2,3-diphenyl-6,7-di-p-tolyl-1,4,5,8-tetraazaphenanthrene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 2,3-diphenyl-6,7-di-p-tolyl-1,4,5,8-tetraazaphenanthrene
• 英文别名: 2,3-Bis(4-methylphenyl)-8,9-diphenylpyrazino[2,3-f]quinoxaline；2,3-bis(4-methylphenyl)-8,9-diphenylpyrazino[2,3-f]quinoxaline
• 化学式: C₃₆H₂₆N₄
• 分子量: 514.629
• InChiKey: NYNOJMKRZGPEIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  40
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetrakis(actonitrile)copper(I) hexafluorophosphate 、 2,3-diphenyl-6,7-di-p-tolyl-1,4,5,8-tetraazaphenanthrene 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 [Cu(2,3-diphenyl-6,7-di-p-tolyl-1,4,5,8-tetraazaphenanthrene)₂]PF₆
  参考文献：
  名称：

  Homoleptic tetraazaphenanthrene-based copper(I) complexes: Synthesis, spectroscopic characterization, crystal structures and computational studies

  摘要：

  Three new Cu(I) complexes containing bidentate N<^>N donor ligands with the general formula [Cu(N<^>N)(2)][PF6] (N<^>N = 2,3-diphenyl-6,7-di-p-tolyl-1,4,5,8-tetraazaphenanthrene (L-1), 2,3-diphenyl-6,7-di(2-thienyl)-1,4,5,8-tetraazaphenanthrene (L-2), and 2,3-diphenyl-6,7-di-p-fluorophenyl-1,4,5,8-tetraazaphenanthrene (L-3), were prepared by the reaction of [Cu(CH3CN) (4)][PF6] with two equivalents of the N<^>N ligand. Single-crystal X-ray diffraction analysis confirmed that in each complex the metal displays a distorted tetrahedral geometry surrounded by the four N atoms of the two sterically hindered substituted tetraazaphenanthrene (TAP) ligands. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT), calculations were used to study the ground state properties and interpret the absorption spectra for these Cu(I) complexes. The calculations show that the lowest-energy excitations of all complexes are dominated by d pi(Cu) --> pi*(L), metal-to-ligand charge transfer, (MLCT) excitations. Electronic difference density maps (EDDMs) were calculated, indicating the change of electron density in the singlet excited states. The degree of filling of the coordination sphere (G parameter) by the ligands was calculated taking into account the ligand-ligand overlap, and compared to the related bis(2,9-disubstituted phenanthroline) Cu(I) complexes. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2014.08.052

文献信息

• Homoleptic tetraazaphenanthrene-based copper(I) complexes: Synthesis, spectroscopic characterization, crystal structures and computational studies
  作者：Reza Kia、Mirko Scholz、Paul R. Raithby、Simone Techert

  DOI：10.1016/j.ica.2014.08.052

  日期：2014.11

  Three new Cu(I) complexes containing bidentate N<^>N donor ligands with the general formula [Cu(N<^>N)(2)][PF6] (N<^>N = 2,3-diphenyl-6,7-di-p-tolyl-1,4,5,8-tetraazaphenanthrene (L-1), 2,3-diphenyl-6,7-di(2-thienyl)-1,4,5,8-tetraazaphenanthrene (L-2), and 2,3-diphenyl-6,7-di-p-fluorophenyl-1,4,5,8-tetraazaphenanthrene (L-3), were prepared by the reaction of [Cu(CH3CN) (4)][PF6] with two equivalents of the N<^>N ligand. Single-crystal X-ray diffraction analysis confirmed that in each complex the metal displays a distorted tetrahedral geometry surrounded by the four N atoms of the two sterically hindered substituted tetraazaphenanthrene (TAP) ligands. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT), calculations were used to study the ground state properties and interpret the absorption spectra for these Cu(I) complexes. The calculations show that the lowest-energy excitations of all complexes are dominated by d pi(Cu) --> pi*(L), metal-to-ligand charge transfer, (MLCT) excitations. Electronic difference density maps (EDDMs) were calculated, indicating the change of electron density in the singlet excited states. The degree of filling of the coordination sphere (G parameter) by the ligands was calculated taking into account the ligand-ligand overlap, and compared to the related bis(2,9-disubstituted phenanthroline) Cu(I) complexes. (C) 2014 Elsevier B.V. All rights reserved.