Effect of Sulfur-Based Substituents on the Electronic Properties of Re(I) dppz Complexes

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• 作者：Michael G. Fraser ; Allan G. Blackman ; Garth I. S. Irwin ; Campbell P. Easton ; Keith C. Gordon
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：June 7, 2010
• 年：2010
• 卷：49
• 期：11
• 页码：5180-5189
• 全文大小：924K
• 年卷期：v.49,no.11(June 7, 2010)
• ISSN：1520-510X

文摘

A series of sulfur-substituted dppz-based ligands and their Re(I)(CO)₃Cl complexes are reported. The sulfur-substituted ligands and complexes show interesting electronic properties atypical of dppz-type systems. Substitution of dppz with thiocyanate (SCN) groups results in behavior typical of an electron withdrawing group. However, substitution of dppz with the electron donating trithiocarbonate (S₂CS) or deca-alkylthioether (Sdec) groups confer intraligand charge-transfer (ICT) from the S adduct to the phenazine lowest unoccupied molecular orbital (LUMO). Upon complexation of the substituted dppz ligand to Re(CO)₃Cl this ICT red-shifts and increases in intensity. Analysis of these observations using density functional theory (DFT) calculations and resonance Raman spectroscopy reveals that these transitions are a mixture of metal-to-ligand charge-transfer (MLCT) and S → phenazine ICT in nature. The synthesized compounds are also characterized using ¹H NMR spectroscopy, IR spectroscopy, and electrochemistry. Single-crystal X-ray analysis was performed on dppz(SCN)₂ (C₂₀H₁₈N₆S₂ a = 8.780 Å, b = 9.792 Å, c = 10.400 Å, α = 95.95°, β = 112.13°, γ = 95.38°, triclinic, P, Z = 2, R1 = 0.0306, wR2 = 0.0829.