4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine;(Z)-1,2-dicyanoethene-1,2-dithiolate;platinum(2+) | 173074-19-6

• 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-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine;(Z)-1,2-dicyanoethene-1,2-dithiolate;platinum(2+)
• CAS: 173074-19-6
• 化学式: C₂₂H₂₄N₄PtS₂
• 分子量: 603.671
• InChiKey: URPRREPMWSMQDJ-LWFKIUJUSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.08
• 重原子数：
  29
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  75.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  dichloro(4,4'-di-tert-butyl-2,2'-bipyridine)platinum(II) 、 disodium cis-1,2-dicyano-1,2-ethylenedithiolate 以 二氯甲烷 、 丙酮 为溶剂， 以68%的产率得到4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine;(Z)-1,2-dicyanoethene-1,2-dithiolate;platinum(2+)
  参考文献：
  名称：

  Tuning the Excited-State Properties of Platinum(II) Diimine Dithiolate Complexes

  摘要：

  Two series of Pt(diimine)(dithiolate) complexes have been prepared in order to investigate the effects of molecular design on the excited-state properties of this chromophore. The first series comprises Pt(dbbpy)(dithiolate) complexes where dbbpy = 4,4'-di-terr-butyl-2,2'-bipyridine and the dithiolates are 1-(tert-butylcarboxy)-1-cyanoethylene-2,2-dithiolate (tbcda), 1-diethylphosphonate-1-cyanoerhylene-2,2-dithiolate (cpdt), 6,7-dimethylquinoxaline-2,3-dithiolate (dmqdt), maleonitriledithiolate (mnt), and toluene-3,4-dithiolate (tdt). The second series comprises Pt(diimine)(tdt) complexes where the diimines are 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), 4,4'-di-tert-butyl-2,2'-bipyridine (dbbpy), 4,4'-dimethyl-2,2'-bipyridine (dmbpy), 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 5-chloro-1,10-phenanthroline (Cl-phen), 4,4'-dichloro-2,2'-bipyridine (Cl(2)bpy), and 4,4'-bis(ethoxycarbonyl)2,2'-bipyridine (EC-bpy). All of the compounds display solvatochromic absorption bands and solution luminescence, which are attributed to a common charge-transfer-to-diimine excited state. The excited-state energies can be tuned by approximately 1 eV through ligand variation. Solution lifetimes range from 1 ns to over 1000 ns and Phi(em) range from 6.4 x 10(-3) to less than 10(-5) in CH2Cl2. Based on these data, the nonradiative and radiative decay rate constants have been calculated. For the Pt(diimine)(tdt) series, the nonradiative decay rate constants increase exponentially with decreasing energy, in agreement with the Energy Gap Law, while those for the Pt(dbbpy)(dithiolate) complexes do not exhibit a similar correlation. Excited-state redox potentials have been estimated for all of the complexes from spectroscopic and electrochemical data. The ability to tune the driving force for bimolecular excited-state electron-transfer reactions has been demonstrated for eight of the complexes using reductive and oxidative quenching experiments.

  DOI：

  10.1021/ja951345y

文献信息

• Tuning the Excited-State Properties of Platinum(II) Diimine Dithiolate Complexes
  作者：Scott D. Cummings、Richard Eisenberg

  DOI：10.1021/ja951345y

  日期：1996.1.1

  Two series of Pt(diimine)(dithiolate) complexes have been prepared in order to investigate the effects of molecular design on the excited-state properties of this chromophore. The first series comprises Pt(dbbpy)(dithiolate) complexes where dbbpy = 4,4'-di-terr-butyl-2,2'-bipyridine and the dithiolates are 1-(tert-butylcarboxy)-1-cyanoethylene-2,2-dithiolate (tbcda), 1-diethylphosphonate-1-cyanoerhylene-2,2-dithiolate (cpdt), 6,7-dimethylquinoxaline-2,3-dithiolate (dmqdt), maleonitriledithiolate (mnt), and toluene-3,4-dithiolate (tdt). The second series comprises Pt(diimine)(tdt) complexes where the diimines are 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), 4,4'-di-tert-butyl-2,2'-bipyridine (dbbpy), 4,4'-dimethyl-2,2'-bipyridine (dmbpy), 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 5-chloro-1,10-phenanthroline (Cl-phen), 4,4'-dichloro-2,2'-bipyridine (Cl(2)bpy), and 4,4'-bis(ethoxycarbonyl)2,2'-bipyridine (EC-bpy). All of the compounds display solvatochromic absorption bands and solution luminescence, which are attributed to a common charge-transfer-to-diimine excited state. The excited-state energies can be tuned by approximately 1 eV through ligand variation. Solution lifetimes range from 1 ns to over 1000 ns and Phi(em) range from 6.4 x 10(-3) to less than 10(-5) in CH2Cl2. Based on these data, the nonradiative and radiative decay rate constants have been calculated. For the Pt(diimine)(tdt) series, the nonradiative decay rate constants increase exponentially with decreasing energy, in agreement with the Energy Gap Law, while those for the Pt(dbbpy)(dithiolate) complexes do not exhibit a similar correlation. Excited-state redox potentials have been estimated for all of the complexes from spectroscopic and electrochemical data. The ability to tune the driving force for bimolecular excited-state electron-transfer reactions has been demonstrated for eight of the complexes using reductive and oxidative quenching experiments.