4,4'-bis[p-diethylamino-α-styryl]-2,2'-bipyridine

• 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-diethylamino-α-styryl]-2,2'-bipyridine
• 英文别名: 4,4'-bis(4-diethylaminostyryl)-[2,2']-bipyridine；trans-4,4'-diethylaminostyryl-2,2'-bipyridine；4,4'-diethylaminostyryl-2,2'-bipyridine；4,4'-bis(NEt2-styryl)-2,2'-bipyridine；4-[(E)-2-[2-[4-[(E)-2-[4-(diethylamino)phenyl]ethenyl]pyridin-2-yl]pyridin-4-yl]ethenyl]-N,N-diethylaniline
• 化学式: C₃₄H₃₈N₄
• 分子量: 502.703
• InChiKey: FIKDOUDCZYDZIY-WGDLNXRISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 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：

  水合三氯化钌 、 4,4'-bis[p-diethylamino-α-styryl]-2,2'-bipyridine 在 lithium chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 bis(4,4'-diethylaminostyryl-2,2'-bipyridine) dichloro ruthenium(II)
  参考文献：
  名称：

  具有八极三（联吡啶）钌（II）部分的大分子结构的合成、光物理和非线性光学特性：树突状结构中超分子自排序的证据

  摘要：

  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。

  DOI：

  10.1021/ja030296j

文献信息

• 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。
• Efficient sensitization of nanocrystalline TiO2 films with high molar extinction coefficient ruthenium complex
  作者：Ke-Jian Jiang、Jiang-bin Xia、Naruhiko Masaki、Shuji Noda、Shozo Yanagida

  DOI：10.1016/j.ica.2007.06.014

  日期：2008.2

  4′-bis[p-diethylamino]-α-styryl]-2,2′-bipyridine, was synthesized. The dye displays extremely high molar extinction coefficient, which is comparable with organic dye. Preliminary test shows the dye-sensitized TiO2 solar cell gives high conversion efficiency up to 8.65% under 1 Sun, while 8.35% is given for N3 based DSCs under the same condition. The dye will be further employed in solid state DSCs with hole transport

  摘要一种新型的杂配多吡啶钌配合物cis-Ru（L1）（L2）（NCS）2，L1 = 4,4'-二羧酸-2,2'-联吡啶（dcbpy），L2 = 4,4'-bis合成了[对二乙氨基]-α-苯乙烯基] -2，2′-联吡啶。该染料显示出极高的摩尔消光系数，与有机染料相当。初步测试显示，染料敏化的TiO2太阳能电池在1个太阳光下可提供高达8.65％的高转换效率，而在相同条件下，基于N3的DSC的转换效率为8.35％。该染料将与空穴传输材料一起用于固态DSC中。
• Diastereoselective Homochiral Self-Assembly Between Anions and Cation in Solution
  作者：Olivier Maury、Jérôme Lacour、Hubert Le Bozec

  DOI：10.1002/1099-0682(20011)2001:1<201::aid-ejic201>3.0.co;2-9

  日期：2001.1

  propeller-like racemic tris(DEAS-bpy) ruthenium(II) cation B [DEAS-bpy = 4,4'-bis(diethylamino[TRISPHAT = tris(tetrachlorobenzenediolato)phosphate(V)]. This phenomenon is clearly shown by 1H NMR spectroscopic studies which reveal: (i) the existence of a rapid equilibrium between their homochiral and heterochiral associations, (ii) at room temperature, the preferential formation of the homochiral ion pairs with

  通过混合螺旋桨状外消旋三（DEAS-bpy）钌（II）阳离子B [DEAS-bpy = 4,4'-双（二乙氨基[TRISPHAT = tris（四氯苯二醇）磷酸盐（V）]，在溶液中发生非对映选择性同手性自组装)]. 1H NMR 光谱研究清楚地显示了这种现象，该研究表明：(i) 在它们的同手性和异手性缔合之间存在快速平衡，(ii) 在室温下，具有比例的同手性离子对的优先形成同手性/异手性 = 72:28，以及 (iii) 在 243 K，几乎纯的同手性关联 (B?,A?2) 和 (B?,A?2)。
• 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.
• Probing the Symmetry of the Nonlinear Optic Chromophore Ru(<i>trans</i>-4,4‘-diethylaminostyryl-2,2‘-bipyridine)₃²⁺:  Insight from Polarized Hyper-Rayleigh Scattering and Electroabsorption (Stark) Spectroscopy
  作者：Fredrick W. Vance、Joseph T. Hupp

  DOI：10.1021/ja9840044

  日期：1999.4.1

  Polarized hyper-Rayleigh scattering (HRS) has been used to interrogate a putative octupolar "super" chromophore Ru(trans-4,4'-diethylaminostyryl-2,2'-bipyridine)(3)(2+) While the hyperpolarizability (beta) is impressive, it is apparent from polarized HRS measurements that the symmetry of the excited state, and thus the hyperpolarizability tensor, is best described as dipolar in nature. Electroabsorption (electronic Stark effect) experiments support these findings, implying that changes in dipole moment (Delta mu) accompany optical excitation. The measured \Delta mu\ contributions from both metal-to-ligand charge transfer and intraligand transitions have been used to model the wavelength-dependent hyperpolarizability; reasonable qualitative agreement between experimental results and a simple three-state, two-level dipolar model is obtained.