4'-(4-biphenylyl)-4,2':6',4"-terpyridine | 1346435-96-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 4'-(4-biphenylyl)-4,2':6',4"-terpyridine
• 英文别名: 4'-(4-biphenylyl)-4,2':6',4''-terpyridine；4'-biphenyl-4-yl-4,2':6',4''-terpyridine；4-(4-Phenylphenyl)-2,6-dipyridin-4-ylpyridine
• CAS: 1346435-96-8
• 化学式: C₂₇H₁₉N₃
• 分子量: 385.468
• InChiKey: GWMUATHHTBGXPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4'-(4-biphenylyl)-4,2':6',4"-terpyridine 、 cadmium(II) acetate dihydrate 以 甲醇 、 氯仿 为溶剂， 反应 504.0h， 生成 [{Cd₂(μ,κ³-O,O':O'-OAc)₂(κ²-O,O'-OAc)₂₍4'-(4-biphenylyl)-4,2':6',4''-terpyridine)}_n]
  参考文献：
  名称：

  含d9和d10金属离子的一维配位聚合物组装体中4'-（4-联苯基）-4,2'：6'，4''-吡啶吡啶域之间的分子识别

  摘要：

  摘要从醋酸锌（II）与4'-（4-联苯基）-4,2'：6'，4''-三联吡啶的反应中组装[{Zn2（μ-OAc）4（1）} n]（1 ）使用Zn（II）：1的1：1、2：1和1：2比率与测试条件无关。游离配体1是在晶胞中与五个独立分子结晶的化合物的罕见例子（Z'= 5）。单晶X射线衍射证实[{Zn2（μ-OAc）4（1）} n]是一维配位聚合物，其中1个桥接{Zn2（μ-OAc）4}节点。每个聚合物链具有之字形构型，并且链通过成对的联苯结构域对和tpy单元对的面对面π堆叠而缔合。比较了[{Zn2（μ-OAc）4（1）} n]的固态结构与相关化合物的固态结构。从锌（II）转移到铜（II）对配位为1的配位聚合物的组装几乎没有影响 [{Cu2（μ-OAc）4（1）} n]与[{Zn2（μ-OAc）4（1）} n]同构。与乙酸镉（II）形成梯形聚合物链，其中包含{Cd2（μ，κ3-O，O'：O'-

  DOI：

  10.1016/j.poly.2013.05.026
• 作为产物：
  描述：

  在 ammonium acetate 、 溶剂黄146 作用下， 反应 5.0h， 以1.85 g的产率得到4'-(4-biphenylyl)-4,2':6',4"-terpyridine
  参考文献：
  名称：

  Controlling interpenetration in CuCN coordination polymers by size of the pendant substituents of terpyridine ligands

  摘要：

  为了系统地研究配体的侧链对配位聚合物组装的影响（例如，控制交叉嵌套），合成了四种具有庞大侧链的三吡啶配体，即4′-(4-甲苯)-4,2′:6′,4′′-三吡啶（L1）、4′-(4-乙基苯)-4,2′:6′,4′′-三吡啶（L2）、4′-(4-异丙基苯)-4,2′:6′,4′′-三吡啶（L3）和4′-联苯-4,2′:6′,4′′-三吡啶（L4）。在相同的溶剂热条件下，CuCN与L1–L4的反应分别生成了四种CuCN配位聚合物：[(CuCN)2L1]n (1)、[(CuCN)2L2]n (2)、[(CuCN)2L3]n (3)和{[(CuCN)3L41.5]·H2O}n (4)。单晶X射线分析显示，化合物1–3具有相同的拓扑结构，均为四重交叉嵌套的三维CuCN网络，而化合物4则是一个非交叉嵌套的CuCN网络。这一成功表明，通过改变三吡啶配体的侧链大小来抑制交叉嵌套现象。

  DOI：

  10.1039/c1ce05565h

文献信息

• A convenient method for synthesis of terpyridines <i>via</i> a cooperative vinylogous anomeric based oxidation
  作者：Fatemeh Karimi、Meysam Yarie、Mohammad Ali Zolfigol

  DOI：10.1039/d0ra04461j

  日期：——

  The presented study is the first report of the synthesis of terpyridines in the presence of a nanomagnetic catalyst instead of harmful reagents. Herein, Fe3O4@O2PO2(CH2)2NH3+CF3CO2− as a retrievable nanocatalyst with magnetic properties was applied for the multi-component reaction between acetylpyridine derivatives (2 or 3 or 4-isomer), aryl aldehydes and ammonium acetate under conventional heating

  本研究是首次报道在纳米磁性催化剂而不是有害试剂存在下合成三联吡啶。在此，Fe 3 O 4 @O 2 PO 2 (CH 2 ) 2 NH 3 + CF 3 CO 2 −作为具有磁性的可回收纳米催化剂，应用于乙酰吡啶衍生物（2或3或4-异构体）之间的多组分反应)、芳基醛和乙酸铵在常规加热条件下，在没有任何溶剂的情况下。通过合作插烯异头氧化路线，以可接受的产率和短暂的反应时间获得了衍生的三联吡啶。Fe 3 O 4 @O 2 PO 2 (CH 2 ) 2 NH 3 + CF 3 CO 2 -在上述反应中表现出较高的回收和再利用能力。
• Do perfluoroarene⋯arene and C–H⋯F interactions make a difference to the structures of 4,2′:6′,4′′-terpyridine-based coordination polymers?
  作者：Edwin C. Constable、Catherine E. Housecroft、Srboljub Vujovic、Jennifer A. Zampese、Aurélien Crochet、Stuart R. Batten

  DOI：10.1039/c3ce41384e

  日期：——

  The consequences for the structures of coordination polymers of introducing fluoro substituents into the terminal phenyl domain of 4′-(biphenyl-4-yl)-4,2′:6′,4′′-terpyridine (1) have been investigated. Reaction between Cu(OAc)2·H2O and 4′-(2′,3′,4′,5′,6′-pentafluorobiphenyl-4-yl)-4,2′:6′,4′′-terpyridine (2) yields the one-dimensional coordination polymer [Cu2(μ-OAc)4(2)]n which contains paddle-wheel Cu2(OAc)4} nodes bridged by ligands 2. The compound is isostructural with [Cu2(μ-OAc)4(1)]n. When Cu(OAc)2·H2O reacts with a 1 : 1 mixture of 1 and 2, [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n co-crystallize with 1 and 2 disordered over one ligand site; the one-dimensional coordination polymer is isostructural with each of [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n indicating that replacing H by F substituents in the peripheral arene ring has no effect on the overall solid-state structure: tpy⋯tpy π-stacking is preserved, arene⋯arene πH⋯πH interactions are replaced by perfluoroarene⋯arene πF⋯πH interactions, and H⋯H contacts are replaced by H⋯F interactions. In stark contrast to the latter observations, the reaction of Zn(OAc)2·2H2O with perfluoro derivative 2 yields [Zn5(OAc)10(2)4·11H2O]n as the dominant one-dimensional polymer; minor amounts of the anticipated polymer [Zn2(μ-OAc)4(2)]n are also formed. The solid-state structure of [Zn5(OAc)10(2)4·11H2O]n consists of quadruple-stranded polymer chains assembled from Zn5(2)4} subchains interconnected by Zn5(OAc)10} units. Within each chain, πF⋯πF and πH⋯πH stacking interactions are dominant, while the observed assembly of chains into sheets and π-stacking between arene units in adjacent sheets mimic the dominant interactions in the single-stranded chains observed in [Zn2(μ-OAc)4(1)]n, [Zn2(μ-OAc)4(2)]n, [Cu2(μ-OAc)4(1)]n, [Cu2(μ-OAc)4(2)]n and [Cu2(μ-OAc)4(1)]n·[Cu2(μ-OAc)4(2)]n.

  4-(联苯-4-基)-4,2-:6-2,4-2-三联吡啶末端苯基结构域引入氟取代基对配位聚合物结构的影响 (1)已被调查。 Cu(OAc)2·H2O与4â2-(2â2,3â2,4â2,5â2,6â2-五氟联苯-4-基)-4,2â2:6â的反应²,4−−−三联吡啶 (2) 产生一维配位聚合物 [Cu2(μ-OAc)4(2)]n ，其中包含由配体 2 桥接的桨轮 Cu2(OAc)4} 节点。该化合物与 [Cu2(μ-OAc)4(1)]n 具有同构结构。当 Cu(OAc)2· 与 1 和 2 的 1-:-1 混合物反应时，[Cu2(μ-OAc)4(1)]n 和 [Cu2(μ-OAc)4(2) ]n 与 1 和 2 在一个配体位点上无序共结晶；一维配位聚合物与 [Cu2(μ-OAc)4(1)]n 和 [Cu2(μ-OAc)4(2)]n 均具有同构结构，表明外围芳环中的 H 被 F 取代基取代对整体固态结构没有影响：tpy–tpy δ-堆积被保留，芳烃–芳烃ÏH–ÏH相互作用被全氟芳烃–芳烃ÏF–ÏH取代相互作用，并且 H–H 接触被 H–F 相互作用取代。与后面的观察形成鲜明对比的是，Zn(OAc)2·2 与全氟衍生物 2 的反应产生了 [Zn5(OAc)10(2)4·11 ]n 作为主要的一维聚合物；还形成了少量预期的聚合物 [Zn2(μ-OAc)4(2)]n。 [Zn5(OAc)10(2)4·11 ]n的固态结构由由Zn5(OAc)10}单元互连的Zn5(2)4}子链组装而成的四链聚合物链组成。在每个链中，δF-δF 和δH-δH 堆积相互作用占主导地位，而观察到的链组装成片材和相邻片材中芳烃单元之间的δ-堆积模仿了主要相互作用在 [Zn2(μ-OAc)4(1)]n、[Zn2(μ-OAc)4(2)]n、[Cu2(μ-OAc)4(1)]n、[ 中观察到的单链Cu2(μ-OAc)4(2)]n 和 [Cu2(μ-OAc)4(1)]n·[Cu2(μ-OAc)4(2)]n。
• Metallohexacycles containing 4′-aryl-4,2′:6′,4′′-terpyridines: conformational preferences and fullerene capture
  作者：Edwin C. Constable、Catherine E. Housecroft、Srboljub Vujovic、Jennifer A. Zampese

  DOI：10.1039/c3ce42012d

  日期：——

  4′-(4-Biphenylyl)-4,2′:6′,4′′-terpyridine (1) reacts with ZnCl2 or ZnBr2 to produce discrete metallohexacycles instead of the expected one-dimensional coordination polymers. Structural determination of [ZnCl2(1)}6] and [ZnBr2(1)}6] reveals that the metallomacrocycles adopt a conformation in which the biphenyl domains are in an alternating up/down arrangement (conformer I). The hexamers pack into tubes; within each tube, biphenyl domains of every second hexamer are interdigitated, and these assemblies then interlock to produce a rigid architecture supported by pyridine–phenyl face-to-face contacts. π-Stacking between 4,2′:6′,4′′-tpy domains operates between adjacent tubes. Reaction of ZnCl2 or ZnBr2 with 4′-(2′,3′,4′,5′,6′-pentafluorobiphenyl-4-yl)-4,2′:6′,4′′-terpyridine (2) leads to [ZnCl2(2)}6] and [ZnBr2(2)}6], each crystallizing in two conformations; the centrosymmetric chair-conformer (II) is dominant with respect to the tub-like conformer I. Both conformers pack into tube assemblies, but that consisting of conformer II is less rigid than that of I. Reaction of 4′-(4-(naphthalen-1-yl)phenyl)-4,2′:6′,4′′-terpyridine (3) with ZnCl2 or ZnBr2 leads to [ZnX2(2)}6] (X = Cl, Br) in conformer I; disordering of the naphthyl substituents is problematic. Assembly of the metallohexacycle in the presence of C60 results in the formation of the host–guest complex [2ZnCl2(3)}6·C60]·6MeOH·16H2O. The [ZnCl2(3)}6] units assemble into a tube-like array that mimics that observed in the parent host. In the host–guest complex, each crystallographically-ordered C60 is trapped between six ordered naphthyl units, three from one hexamer and three from its interdigitated partner, and the C60–six-naphthyl unit sits centrally within a second [ZnCl2(3)}6] macrocycle. In contrast to previously described tube-like host–guest assemblies featuring fullerene entrapment, [2ZnCl2(3)}6·C60] is unusual in having an ordered array of C60 molecules present in every other available cavity, despite the fact that sterically, the ‘empty’ cavity could, in principle, host a C60 guest.

  ，因为它们是共价键，而苯基取代基的失序则不是问题，因为它们是离子键。