Characterization of the lowest excited states of metal complexes in the near infrared-region

近红外区域金属配合物最低激发态的表征

• 批准号: 02403013
• 负责人: KAIZU Youkoh
• 金额: $ 13.82万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02403013/
• 关键词: Electronic absorption spectra in the near infrared region; Lutetium phthalocyanine dimer radical; Low-spin Ru(III) complexes; Electronic state of metal complexes; 赤外・近赤外領域分光; 低い電子状態; ルテニウム(III)錯体の最低(d,d^*)状態; Yb^<+3>錯体の振電バンド; トリス(βージケトナト)ルテニウム(III

Electronic adsorption bands of Ru(III) complexes, Ru(acac)_3, Ru(dpm)_3, Ru(tfa)_3, [Ru(bpy)_3]^<3+> and [Ru(NH_3)_6]^<3+>, were observes at the near infrared region by using an FT-IR spectrometer. The bands, sppeared in the near infrared region (4000*7000cm^<-1>) are assigned to the (d,d^*) transition ^2T_2*^6A_1, and ligand field and Racah parameters are estimated based on the assignment.The ground state and the lowest excited states of lutetium phthalocyanine dimer radical [Lu(Pc)_2], and those of related compounds, [Lu(Nc)_2] and [Lu(Nc)(Pc)] are studied by CI calculation on localized orbital basis set. The orbitals, which are localized on either of two ligands, are obtained by a unitarytransformation of semiempirical SCMO's of the dimer. The lowest three band 7X10^3, 10X10^3 and 15X10^3cm^<-1> for [Lu(Pc)_2]; 6X10^3cm^<-1>, 8X10^3cm^<-1> and 13X10^3cm^<-1> for [Lu(Nc)_2] are assigned to the excited state 1B_1, 2E_1, and 3E_1, respectively. The ground state of the C_<4v> heterodimer, [Lu(Nc)(Pc)], has a population of a hole more in Nc ring than in Pc ring. The population shifts toward Pc in 2A_2 excited state.

用傅立叶变换红外光谱仪在近红外区观察到Ru（acac）_3、Ru（dpm）_3、Ru（tfa）_3、[Ru（bpy）_3]^<3+>和[Ru（NH_3）_6]^<3+>配合物的电子吸附带。用<-1>定域轨道基组CI计算方法研究了酞菁镥二聚体自由基[Lu（Pc）_2]及其相关化合物[Lu（Nc）_2]和[Lu（Nc）（Pc）]的基态和最低激发态.通过对二聚体的半经验SCMO进行么正变换，得到了位于两个配体之一上的轨道。[Lu（Pc）_2]的最低三个带7X10^3、10X10^3和15X10^3cm^<-1>，[Lu（Nc）_2]的最低三个带6X10^3cm^、<-1>8X10^3cm^<-1>和13X10^3cm^<-1>分别归属于激发态1B_1、2E_1和3E_1。C_<4v>异二聚体的基态[Lu（Nc）（Pc）]在Nc环上比在Pc环上具有更多的空穴布居。在2A_2激发态，粒子数向Pc方向移动。

项目成果

N.Ishikawa: "Localized orbital study of the electronic structure of Phthalocyanine dimers." J.Phys.Chem.96. 8832-8839 (1992)

N.Ishikawa：“酞菁二聚体电子结构的局域轨道研究。”

Naoto Ishikawa: "Localized orbital study on the electronic structure of phthalocyanine dimers." J.Phys.Chem. 96,(22). 8832-8839 (1992)

Naoto Ishikawa：“酞菁二聚体电子结构的局域轨道研究。”

Hiroshi Kobayashi: "Electronic transfer between lignads in the tris(2,2'-bipyridine)complexes consisting of mono-anion radicals: delocalization versus localization." Mol.Phys.

Hiroshi Kobayashi：“由单阴离子自由基组成的三（2,2-联吡啶）复合物中配体之间的电子转移：离域与本地化。”

Takuhiro Otsuka: "The crystal water affecting the ^2E_g→ ^4A_<2g> relaxation in tris-(oxalato)chromate(III) complexes." Bull.Chem.Soc.Jpn.65. 3378-3385 (1992)

Takuhiro Otsuka：“结晶水影响三(草酸根)铬酸盐(III)配合物中的^2E_g→^4A_<2g>弛豫。”Bull.Chem.Soc.Jpn.65（1992）。

Hiroshi Kobayashi: "Electronic transfer between ligands in the tris(2,2'-bipyri-dine)complexes consisting of mono-anion radicals:delocalization versus localization." Mol.Phys.,.

Hiroshi Kobayashi：“由单阴离子自由基组成的三（2,2-联吡啶）复合物中配体之间的电子转移：离域与定位。”