4,4'-bis[(p-dibutylamino)styryl]-[2,2']-bipyridine | 162440-78-0

• 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'-bis[(p-dibutylamino)styryl]-[2,2']-bipyridine
• 英文别名: 4,4'-bis(4-dibutylaminostyryl)-[2,2']-bipyridine；4,4'-bis(dibuthylaminostyryl)-[2,2']-bipyridine；4,4'-bis(dibutylaminostyryl)-[2,2']bipyridine；4,4'-dibutylaminostyryl-2,2'-bipyridine；4,4'-bis(NBu2-styryl)-2,2'-bipyridine；4,4'-bis[p-(N,N-dibutylamino)styryl]-2,2'-bipyridine；N,N-dibutyl-4-[(E)-2-[2-[4-[(E)-2-[4-(dibutylamino)phenyl]ethenyl]pyridin-2-yl]pyridin-4-yl]ethenyl]aniline
• CAS: 162440-78-0
• 化学式: C₄₂H₅₄N₄
• 分子量: 614.918
• InChiKey: VBJAUVRUKPNEAE-WXUKJITCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.3
• 重原子数：
  46
• 可旋转键数：
  19
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  32.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  五羰基氯铼(I) 、 4,4'-bis[(p-dibutylamino)styryl]-[2,2']-bipyridine 以 甲苯 为溶剂， 以57%的产率得到(4,4'-bis(dibuthylaminostyryl)-[2,2']-bipyridine)Re(I)Cl(CO)3
  参考文献：
  名称：

  Design and synthesis of 4,4′-π-conjugated[2,2′]-bipyridines: a versatile class of tunable chromophores and fluorophores

  摘要：

  合成了一系列4,4'-二取代的[2,2'-]联吡啶，其中的π-共轭取代基包括供体（受体）取代的苯乙烯基、噻吩乙烯基、苯亚胺基和苯偶氮基团。提供了三个含有-CC-、-CN-和-NN-连接子的配体的X射线结构。这些发色团显示了良好的至优良的热稳定性，分解温度高达350°C。讨论了末端基团和π-连接子性质对光学特性的强烈影响。还研究了4,4'-二丁氨基苯乙烯基-[2,2'-]联吡啶的分级质子化和其与不同金属部分[Zn(II)、Hg(II)、Pd(II)、Re(I)、Re(VII)]的配位行为。发现这些外源添加剂可以轻易地在广泛的波长范围内调节吸收和发射最大值（360 < λabs < 560 nm ; 482 < λem < 646 nm）。

  DOI：

  10.1039/b106096c
• 作为产物：
  描述：

  4-(二丁基氨基)苯甲醛 在 4-甲基苯磺酸吡啶 、 lithium diisopropyl amide 作用下， 以 甲苯 为溶剂， 反应 7.5h， 生成 4,4'-bis[(p-dibutylamino)styryl]-[2,2']-bipyridine
  参考文献：
  名称：

  Synthesis and characterization of 4-alkenyl and 4,4′-dialkenyl-2,2′-bipyridyl ligands bearing π-donor substituents

  摘要：

  一系列新的π-供体单取代和双取代乙烯基吡啶（供体=4-R₂N-C₆H₄-; 4-RO-C₆H₄-; (C₅H₅)Fe(C₅H₄-); (C₅H₅)Ru(C₅H₄-)）的合成已通过4,4′-二甲基-2,2′-联吡啶的单取代和二锂物种以及4-壬基-4′-甲基-2,2′-联吡啶的单体物种与适当的醛的反应而实现。它们的1H NMR和UV–visible特性已报道。关键词：2,2′-联吡啶，π-供体取代基，UV–visible，1H NMR，非线性光学。

  DOI：

  10.1139/v97-036

文献信息

• Synthesis, Photophysical and Nonlinear Optical Properties of Macromolecular Architectures Featuring Octupolar Tris(bipyridine) Ruthenium(II) Moieties:  Evidence for a Supramolecular Self-Ordering in a Dentritic Structure
  作者：Thomas Le Bouder、Olivier Maury、Arnaud Bondon、Karine Costuas、Edmond Amouyal、Isabelle Ledoux、Joseph Zyss、Hubert Le Bozec

  DOI：10.1021/ja030296j

  日期：2003.10.1

  and nonlinear optical properties of several new multi-octupolar tris(bipyridine) ruthenium complexes are reported. The preparation on these complexes is based on the initial construction of multipodal 4,4'-dialkylaminostyryl-2,2'-bipyridine ligands (DAAS-bpy). Thermally stable polyimides featuring octupolar ruthenium trisbipyridyl complexes have been readily obtained by a polycondensation reaction. The

  报道了几种新的多八极三（联吡啶）钌配合物的合成、光物理和非线性光学特性。这些复合物的制备基于多足 4,4'-二烷基氨基苯乙烯基-2,2'-联吡啶配体 (DAAS-bpy) 的初步构建。以八极三联吡啶配合物为特征的热稳定聚酰亚胺已通过缩聚反应容易地获得。二足和三足联吡啶与钌 (II) 的受控配位策略也已成功用于构建双金属、三金属以及第一个由七个金属八极组成的金属树枝状聚合物。这些多金属物质在可见光和长寿命发光中表现出非常强的吸收带。这些大分子的二次 NLO 敏感性 beta 的特点是谐波光散射在 1.91 microm 并与相应的单金属物种的那些进行比较。NLO 研究清楚地证明了金属树枝状聚合物中的准超分子排序。
• New bipyridyl ligands bearing azo- and imino-linked chromophores. Synthesis and nonlinear optical studies of related dipolar zinc complexes†
  作者：Adam Hilton、Thierry Renouard、Olivier Maury、Hubert Le Bozec、Isabelle Ledoux、Joseph Zyss

  DOI：10.1039/a908197f

  日期：——

  The synthesis and optical properties of 4,4′-bis(dialkylaminophenylazo)-2,2′-bipyridine and 4,4′-bis(dialkylaminophenylimino)-2,2′-bipyridine ligands are described; the corresponding dipolar bipyridyl zinc dichloride complexes have been prepared and their second order nonlinear optical properties determined by electric field-induced second harmonic generation (EFISH) at 1.34 µm.

  4,4'-双(二烷基氨基苯基偶氮)-2,2'-联吡啶和4,4'-双(二烷基氨基苯基亚氨基)-2,2'-联吡啶配体的合成及其光学性质被描述；相应的二极性联吡啶二氯化锌配合物已被制备，并通过在1.34微米处的电场诱导二次谐波产生（EFISH）测定了它们的二阶非线性光学性质。
• Effects of the Metal Center and Substituting Groups on the Linear and Nonlinear Optical Properties of Substituted Styryl-Bipyridine Metal(II) Dichloride Complexes: DFT and TDDFT Computational Investigations and Harmonic Light Scattering Measurements
  作者：Azza Baccouche、Benjamin Peigné、Fatima Ibersiene、Dalila Hammoutène、Ahmed Boutarfaı̈a、Abdou Boucekkine、Christophe Feuvrie、Olivier Maury、Isabelle Ledoux、Hubert Le Bozec

  DOI：10.1021/jp1014065

  日期：2010.4.29

  UV-visible absorption spectroscopy and harmonic light scattering measurements coupled with density functional theory (DFT) calculations have been carried out for a series of 4,4'-bis(X-styry1)-2,2'-bipyridine M(II) dichloride complexes (M = Co, Ni, Cu, Zn; X = H, OMe, SMe, NMe2, NEt2, CN, NO2). The roles of the metal and the substituent X on their coordination geometries, absorption, and quadratic nonlinear optical properties have been investigated. We show that these complexes all exhibit a high-spin configuration and display a distorted tetrahedral metallic environment except the copper ones, which are distorted squareplanar complexes. When X is a strong electron-donating group (X = NMe2, NEt2) TDDFT calculations clearly demonstrate that, whereas the Zn complexes show an ILCT transition in the visible range, the Co, Ni, and Cu complexes exhibit additional MLCT and LLCT transitions. These latter transitions are vectorially opposed to the ILCT and could contribute to the decrease of the experimental quadratic hyperpolarizability beta values, in the order Zn > Ni approximate to Cu > Co. The computation of the beta values using TDDFT for the whole series of the closed-shell Zn(II) complexes featuring different X substituents established that the NLO activity increases with the donating strength of X and more generally with the decrease of the HOMO-LUMO energy gap. When X is a strong withdrawing group, the drastic decrease of the NLO response is explained by the negligible participation of the HOMO-LUMO transitions.
• Design and synthesis of 4,4′-π-conjugated[2,2′]-bipyridines: a versatile class of tunable chromophores and fluorophores
  作者：Maury、Guegana、Renouard、Hilton、Dupau、Sandon、Toupet、Le Bozec

  DOI：10.1039/b106096c

  日期：2001.12.3

  A series of 4,4′-disubstituted[2,2′]-bipyridines, featuring π-conjugated substituents such as donor-(acceptor-) substituted styryl, thienylvinyl, phenylimino and phenylazo groups, have been synthesized. X-Ray structures are provided for three ligands containing –CC–, –CN– and –NN– linkers, respectively. These chromophores display good to excellent thermal stabilities with decomposition temperatures of up to 350 °C. The strong influence of the nature of the endgroups and π-linkers on the optical properties is discussed. The stepwise protonation of 4,4′-dibutylaminostyryl-[2,2′]-bipyridine and its coordination behavior to different metallic moieties [Zn(II), Hg(II), Pd(II), Re(I), Re(VII)] have also been investigated. It is found that the absorption and emission maxima can be easily tuned by these exogenous additives over a wide range of wavelengths (360 < λabs < 560 nm ; 482 < λem < 646 nm).

  合成了一系列4,4'-二取代的[2,2'-]联吡啶，其中的π-共轭取代基包括供体（受体）取代的苯乙烯基、噻吩乙烯基、苯亚胺基和苯偶氮基团。提供了三个含有-CC-、-CN-和-NN-连接子的配体的X射线结构。这些发色团显示了良好的至优良的热稳定性，分解温度高达350°C。讨论了末端基团和π-连接子性质对光学特性的强烈影响。还研究了4,4'-二丁氨基苯乙烯基-[2,2'-]联吡啶的分级质子化和其与不同金属部分[Zn(II)、Hg(II)、Pd(II)、Re(I)、Re(VII)]的配位行为。发现这些外源添加剂可以轻易地在广泛的波长范围内调节吸收和发射最大值（360 < λabs < 560 nm ; 482 < λem < 646 nm）。
• Synthesis and characterization of 4-alkenyl and 4,4′-dialkenyl-2,2′-bipyridyl ligands bearing π-donor substituents
  作者：Manuel Bourgault、Thierry Renouard、Barbara Lognoné、Chakour Mountassir、Hubert Le Bozec

  DOI：10.1139/v97-036

  日期：1997.3.1

  The synthesis of a new series of π-donor mono-and disubstituted vinyl bipyridines (donor = 4-R₂N-C₆H₄-; 4-RO-C₆H₄-; (C₅H₅)Fe(C₅H₄-); (C₅H₅)Ru(C₅H₄-)) has been achieved by reaction of the mono- and dilithio species of 4,4′-dimethyl-2,2′-bipyridine and the monolithic species of 4-nonyl-4′-methyl-2,2′-bipyridine with the appropriate aldehydes. Their ¹H NMR and UV–visible characterizations are reported. Keywords: 2,2′-bipyridines, π-donor substituents, UV–visible, ¹H NMR, nonlinear optics.

  一系列新的π-供体单取代和双取代乙烯基吡啶（供体=4-R₂N-C₆H₄-; 4-RO-C₆H₄-; (C₅H₅)Fe(C₅H₄-); (C₅H₅)Ru(C₅H₄-)）的合成已通过4,4′-二甲基-2,2′-联吡啶的单取代和二锂物种以及4-壬基-4′-甲基-2,2′-联吡啶的单体物种与适当的醛的反应而实现。它们的1H NMR和UV–visible特性已报道。关键词：2,2′-联吡啶，π-供体取代基，UV–visible，1H NMR，非线性光学。