Tuning Excited States of Bipyridyl Platinum(II) Chromophores with 蟺-Bonded Catecholate Organometallic Ligands: Synthesis, Structures, TD-DFT Calculations, and Photophysical Properties

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• 作者：Jamal Moussa ; Lise-Marie Chamoreau ; Alessandra Degli Esposti ; Maria Pia Gullo ; Andrea Barbieri ; Hani Amouri
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：July 7, 2014
• 年：2014
• 卷：53
• 期：13
• 页码：6624-6633
• 全文大小：471K
• ISSN：1520-510X

文摘

A series of bipyridyl (bpy) Pt(II) complexes with 蟺-bonded catecholate (cat) [(bpy)Pt(L_M)][BF₄]_n (2鈥?b>5) (L_M = Cp*Rh(cat), n = 2; Cp*Ir(cat), n = 2; Cp*Ru(cat), n = 1; and (C₆H₆)Ru(cat), n = 2) were prepared and fully characterized. The molecular structures of the four compounds were determined and showed that the solid-state packing is different and dependent on the 蟺-bonded catecholate unit. For instance, while the (bpy)Pt(II) complexes 2 and 3 with rhodium and iridium catecholates did not show any Pt路路路Pt interactions those with the ruthenium catecholates 4 and 5 showed the presence of Pt路路路Pt and 蟺鈥撓€ interactions among individual units and generated one- and two-dimensional supramolecular chains. The photophysical properties of these compounds 2鈥?b>5 were investigated and showed that all compounds are luminescent at low temperature, in contrast to the well-known parent compound [(C₆H₄O₂)Pt(bpy)] (1), which is weakly luminescent at 77 K. Time-dependent density functional theory studies are advanced to explain this difference in behavior and to highlight the role of the 蟺-bonded catecholate system.