2,5-Dibromo-7,7,8,8-tetracyano-p-quinodimethane | 56403-70-4

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物 - 醌二甲烷类
• 英文名称: 2,5-Dibromo-7,7,8,8-tetracyano-p-quinodimethane
• 英文别名: 2,2'-(2,5-Dibromocyclohexa-2,5-diene-1,4-diylidene)dimalononitrile；2-[2,5-dibromo-4-(dicyanomethylidene)cyclohexa-2,5-dien-1-ylidene]propanedinitrile
• CAS: 56403-70-4
• 化学式: C₁₂H₂Br₂N₄
• 分子量: 361.983
• InChiKey: OJFNHXWMRQGERY-UHFFFAOYSA-N

物化性质

• 熔点：
  316-318 °C (decomp)
• 沸点：
  82.6±40.0 °C(Predicted)
• 密度：
  2.067±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  95.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N,N-二羟乙基苯胺 、 2,5-Dibromo-7,7,8,8-tetracyano-p-quinodimethane 以 氯苯 为溶剂， 反应 24.0h， 以45%的产率得到
  参考文献：
  名称：

  Synthesis and optical properties of new tricyano-p-quinodimethane dyes: molecular and polymeric systems

  摘要：

  The reaction of N,N-bis(2-hydroxyethyl)aniline 1 with tetracyano-p-quinodimethane (TCNQ) 2 yields the photochromic red chromophore 3 [lambda(max) (acetone/dichloromethane) 497 nm] which upon UV irradiation is converted into the blue zwitterionic form 3' (lambda(max) 680 nm) by a novel intramolecular charge transfer process involving a D-quinoid-aryl-A-->D+-aryl-quinoid-A(-) conversion. The analogous process occurs in the polyimide derived system 8. Different products are isolated from reactions of 1 with the stronger electron accepters TCNQBr(2) and TCNQF(4). (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00610-9
• 作为产物：
  描述：

  Dicyano-[2,5-dibromo-4-(dicyano-methoxycarbonyl-methyl)-phenyl]-acetic acid methyl ester 生成 2,5-Dibromo-7,7,8,8-tetracyano-p-quinodimethane
  参考文献：
  名称：

  Synthesis of substituted 7,7,8,8-tetracyanoquinodimethanes

  摘要：

  DOI：

  10.1021/jo00909a019

文献信息

• Synthesis of substituted TCNQ derivatives using electrophilic cyanide derived from thiocyanate and selenocyanate reagents
  作者：Martin R. Bryce、Masihul Hasan、Geoffrey J. Ashwell

  DOI：10.1039/c39890000529

  日期：——

  A range of TCNQ derivatives have been efficiently prepared using 2-chlorobenzyl thiocyanate or arylselenocyanates as sources of electrophilic cyanide.

  使用2-氯苄基硫氰酸酯或芳基硒酸酯作为亲电子氰化物的来源，已经有效地制备了多种TCNQ衍生物。
• Langmuir–Blodgett Films of Charge-Transfer Complexes: Ethylenedithio-Substituted Amphiphilic Bis-TTF Macrocycle and F₄TCNQ or Br₂TCNQ
  作者：Toru Endo、Tomoyuki Akutagawa、Teppei Kajiwara、Keiko Kakiuchi、Yoko Tatewaki、Shin-ichiro Noro、Takayoshi Nakamura

  DOI：10.1246/bcsj.82.968

  日期：2009.8.15

  Charge-transfer (CT) complexes between ethylenedithio-substituted bis-TTF macrocycle 1a, as an amphiphilic electron donor, and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) derivatives, as electron acceptors, were fabricated as Langmuir–Blodgett (LB) films. For the 1a–F4TCNQ LB film deposited at a surface pressure of 5 mN m−1 onto a substrate surface, the stoichiometry between the donor and acceptor was determined as 1:2 using XPS measurements. In contrast, a donor/acceptor ratio of 1:0.3 was observed for the 1a–Br2TCNQ LB film, indicating that a fraction of Br2TCNQ was lost during the LB film formation process. Similarity of the round-shaped domains that cover the surfaces of the 1a–Br2TCNQ and neutral 1a LB films indicates the presence of neutral 1a within the 1a–Br2TCNQ LB film. For the (1a2+)(F4TCNQ−)2 LB film, the presence of a CN-stretching frequency signifies the formation of a fully ionic electronic ground state. The LB film of 1a–Br2TCNQ exhibited a broad absorption at ca. 3 × 103 cm−1, which is characteristic of an intermolecular CT transition for a partial CT state. 1a–Br2TCNQ LB film consisted of neutral 1a and CT complex of 1a–Br2TCNQ. The room temperature conductivity of the 1a–Br2TCNQ LB film (1.2 × 10−2 S cm−1) was two orders of magnitude higher than that of 1a–F4TCNQ (3.9 × 10−4 S cm−1).

  作为两亲性电子给体的亚乙二硫代双 TTF 大环 1a 与作为电子受体的 7,7,8,8- 四氰基对醌二甲烷 (TCNQ) 衍生物之间的电荷转移 (CT) 复合物被制成了朗缪尔-布洛杰特 (LB) 薄膜。对于在 5 mN m-1 的表面压力下沉积到基底表面的 1a-F4TCNQ LB 薄膜，通过 XPS 测量确定了供体和受体之间的配比为 1:2。相比之下，1a-Br2TCNQ枸杞薄膜的供体/受体比为 1:0.3，表明在枸杞薄膜形成过程中损失了一部分 Br2TCNQ。覆盖在 1a-Br2TCNQ 和中性 1a LB 薄膜表面的圆形畴具有相似性，这表明在 1a-Br2TCNQ LB 薄膜中存在中性 1a。对于 (1a2+)(F4TCNQ-)2 LB 薄膜来说，CN 拉伸频率的出现标志着完全离子电子基态的形成。1a-Br2TCNQ 的枸杞薄膜在约 3 × 103 cm-1 处显示出宽吸收，这是由于枸杞薄膜中的枸杞离子在枸杞基态上的吸收率较低。3 × 103 cm-1 处的宽吸收，这是部分 CT 态分子间 CT 转变的特征。1a-Br2TCNQ LB 薄膜由中性 1a 和 1a-Br2TCNQ 的 CT 复合物组成。1a-Br2TCNQ LB 薄膜的室温电导率（1.2 × 10-2 S cm-1）比 1a-F4TCNQ 的室温电导率（3.9 × 10-4 S cm-1）高出两个数量级。
• Control of Charge Transfer in a Series of Ru₂^II,II/TCNQ Two-Dimensional Networks by Tuning the Electron Affinity of TCNQ Units: A Route to Synergistic Magnetic/Conducting Materials
  作者：Hitoshi Miyasaka、Natsuko Motokawa、Satoshi Matsunaga、Masahiro Yamashita、Kunihisa Sugimoto、Tatsuya Mori、Naoki Toyota、Kim R. Dunbar

  DOI：10.1021/ja909489s

  日期：2010.2.10

  5+)}] for the 2-D network. Such a charge (or electron) transfer results in magnetic exchange interactions between [Ru(2)] units (S = 1 for [Ru(2)(II,II)] and S = 3/2 for [Ru(2)(II,III)](+)) via TCNQR(x)(*-) S = 1/2 radicals that lead to long-range magnetic ordering in the layer. In the present series, only 5 demonstrated the full electron transfer (1-e(-) transfer) to the mixed-valence state, whereas

  二维（2-D）渔网型网络化合物的同构系列，[Ru(2)(O(2)CCF(3))(4)}(2)(TCNQR(x))] xn( solv) (R(x) = H(4), 1; Br(2), 2; Cl(2), 3; F(2), 4; F(4), 5), 已从反应合成桨轮二钌 (II, II) 络合物 [Ru(2)(II,II)(O(2)CCF(3))(4)] 和中性 TCNQ 衍生物 (TCNQR(x) = 2,3, 5,6- 或 2,5- 卤素取代的 7,7,8,8-四氰基醌二甲烷）在厌氧条件下。为了与1-5进行比较，还合成了相应的Rh化合物1-Rh-5-Rh，它们具有抗磁性和氧化还原活性。根据 TCNQR(x) 的电子亲和势，这与其第一还原电位有关，Ru(2) 系列 (1-5) 具有从 [Ru(2)(II,II) 电荷转移所需的驱动力(O(2)CCF(3))(4)] 到 TCNQR(x)，这会导致
• Langmuir–Blodgett alignment of zwitterionic optically non-linear D–π–A materials
  作者：Geoffrey J. Ashwell、Emma J. C. Dawnay、Andrzej P. Kuczynski、Marek Szablewski、Ian M. Sandy、Martin R. Bryce、Andrew M. Grainger、Masihul Hasan

  DOI：10.1039/ft9908601117

  日期：——

  The synthesis, Langmuir–Blodgett (LB) deposition and charge-transfer spectra of Z-β-(1-alkyl-4-quinolinium)-α-cyano-4-styryldicyanomethanide (R-Q3CNQ where R = C6H13 to C20H41) and four substituted analogues are described. The deposition is Z-type and the properties are dependent upon the hydrophobic chain length. C6H13-Q3CNQ to C14H29-Q3CNQ form green LB films (λmax= 614 ± 4 nm; HWHM = 37 ± 2 nm)

  Z - β-（1-烷基-4-喹啉鎓）-α-氰基-4-苯乙烯基二氰基甲烷（R-Q3CNQ，其中R = C 6 H 13至C的合成，Langmuir-Blodgett（LB）沉积和电荷转移谱描述了20 H 41）和四个取代的类似物。沉积是Z型的，并且性质取决于疏水链的长度。Ç 6 ħ 13 -Q3CNQ至C 14 ħ 29层-Q3CNQ形式绿色LB膜（λ最大= 614±4纳米; HWHM = 37±2纳米），并占据28-34埃2每分子至少为25mN米-1。与此相反，C 15 ħ 31 -Q3CNQ至C 20 ħ 41 -Q3CNQ占据40-50埃2每分子; 它们的薄膜是紫色的，λmax = 565±4 nm，HWHM = 22±1 nm。该变化归因于分子倾斜的变化，该变化导致转变从分子间过程转变为分子内过程。C 16 H 33 -Q3CNQ多层膜表现出很强的二次谐波产生（SHG），强度随LB层数的增加而平方增加。
• A new metal–organic hybrid material with intrinsic resistance-based bistability: monitoring in situ room temperature switching behavior
  作者：Zhongyue Zhang、Hanhua Zhao、Michio M. Matsushita、Kunio Awaga、Kim R. Dunbar

  DOI：10.1039/c3tc31577k

  日期：——

  Two new silver containing materials with TCNQ derivatives were prepared by electrocrystallization. Synchrotron radiation diffraction studies were conducted to determine the structures of the new phases which exhibit unprecedented high room temperature conductivity. The I–V characteristics reveal a room-temperature switching behaviour and memory effect based on intrinsic negative differential resistance (NDR). EPR spectroscopic measurements performed under an applied electric field indicate a g-tensor shift that is correlated to the amplitude of current.

  通过电结晶法制备了两种新的含银材料，并带有TCNQ衍生物。同步辐射衍射研究用于确定新相的结构，这些新相具有前所未有的高室温电导率。I-V特性揭示了基于固有负微分电阻（NDR）的室温开关行为和记忆效应。在外加电场下进行的EPR光谱测量表明，g-张量位移与电流幅度相关。