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Three zinc iodide complexes based on phosphane ligands: syntheses, structures, optical properties and TD–DFT calculations
Author(s) -
Chen Di,
Wang Qiu-Hua,
Chai Wen-Xiang,
Song Li
Publication year - 2018
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229618002607
Subject(s) - iodide , zinc , chemistry , zinc compounds , computational chemistry , combinatorial chemistry , inorganic chemistry , organic chemistry
Three zinc iodide complexes based on phosphane ligands, namely diiodidobis(triphenylphosphane‐κ P )zinc(II), [ZnI 2 (C 18 H 15 P 2 ) 2 ], ( 1 ), diiodidobis[tris(4‐methylphenyl)phosphane‐κ P ]zinc(II), [ZnI 2 (C 21 H 21 P 2 ) 2 ], ( 2 ), and [bis(diphenylphosphoryl)methane‐κ 2 O , O ′]zinc(II) tetraiodidozinc(II), [Zn(C 25 H 22 O 2 P 2 ) 3 ][ZnI 4 ], ( 3 ), have been synthesized and characterized. Single‐crystal X‐ray diffraction revealed that the structures of ( 1 ) and ( 2 ) are both mononuclear four‐coordinated ZnI 2 complexes containing two monodentate phosphane ligands, respectively. Surprisingly, ( 2 ) spontaneously forms an acentric structure, suggesting it might be a potential second‐order NLO material. The crystal structure of complex ( 3 ) is composed of two parts, namely a [Zn(dppmO 2 ) 3 ] 2+ cation [dppmO 2 is bis(diphenylphosphoryl)methane] and a [ZnI 4 ] 2− anion. The UV–Vis absorption spectra, thermal stabilities and photoluminescence spectra of the title complexes have also been studied. Time‐dependent density functional theory (TD–DFT) calculations reveal that the low‐energy UV absorption and the corresponding light emission both result from halide‐ligand charge‐transfer (XLCT) excited states.