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


Reference:

Fuertes Lorda, S., Brayshaw, S. K., Raithby, P. R., Schiffers, S. and Warren, M. R., 2012. New C∧N∧C Bis-Cyclometalated Platinum(II) Complexes: Synthesis, Structures, and Photophysical Properties. Organometallics, 31 (1), pp. 105-119.

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    Official URL:

    http://dx.doi.org/10.1021/om200589q

    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.

    Details

    Item Type Articles
    CreatorsFuertes Lorda, S., Brayshaw, S. K., Raithby, P. R., Schiffers, S. and Warren, M. R.
    DOI10.1021/om200589q
    DepartmentsFaculty of Science > Chemistry
    Publisher StatementRaithby_Organometallics_2012_31_1_105.pdf: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/om200589q
    RefereedYes
    StatusPublished
    ID Code28699

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