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

Sara Fuertes Lorda, Simon K Brayshaw, Paul R Raithby, Stefanie Schiffers, Mark R Warren

Research output: Contribution to journalArticle

35 Citations (Scopus)
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Abstract

The reaction of a new ligand, ethyl 2,6-diphenylisonicotinate (EtO(2)C-CAN boolean AND C-H(2)), with K(2)PtCl(4) in acetic acid affords the monocyclometalated complex [{(EtO(2)C-CANAC-H)Pt(mu-Cl)}(2)] (1), which transforms to the bis-cyclometalated derivative [Pt(EtO(2)C-C boolean AND N boolean AND C)(DMS0)] (2) when heated in hot DMSO. Complex 2 is the precursor for preparing a new series of neutral mononuclear bis-cyclometalated complexes [Pt(EtO(2)C-CAN boolean AND C)(L)] (L = tht (3), PPh(3) (4), CN-(t)Bu (5), py (6), py-tBu (7), py-NH(2) (8), py-CN (9), py-CONH(2) (10)). These new complexes have been characterized spectroscopically, and structures of 2-10 have been determined crystallographically. Within each crystal structure the individual molecules pack in a head-to-tail arrangement. Noncovalent interactions, including pi center dot center dot center dot pi; C-H center dot center dot center dot O, C-H center dot center dot center dot N, N-H center dot center dot center dot Pt, N-H center dot center dot center dot pi, C-H center dot center dot center dot O, and N-H center dot center dot center dot O, contribute significantly to the supramolecular structures displayed by these complexes in the solid state. All complexes display UV-vis 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.
Original languageEnglish
Pages (from-to)105-119
Number of pages15
JournalOrganometallics
Volume31
Issue number1
DOIs
Publication statusPublished - 2012

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