[pentacyanoiron(II)-N-(2-pyrimidyl)-4,4'-bipyridinium](2-) | 917201-39-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: [pentacyanoiron(II)-N-(2-pyrimidyl)-4,4'-bipyridinium](2-)
• CAS: 917201-39-9
• 化学式: C₁₉H₁₁FeN₉
• 分子量: 421.204
• InChiKey: HBNZQCDRZKAMGL-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  [Fe(CN)3(CNH)2(N-(2-pyrimidyl)-4,4'-bipyridinium)] 在 Et₃N 作用下， 以 水 为溶剂， 生成 [pentacyanoiron(II)-N-(2-pyrimidyl)-4,4'-bipyridinium](2-)
  参考文献：
  名称：

  Pentacyanoiron(II) as an Electron Donor Group for Nonlinear Optics:  Medium-Responsive Properties and Comparisons with Related Pentaammineruthenium(II) Complexes

  摘要：

  In this article, we describe a series of complex salts in which electron-rich {Fe-II(CN)(5)}(3-) centers are coordinated to pyridyl ligands with electron-accepting N-methyl/aryl-pyridinium substituents. These compounds have been characterized by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d -> pi* metal-to-ligand charge-transfer (MLCT) bands. The relatively large static first hyperpolarizabilities, beta(0), increase markedly on moving from aqueous to methanol solutions, accompanied by large red-shifts in the MLCT transitions. Acidification of aqueous solutions allows reversible switching of the linear and NLO properties, as shown via both HRS and Stark experiments. Time-dependent density functional theory and finite field calculations using a polarizable continuum model yield relatively good agreement with the experimental results and confirm the large decrease in beta(0) on protonation. The Stark-derived beta(0) values are generally larger for related {Ru-II(NH3)(5)}(2+) complexes than for their {Fe-II(CN) (5)} (3-) analogues, consistent with the HRS data in water. However, the HRS data in methanol show that the stronger solvatochromism of the Fe-II complexes causes their NLO responses to surpass those of their Ru-II counterparts upon changing the solvent medium.

  DOI：

  10.1021/ja063449m