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Facile Approaches to Phosphorescent Bis(cyclometalated) Pentafluorophenyl Pt IV Complexes: Photophysics and Computational Studies
Author(s) -
Giménez Nora,
Lara Rebeca,
Moreno M. Teresa,
Lalinde Elena
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605809
Subject(s) - phosphorescence , photochemistry , chemistry , physics , fluorescence , quantum mechanics
A convenient and general strategy for the synthesis of stable bis(cyclometalated) pentafluorophenyl Pt IV complexes fac ‐[Pt(C^N) 2 (C 6 F 5 )Cl] ( 3 a – f ) and mer ‐[Pt(C^N) 2 (C 6 F 5 )(CN)] ( 4 c , d ) has been developed. Complexes 3 were selectively generated by low‐temperature oxidation of the cyclometalated Pt II complexes [Pt(C^N)(HC^N)(C 6 F 5 )] 2 [prepared from cis ‐[Pt(C 6 F 5 ) 2 (HC^N) 2 ] ( 1 ) intermediates] with PhICl 2 and subsequent metalation of the pendant HC^N ligand. Complexes 3 a , b were also alternatively generated by irradiation (Hg lamp, 400 W) of complexes 2 a , b , respectively, in CH 2 Cl 2 . This latter reaction proceeds via the hydride Pt IV species cis ‐[Pt(C^N) 2 (C 6 F 5 )H], detected as the only intermediate species. The molecular structures of 1 a , d , 2 a , and 3 a , b , d , e were confirmed by X‐ray diffraction. The substitution of Cl − by CN − in fac ‐[Pt(C^N) 2 (C 6 F 5 )Cl] [C^N=2‐phenylbenzothiazole ( 3 c ), 2‐(4‐bromophenyl)benzothiazole ( 3 d )] evolved with isomerization to give rise to the isomers ( OC‐ 6–42)‐[Pt(C^N) 2 (C 6 F 5 )(CN)] ( 4 c , 4 d ) having a mer disposition of the cyclometalated and C 6 F 5 groups (X‐ray, 4 c ). All the complexes are luminescent and their electronic spectra have been compared and interpreted with the aid of time‐dependent DFT calculations.