New CNC Bis-Cyclometalated Platinum(II) Complexes: Synthesis, Structures, and Photophysical Properties

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• 作者：Sara Fuertes ; Simon K. Brayshaw ; Paul R. Raithby ; Stephanie Schiffers ; Mark R. Warren
• 刊名：Organometallics
• 出版年：2012
• 出版时间：January 9, 2012
• 年：2012
• 卷：31
• 期：1
• 页码：105-119
• 全文大小：782K
• 年卷期：v.31,no.1(January 9, 2012)
• ISSN：1520-6041

文摘

The reaction of a new ligand, ethyl 2,6-diphenylisonicotinate (EtO₂C鈥揅NC鈥揌₂), with K₂PtCl₄ in acetic acid affords the monocyclometalated complex [{(EtO₂C鈥揅NC鈥揌)Pt(渭-Cl)}₂] (1), which transforms to the bis-cyclometalated derivative [Pt(EtO₂C鈥揅NC)(DMSO)] (2) when heated in hot DMSO. Complex 2 is the precursor for preparing a new series of neutral mononuclear bis-cyclometalated complexes [Pt(EtO₂C鈥揅NC)(L)] (L = tht (3), PPh₃ (4), CN-^tBu (5), py (6), py-^tBu (7), py-NH₂ (8), py-CN (9), py-CONH₂ (10)). These new complexes have been characterized spectroscopically, and structures of 2鈥?b>10 have been determined crystallographically. Within each crystal structure the individual molecules pack in a head-to-tail arrangement. Noncovalent interactions, including 蟺路路路蟺, C鈥揌路路路O, C鈥揌路路路N, N鈥揌路路路Pt, N鈥揌路路路蟺, C鈥揌路路路蟺, and N鈥揌路路路O, contribute significantly to the supramolecular structures displayed by these complexes in the solid state. All complexes display UV鈥搗is absorptions in dichloromethane solution. Excitation and emission studies as well as lifetime measurements are described and can be correlated to the solid-state structures of the complexes. DFT and TDDFT computational studies have been performed on 5 and 8 which support the conclusions drawn from the photophysical studies.