title: Trifluoropropynyl as a surrogate for the cyano ligand and intense, room-temperature, metal-centered emission from its Rh(III) complex.
abstract: The trifluoropropynyl ligand -C≡CCF(3) was studied as a possible surrogate for the cyano ligand. Complexes of the type trans-[M(cyclam)(C≡CCF(3))(2)]OTf (where M = Cr(3+), Co(3+), and Rh(3+); OTf = trifluoromethanesulfonate) were prepared and then characterized by electronic spectroscopy and by cyclic voltammetry for the Co(3+) complex. The UV-vis spectra for all three bear a remarkable similarity to that of the trans-M(cyclam)(CN)(2)(+) cations. The trifluoropropynyl complex of Co(3+) shows electrochemical behavior nearly identical with that of its dicyano analogue. Metal-centered phosphorescence from the Rh(III) complex in room-temperature aqueous solution has a quantum yield of 0.12 and a lifetime of 73 μs, nearly 10 times higher than those of its dicyano analogue.
authors.affiliation: Department of Chemistry, Furman University, Greenville, South Carolina 29613, USA.
authors.forename: Chivin
authors.initials: C
authors.lastname: Sun
authors.forename: Parth U
authors.initials: PU
authors.lastname: Thakker
authors.forename: Levan
authors.initials: L
authors.lastname: Khulordava
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Tobben
authors.forename: Seth M
authors.initials: SM
authors.lastname: Greenstein
authors.forename: David L
authors.initials: DL
authors.lastname: Grisenti
authors.forename: Andrew G
authors.initials: AG
authors.lastname: Kantor
authors.forename: Paul S
authors.initials: PS
authors.lastname: Wagenknecht