 7,8,8 -四氰基p-quinodimethane（TCNQ），用作A单元。在这项研究中，制造了十五个新颖的中性带电DA链成员，以表征DA和D 2 A系统的离子图。
• Layered ferrimagnets constructed from charge-transferred paddlewheel [Ru₂] units and TCNQ derivatives: the importance of interlayer translational distance in determining magnetic ground state
  作者：Wataru Kosaka、Zhaoyuan Liu、Hitoshi Miyasaka

  DOI：10.1039/c8dt01566j

  日期：——

  1–3 became three-dimensional ferrimagnets with Curie temperatures TC = 93, 93, and 92 K, respectively, owing to the presence of interlayer ferromagnetic interactions. The interlayer translational distances (l2) for the three compounds were 10.56, 10.54, and 10.84 Å, respectively, which agreed with the empirical prediction based on the threshold value of l2 > 10.3 Å for a valid ferromagnetic interaction

  使用桨轮型二钌（II，II）络合物[Ru 2（3,5-F 2 PhCO 2）4（THF）2 ]（3,5-F 2）进行供体（D）/受体（A）组装反应PhCO 2 - = 3,5-二氟苯甲酸甲酯;以下简称为的[Ru 2 ]）为d和7,7,8,8-四氰基p -quinodimethane衍生物（TCNQR X ; 2,5- ř取代TCNQ），为在DCM / TCE或DCE溶剂系统（DCM =二氯甲烷，TCE = 1,1,2,2-四氯乙烷，DCE = 1,2-二氯乙烷）中导致形成D 2A型二维分层化合物[Ru 2（3,5-F 2 PhCO 2）4 } 2 TCNQR x }]· n solv（R x = H 2（1），R x = Me 2，（2），并且R x =（OEt）2（3））。所有化合物均具有相似的二维鱼网型结构，其中两个[Ru 2 ]单元与TCNQR x的四个氰基完全配位。化合物1-3
• Magnet Creation by Guest Insertion into a Paramagnetic Charge-Flexible Layered Metal–Organic Framework
  作者：Jun Zhang、Wataru Kosaka、Hiroyasu Sato、Hitoshi Miyasaka

  DOI：10.1021/jacs.1c01537

  日期：2021.5.12

  Changing nonmagnetic materials to spontaneous magnets is an alchemy-inspiring concept in materials science; however, it is not impossible. Here, we demonstrate chemical modification from a nonmagnet to a bulk magnet of either a ferrimagnet or antiferromagnet, depending on the adsorbed guest molecule, in an electronic-state-flexible layered metal–organic framework, [Ru2(2,4-F2PhCO2)4}2TCNQ(EtO)2] (1;

  将非磁性材料转换为自发磁体是材料科学中启发炼金术的概念。但是，这并非不可能。在这里，我们展示了在电子态柔性层状金属-有机框架中，根据吸附的客体分子，从非磁体到铁磁体或反铁磁体的体磁体的化学修饰，[Ru 2（2,4-F 2 PhCO 2）4 } 2 TCNQ（EtO）2 ]（1 ; 2,4-F 2 PhCO 2 – = 2,4-二氟苯甲酸酯； TCNQ（EtO）2 = 2,5-二乙氧基-7,7,8， 8-四氰基喹二甲烷）。无客人用的顺磁铁1经历热驱动的Intraattice电子转移，涉及380 K的结构转变。1吸附数种有机分子，例如苯（PhH），对二甲苯（PX），1,2-二氯乙烷（DCE），二氯甲烷（DCM）和二硫化碳（CS 2），形成具有完整结晶度的1-solv。这引起了向内的电子转移以产生亚铁磁有序的磁性层。因此，根据由相应的客体分子调节的层间环境，磁相被更改为客体PhH，PX，DCE和DCM的亚铁磁体或CS
• A metal–organic framework that exhibits CO2-induced transitions between paramagnetism and ferrimagnetism
  作者：Jun Zhang、Wataru Kosaka、Yasutaka Kitagawa、Hitoshi Miyasaka

  DOI：10.1038/s41557-020-00577-y

  日期：2021.2

  diruthenium(ii) clusters as the electron donor (D) with diethoxytetracyanoquinodimethane as the electron acceptor (A). On CO2 uptake, it undergoes an in-plane electron transfer and a structural transition to adopt a [D–A–D] paramagnetic form. This magnetic phase change, and the accompanying modifications to the electronic conductivity and permittivity of the MOF, are electronically stabilized by the guest

  如果有足够的构造块，金属有机框架（MOF）可以将磁有序性和孔隙率结合在一起。这使MOF成为开发刺激反应性材料的有前途的平台，这些材料会根据其孔中是否存在客体分子而表现出截然不同的磁性。在这里，我们报告了一个CO 2响应磁性MOF，该MOF在吸附CO 2时从亚铁磁转变为顺磁，并在CO 2解吸时返回到亚铁磁状态。亚铁磁性材料是具有[D + –A − –D]分子式的层状MOF ，由三氟苯甲酸酯桥连的桨轮型二钌（ii）以二乙氧基四氰基喹二甲烷为电子受体（A）聚集为电子供体（D）。在吸收CO 2时，它经历面内电子转移和结构转变，以采用[D–A–D]顺磁性形式。通过容纳在框架中的客体CO 2分子，该磁性相变以及对MOF的电子电导率和介电常数的随之而来的修饰被电子稳定。