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Rhenium(I) Complexes with Alkynylphosphane Ligands: Structural, Photophysical, and Theoretical Studies
Author(s) -
Kondrasenko Ilya,
Kisel Kristina S.,
Karttunen Antti J.,
Jänis Janne,
Grachova Elena V.,
Tunik Sergey P.,
Koshevoy Igor O.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201403053
Subject(s) - rhenium , chemistry , luminescence , denticity , time dependent density functional theory , ligand (biochemistry) , phenanthroline , solid state , electronic structure , photochemistry , crystallography , coordination complex , stereochemistry , density functional theory , computational chemistry , inorganic chemistry , crystal structure , organic chemistry , metal , biochemistry , physics , receptor , optoelectronics
A family of mono‐ and bidentate alkynylphosphanes has been used for the preparation of the rhenium(I) phenanthroline complexes [Re(phen)(CO) 2 (L) 2 ] + (L = monophosphane), [{Re(phen)(CO) 3 } 2 (L)] 2+ (L = diphosphane), and [{Re(phen)(CO) 2 } 2 (L) 2 ] 2+ (L = diphosphane). The dicarbonyl compounds display intense luminescence at 298 K both in solution and in the solid state ( Φ em ≤ 44 %). The tricarbonyl complexes demonstrate a strong dependence of the emission efficiency on the ancillary ligand L through a pronounced π–π* contribution of the diphosphane to the electronic transitions, as confirmed by TDDFT studies. In the solid state, the complexes [Re(phen)(CO) 2 (L) 2 ] + display significant luminescence rigidochromism that is influenced by the structure of the phosphane substituents. The latter provide a means to fine‐tune the photophysical properties of this class of luminophores through variation of the stereochemical characteristics of the ligands that are not directly involved in the electronic transitions.