Control of Spin purity in excited state using distortion of coordination structure in transition metal compounds

利用过渡金属化合物中配位结构的畸变控制激发态的自旋纯度

• 批准号: 14540515
• 负责人: NOZAWA Koichi
• 金额: $ 2.37万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540515/
• 关键词: Intersystem crossing; Spin-Orbit interaction; phosphorescence; Singlet MLCT; triplet MLCT; Franck-Condon Analysis; ケイ光; 銅(I)錯体; 白金(O)錯体

Photophysical properties of singlet and triplet metal-to-ligand charge transfer states (MLCT) of d^<10> metal compounds with tetrahedral structure, e.g., [Cu(I)(diimine)_2]^+ or [Pt(0)(binap)_2] have been studied. The lifetimes of 'MLCT were determined to be 13-16 ps for the Cu(I) compounds and 3.2 ps for the Pt(O) compound, much longer than expected from strong spin-orbit coupling constant of Cu-3d (880 cm^<-1>) or Pt-5d (4000 cm^<-1>) orbitals. Theoretical analysis based on density functional theory revealed that structural distortion in the MLCT states causes large energy splitting between HOMO and HOMO -1, which prevents a very fast ISC due to the strong spin-orbit interactions between these orbitals. Although the phosphorescence observed at lower temperatures is due to intensity borrowing from ^1MLCT→GS transition the large energy difference between HOMO and HOMO -2 reduces the extent of mixing between the lowest ^3MLCT and ^1MLCT due to spin-orbit interaction, thereby decreasing … More the radiative rate of the phosphorescence.A PC-clustering computer system with the peak' performance of 90Gflops was developed. To understand ultrafast photochemical processes following the light excitation of Ru(II)-Co(III) binuclear compounds, potential energy curves along with both intramolecular coordinates and solvent coordinates were calculated and the magnitudes of intramolecular electronic interaction energy between these potential curves were evaluated. It was revealed that ultrafact energy and electron transfer from MLCT state of the Ru(II) moiety to the Co(III) moiety occurred with vibronic coupling due to asymmetric vibrations which mixed d_<x2-y2> orbital on cobalt and π-orbitals on nitrogen coordinating to the cobalt.A new method to assess the geometries obtained from quantum chemical calculations using experimental emission spectra was developed. The fluorescence spectra simulated from geometries obtained using several quantum chemical models such as UHF, UDFT, TDDFT, CIS, and CASSCF were compared with the experimental ones, confirming the accuracy of UDFT and TDDFT calculation on geometries. Less

具有四面体结构的d^金属化合物的单重态和三重态金属-配体电荷转移态（MLCT）的光物理性质<10>，例如，[Cu（I）（diimine）_2]^+或[Pt（0）（binap）_2]的反应。对于Cu（I）化合物，MLCT的寿命被确定为13-16 ps，对于Pt（O）化合物，MLCT的寿命被确定为3.2 ps，比从Cu-3d（880 cm-3）或Pt-5d（4000 cm-3）轨道的强自旋-轨道耦合常数所预期的长得多<-1><-1>。基于密度泛函理论的理论分析表明，MLCT态的结构畸变导致HOMO和HOMO-1之间的大的能量分裂，由于这些轨道之间的强自旋轨道相互作用，这阻止了非常快的ISC。虽然在较低温度下观察到的磷光是由于从^1MLCT→GS跃迁借用的强度，但由于自旋轨道相互作用，HOMO和HOMO-2之间的大能量差降低了最低^3MLCT和^1MLCT之间的混合程度，从而降低了 ...更多信息 研制了一个峰值性能为90 Gflops的PC集群计算机系统。为了理解超快光化学过程的光激发下的Ru（II）-Co（III）双核化合物，势能曲线沿着分子内坐标和溶剂坐标计算和分子内电子相互作用能的大小之间的这些潜在的曲线进行了评估。结果表明，Ru（II）的MLCT态向Co（III）的超事实能量转移和电子转移是由于Co（III）的d轨道和Co（III）配位的氮原子的π轨道的不对称振动引起的电子振动耦合引起<x2-y2>的.将UHF、UDFT、TDDFT、CIS和CASSCF等量子化学模型计算的荧光光谱与实验结果进行了比较，证实了UDFT和TDDFT计算的准确性。少

项目成果

M.Abe, T.Kawakami, K.Noz, M.Nojima: "Mechanism of Stereo- and Regioselectivity in the Paterno-Buchi Reaction of Furan Derivatives with Aromatic Carbonyl Compounds : Importance of the Conformational Distribution in the Intermediary Triplet 1,4-Diradicals.

M.Abe、T.Kawakami、K.Noz、M.Nojima：“呋喃衍生物与芳香族羰基化合物的 Paterno-Buchi 反应中的立体和区域选择性机制：中间三联体 1,4- 中构象分布的重要性

Zainul Abedin Siddique 他: "Structure-dependent photophysical properties of singlet and triplet metal-to-ligand charge transfer state in copper(I) 〜"Inorg.Chem.. 42. 6366-6378 (2003)

Zainul Abedin Siddique 等人：“铜 (I) 中单线态和三线态金属到配体电荷转移态的结构依赖性光物理性质 ~” Inorg.Chem.. 42. 6366-6378 (2003)

Manabu Abe, Waldemar Adam, Weston Thatcher Borden, Masanori Hattori, David A.Hrovat, Masatomo Nojima, Koichi Nozaki, Jakob Wirz: "Effects of Spiroconjugation on the Calculated Singlet-Triplet Energy Gap in 2,2-Diallcoxycyclopentane-1,3-diyls and on the Ex

Manabu Abe、Waldemar Adam、Weston Thatcher Borden、Masanori Hattori、David A.Hrovat、Masatomo Nojima、Koichi Nozaki、Jakob Wirz：“螺共轭对 2,2-二烷氧基环戊烷-1,3- 中计算的单重态-三重态能隙的影响

Zainul Abedin Siddique, Takeshi Ohno, Koichi Nozaki, Taro Tsuboinura: "Intense fluorescence from metal-to-ligand charge transfer state in [Pt(0)(binap)_2] [binap = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]"Inorg.Chem.. 43(2). 663-673 (2004)

Zainul Abedin Siddique、Takeshi Ohno、Koichi Nozaki、Taro Tsuboinura：“[Pt(0)(binap)_2] [binap = 2,2-双(二苯基膦)-1 中金属到配体电荷转移态的强荧光”

Z.A.Siddique, K.Nozaki: "Intense fluorescence of metal-to-ligand charge transfer state in [Pt(0)(binap)_2] [binap=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]"Inorganic Chemistry. 43. 663-673 (2004)

Z.A.Siddique、K.Nozaki：“[Pt(0)(binap)_2] [binap=2,2-双(二苯基膦)-1,1-联萘]中金属到配体电荷转移状态的强荧光