| 异核Au基电荷转移配合物的结构与Au-Rh配合物取代基效应和激发态的理论研究 |
| Theoretical Studies on the Au-based Charge-Transfer Complexes and Substituent Effects and Excited States of the Heterobimetallic Au-Rh Analogue |
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| 摘要: 采用SVWN、XαVWN和MP2方法优化了Au基电荷转移配合物[AuⅠMⅠ(CNH)2(PH2CH2PH2)2]2+(M=Co(1)，Rh (2)和Ir(3))的基态结构。计算表明3种方法都能描述Au-M弱相互作用(Au-M距离在0.268～0.302 nm范围内，伸缩振动频率在99～139 |
| 关键词: 异核Au基电荷转移配合物 激发态 取代基效应 密度泛函和从头算方法 |
| 基金项目: |
| Abstract: The ground-state structures of the Au-based charge-transfer complexes, [AuⅠMⅠ(CNH)2(PH2CH2PH2)2]2+(M=Co(1)，Rh (2) and Ir(3)), were optimized using the SVWN, XαVWN and MP2 methods. It was shown that the weak Au-M interaction was reasonably described. This is evident in the calculated Au-M distances (0.268～0.302 nm), stretching frequencies (99～139 cm-1) and bond orders (0.022～0.055). Among these methods, the distances calculated by the SVWN functional are closest to the reported experimental values. To confirm the substituent approximation and the choice of methods, we optimized the structures of [AuⅠRhⅠ(CNR′)2(PR2CH2PR2)2]2+(R=H，R′=Me (2a) and tBu (2b); R=Me, R′=H (2c) and Me (2d)) and [AuⅠMⅡ(CN)2(PH2CH2PH2)2]+(M=Ni (4)，Pd (5) and Pt (6)) at the SVWN level. The CIS (single excitation configuration interaction) calculations revealed that complex 2 features the lowest-energy metal-localized singlet and triplet excited states, along with the promotion of electrons into bonding orbitals. Associated with different TD-DFT (time-dependent density functional theory) methods and solvent-effect models, the fluorescent and phosphorescent emissions were predicted at 2.26～2.82 and 1.83～1.66 eV, respectively, in agreement with experimental values of 2.48 and 2.03 eV. We attributed these emission to the admixture of σ*[dz2(Rh)-dz2-y2(Au)]→σ[spz(Au-Rh)] (Metal-centered, MC), dz2(Rh)→spz(Au) (Metal to metal charge transfer, MMCT) and metal to ligand charge transfer (MLCT) transition characters. |
| Keywords: heterobimetallic Au-based charge-transfer complex excited state substituent effect DFT and ab initio method |
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| 郭元茹,潘清江.异核Au基电荷转移配合物的结构与Au-Rh配合物取代基效应和激发态的理论研究[J].无机化学学报,2009,25(3):439-446. |
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