4,4'-bis(4-bromophenyl)-6,6'-dimethyl-2,2'-bipyridine | 1427205-00-2

• 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(4-bromophenyl)-6,6'-dimethyl-2,2'-bipyridine
• 英文别名: 4-(4-Bromophenyl)-2-[4-(4-bromophenyl)-6-methylpyridin-2-yl]-6-methylpyridine；4-(4-bromophenyl)-2-[4-(4-bromophenyl)-6-methylpyridin-2-yl]-6-methylpyridine
• CAS: 1427205-00-2
• 化学式: C₂₄H₁₈Br₂N₂
• 分子量: 494.228
• InChiKey: BAFSJZRLTBUJRD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4'-bis(4-bromophenyl)-6,6'-dimethyl-2,2'-bipyridine 、 二苯胺 在 二(三叔丁基膦)钯 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 以71.4%的产率得到4,4'-bis(4-diphenylaminophenyl)-6,6'-dimethyl-2,2'-bipyridine
  参考文献：
  名称：

  杂配双（二亚胺）铜（I）染料中辅助配体中的炔基间隔基是否有利于染料敏化太阳能电池中的染料性能？

  摘要：

  4,4'-双(4-二甲氨基苯基)-6,6'-二甲基-2,2'-联吡啶的合成 (1),4,4'-双(4-二甲氨基苯乙炔基)-6,6'-二甲基-2,2'-联吡啶 (2)、4,4'-双(4-二苯基氨基苯基)-6,6'-二甲基-2,2'-联吡啶 (3) 和 4,4'-双(4-报道了二苯氨基苯乙炔基)-6,6'-二甲基-2,2'-联吡啶 (4) 及其均配铜 (I) 配合物 [CuL2][PF6] (L = 1–4) 的制备和表征。除了分配给配体内和金属到配体电荷转移组合的可见光区域的吸收之外，配合物的溶液吸收光谱还表现出以配体为中心的吸收。杂配体 [Cu(5)(Lancillary)]+ 染料，其中 5 是锚定配体 ((6,6'-二甲基-[2,2'-联吡啶]-4,4'-二基)双(4,1-亚苯基））双（膦酸）和 Lancillary = 1–4 已组装在染料敏化太阳能电池（DSC）中的掺氟氧化锡（FTO）-TiO2

  DOI：

  10.3390/molecules25071528

文献信息

• Improving the photoresponse of copper(i) dyes in dye-sensitized solar cells by tuning ancillary and anchoring ligand modules
  作者：Biljana Bozic-Weber、Sven Y. Brauchli、Edwin C. Constable、Sebastian O. Fürer、Catherine E. Housecroft、Frederik J. Malzner、Iain A. Wright、Jennifer A. Zampese

  DOI：10.1039/c3dt51416a

  日期：——

  The syntheses of five homoleptic copper(I) complexes [CuL2][PF6] are described in which L is a 4,4′-di(4-bromophenyl)-6,6′-dialkyl-2,2′-bipyridine ligand (compounds 1–4 with methyl, nbutyl, isobutyl and hexyl substituents, respectively) or 4,4′-di(4-bromophenyl)-6,6′-diphenyl-2,2′-bipyridine (5). The new ligands 2–5 and copper(I) complexes [CuL2][PF6] (L = 1–5) have been fully characterized. The single crystal structures of 2[Cu(1)2][PF6]}·3Me2CO, [Cu(2)2][PF6], 2[Cu(3)2][PF6]}·Et2O and [Cu(5)2][PF6]·CH2Cl2 have been determined. The first three structures show similar distorted tetrahedral environments for the Cu+ ions with angles between the least squares planes of the bpy domains of 85.6, 86.4 and 82.9°, respectively; in contrast, the Cu+ ion in [Cu(5)2][PF6]·CH2Cl2 is in a flattened coordinate environment due to intra-cation face-to-face π-interactions. The solution absorption spectra of the complexes with ligands 1–4 are virtually identical with an MLCT band with values of λmax = 481–488 nm. In contrast, the absorption spectrum of [Cu(5)2][PF6] shows two broad bands in the visible region. Cyclic voltammetric data show that oxidation of the copper(I) centre occurs at a more positive potential in [Cu(2)2][PF6], [Cu(3)2][PF6] and [Cu(4)2][PF6] than in [Cu(1)2][PF6] or [Cu(5)2][PF6] with the latter being oxidized at the lowest potential. The complexes have been used to prepare dye-sensitized solar cells (DSCs) incorporating heteroleptic dyes of type [Cu(L)(Lanchor)]+ where L is 1–5 and Lanchor is a 6,6′-dimethyl-2,2′-bipyridine functionalized in the 4- and 4′-positions with phosphonic acid groups with (Lanchor = 7) and without (Lanchor = 6) a spacer between the metal-binding and anchoring domains. The presence of the spacer results in enhanced performances of the dyes, and the highest energy conversion efficiencies are observed for the dyes [Cu(3)(7)]+ (η = 2.43% compared to 5.96% for standard dye N719) and [Cu(5)(7)]+ (η = 2.89% compared to 5.96% for N719). Measurements taken periodically over the course of a week indicate that the cells undergo a ripening process (most clearly seen for [Cu(5)(6)]+ and [Cu(5)(7)]+) before their optimum performances are achieved. IPCE (EQE) data are presented and confirm that, although the photo-to-current conversions are promising (37–49% for λmax ≈ 480 nm), the copper(I) dyes do not realize the broad spectral response exhibited by N719.

  描述了合成五种均配铜(I)配合物[CuL2][PF6]的过程，其中L是4,4′-二(4-溴苯基)-6,6′-二烷基-2,2′-联吡啶配体（化合物1-4分别具有甲基、正丁基、异丁基和己基取代基）或4,4′-二(4-溴苯基)-6,6′-二苯基-2,2′-联吡啶（5）。新配体2-5和铜(I)配合物[CuL2][PF6]（L=1-5）已得到充分表征。已测定2[Cu(1)2][PF6]}·3Me2CO，[Cu(2)2][PF6]，2[Cu(3)2][PF6]}·Et2O和[Cu(5)2][PF6]·CH2Cl2的单晶结构。前三个结构显示Cu+离子处于类似扭曲的四面体环境中，bpy域的最小二乘平面的夹角分别为85.6、86.4和82.9°；相比之下，[Cu(5)2][PF6]·CH2Cl2中的Cu+离子由于阳离子内部的面对面的π相互作用处于扁平的配位环境中。配合物与配体1-4的溶液吸收光谱几乎相同，具有λmax=481-488 nm的MLCT带。相比之下，[Cu(5)2][PF6]的吸收光谱在可见区显示出两个宽阔的带。循环伏安数据表明，铜(I)中心的氧化在[Cu(2)2][PF6]、[Cu(3)2][PF6]和[Cu(4)2][PF6]中比在[Cu(1)2][PF6]或[Cu(5)2][PF6]中发生在更高的电位，后者被氧化在最低电位。这些配合物已被用于制备染料敏化太阳能电池(DSCs)，整合了[Cu(L)(Lanchor)]+型杂配体染料，其中L是1-5，Lanchor是6,6′-二甲基-2,2′-联吡啶，在4-和4′-位置带有膦酸基团（Lanchor=7）和没有间隔基（Lanchor=6）在金属结合和锚定域之间。间隔基的存在导致染料性能增强，最高的能量转换效率在染料[Cu(3)(7)]+（η=2.43%，而标准染料N719为5.96%）和[Cu(5)(7)]+（η=2.89%，而N719为5.96%）中观察到。一周内的定期测量表明，电池经历了一个成熟过程（最明显的是[Cu(5)(6)]+和[Cu(5)(7)]+），然后达到最佳性能。IPCE（EQE）数据显示，尽管光对电流的转换有希望（λmax≈480 nm时为37-49%），但铜(I)染料未能实现N719展示的宽光谱响应。
• Peripheral halo-functionalization in [Cu(N^N)(P^P)]⁺ emitters: influence on the performances of light-emitting electrochemical cells
  作者：Fabian Brunner、Laura Martínez-Sarti、Sarah Keller、Antonio Pertegás、Alessandro Prescimone、Edwin C. Constable、Henk J. Bolink、Catherine E. Housecroft

  DOI：10.1039/c6dt02665f

  日期：——

  heteroleptic [Cu(N^N)(P^P)][PF6] complexes is described in which P^P = bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) and N^N = 4,4′-diphenyl-6,6′-dimethyl-2,2′-bipyridine substituted in the 4-position of the phenyl groups with atom X (N^N = 1 has X = F, 2 has X = Cl, 3 has X = Br, 4 has X = I; the benchmark N^N ligand with X = H is 5). These complexes

  描述了一系列杂合[Cu（N ^ N）（P ^ P）] [PF 6 ]配合物，其中P ^ P =双（2-（二苯基膦基）苯基）醚（POP）或4,5-双（ （二苯基膦基）-9,9-二甲基an吨（xantphos）和N ^ N = 4,4'-二苯基-6,6'-二甲基-2,2'-联吡啶在苯基的4位上被原子X（ N ^ N = 1有X = F，2具有X = Cl，3具有X = Br，4具有X = I; X = H的基准N ^ N配体为5）。这些配合物已通过多核NMR光谱，质谱，元素分析和循环伏安法进行了表征。还报道了代表性的单晶结构。该溶液的吸收光谱的特征在于高能量带（从配体为中心的过渡产生的）上从X = H将X = I被红移，并且具有广泛的金属到配体的电荷传输带λ最大值在范围387–395 nm。十种络合物是溶液中的黄色发射器，固态时是黄色或橙黄色的发射器。对于给定的N ^ N配体，溶液的光致发光（PL）光谱显示从[Cu（N
• Factors controlling the photoresponse of copper(<scp>i</scp>) diimine dyes containing hole-transporting dendrons in dye-sensitized solar cells: substituent and solvent effects
  作者：Sven Y. Brauchli、Biljana Bozic-Weber、Edwin C. Constable、Nik Hostettler、Catherine E. Housecroft、Jennifer A. Zampese

  DOI：10.1039/c4ra03700f

  日期：——

  efficiencies are obtained with the second-generation dyes [Cu(13)(L)]+ (L = 7–11 with Me, nBu, isoBu, hexyl, Ph groups); [Cu(13)(12)]+ (12 contains 2-naphthyl groups in the 6,6′-positions) and its first-generation analogue [Cu(13)(6)]+ perform poorly. When CH2Cl2 is used in the dipping cycle, DSCs with dyes [Cu(13)(1)]+ and [Cu(13)(7)]+ (6,6′-Me2-substituted) show the highest VOC, JSC and η values,

  带有不同的6,6'-取代基（Me，n Bu，iso Bu，己基，Ph和2-萘基）并带有第一代（配体1-6）的两个2,2'-联吡啶（bpy）配体系列据报道，第二代（配体7-12）空穴在4,4'-位上传输树突。它们已被掺入均相铜（I）配合物[CuL 2 ] [PF 6 ]。用锚定配体（（6,6'-二甲基-[2,2'-联吡啶] -4,4'-二基）双（4,1-亚苯基））双（膦酸）功能化的FTO / TiO 2电极，将13滴入[CuL]的CH 2 Cl 2或丙酮溶液中2 ] [PF 6 ]产生两个系列的表面结合型杂色染料。评估了它们在染料敏化太阳能电池（DSC）中的性能。染料功能化电极的固态吸收光谱表明，如果在染料浸渍循环中使用丙酮而不是CH 2 Cl 2，则染料吸收量更大，并且使用丙酮制得的DSC通常比使用CH 2 Cl制得的类似DSC更好。 2。使用丙酮浸渍溶液，第二代染料[Cu（ 13）（L）]
• Back to the future: asymmetrical DπA 2,2′-bipyridine ligands for homoleptic copper(<scp>i</scp>)-based dyes in dye-sensitised solar cells
  作者：Guglielmo Risi、Mike Devereux、Alessandro Prescimone、Catherine E. Housecroft、Edwin C. Constable

  DOI：10.1039/d3ra00437f

  日期：——

  push–pull strategy with electron-releasing and electron-withdrawing (anchoring) ligands. In a new paradigm we have designed new DπA ligands incorporating diarylaminophenyl donor substituents and phosphonic acid anchoring groups. These new ligands function as organic dyes. For two separate classes of DπA ligands with 2,2′-bipyridine metal-binding domains, the DSCs containing the copper(I) complexes [Cu(DπA)2]+

  在染料敏化太阳能电池 (DSC) 中用作敏化剂的金属络合物通常使用具有电子释放和吸电子（锚定）配体的推拉策略构建。在一个新的范例中，我们设计了新的 DπA 配体，其中包含二芳基氨基苯基供体取代基和膦酸锚定基团。这些新配体起到有机染料的作用。对于具有 2,2'-联吡啶金属结合结构域的两类不同的 DπA 配体，含有铜 ( I ) 配合物 [Cu(DπA) 2 ] +的 DπA 比推拉类似物 [Cu(DD)(机管局）] +。此外，我们首次证明配合物 [Cu(DπA) 2 ] +在 DSC 中表现优于有机 DπA 染料。借助密度泛函理论 (DFT) 和瞬态 DFT (TD-DFT) 研究，综合研究和器件性能合理化。
• Are Alkynyl Spacers in Ancillary Ligands in Heteroleptic Bis(diimine)copper(I) Dyes Beneficial for Dye Performance in Dye-Sensitized Solar Cells?
  作者：Guglielmo Risi、Mariia Becker、Catherine E. Housecroft、Edwin C. Constable

  DOI：10.3390/molecules25071528

  日期：——

  The syntheses of 4,4′-bis(4-dimethylaminophenyl)-6,6′-dimethyl-2,2′-bipyridine (1), 4,4′-bis(4-dimethylaminophenylethynyl)-6,6′-dimethyl-2,2′-bipyridine (2), 4,4′-bis(4-diphenylaminophenyl)-6,6′-dimethyl-2,2′-bipyridine (3), and 4,4′-bis(4-diphenylaminophenylethynyl)-6,6′-dimethyl-2,2′-bipyridine (4) are reported along with the preparations and characterisations of their homoleptic copper(I) complexes

  4,4'-双(4-二甲氨基苯基)-6,6'-二甲基-2,2'-联吡啶的合成 (1),4,4'-双(4-二甲氨基苯乙炔基)-6,6'-二甲基-2,2'-联吡啶 (2)、4,4'-双(4-二苯基氨基苯基)-6,6'-二甲基-2,2'-联吡啶 (3) 和 4,4'-双(4-报道了二苯氨基苯乙炔基)-6,6'-二甲基-2,2'-联吡啶 (4) 及其均配铜 (I) 配合物 [CuL2][PF6] (L = 1–4) 的制备和表征。除了分配给配体内和金属到配体电荷转移组合的可见光区域的吸收之外，配合物的溶液吸收光谱还表现出以配体为中心的吸收。杂配体 [Cu(5)(Lancillary)]+ 染料，其中 5 是锚定配体 ((6,6'-二甲基-[2,2'-联吡啶]-4,4'-二基)双(4,1-亚苯基））双（膦酸）和 Lancillary = 1–4 已组装在染料敏化太阳能电池（DSC）中的掺氟氧化锡（FTO）-TiO2