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.

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
Creators	Fuertes Lorda, S., Brayshaw, S. K., Raithby, P. R., Schiffers, S. and Warren, M. R.
DOI	10.1021/om200589q
Departments	Faculty of Science > Chemistry
Publisher Statement	Raithby_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
Refereed	Yes
Status	Published
ID Code	28699