title: Emission Tuning of Luminescent Copper(I) Complexes by Vapor-Induced Ligand Exchange Reactions.
abstract: We have synthesized two luminescent mononuclear Cu(I) complexes, [Cu(PPh2Tol)(THF)(4Mepy)2](BF4) (1) and [Cu(PPh2Tol)(4Mepy)3](BF4) (2) (PPh2Tol = diphenyl(o-tolyl)phosphine, 4Mepy = 4-methylpyridine, THF = tetrahydrofuran), and investigated their crystal structures, luminescence properties, and vapor-induced ligand exchange reactions in the solid state. Both coordination complexes are tetrahedral, but one of the three 4Mepy ligands of complex 2 is replaced by a THF solvent molecule in complex 1. In contrast to the very weak blue emission of the THF-bound complex 1 (wavelength of emission maximum (λem) = 457 nm, emission quantum yield (Φem) = 0.02) in the solid state at room temperature, a very bright blue-green emission was observed for 2 (λem= 484 nm, Φem= 0.63), suggesting a contribution of the THF ligand to nonradiative deactivation. Time-dependent density functional theory calculations and emission lifetime measurements suggest that the room-temperature emissions of the complexes are due to thermally activated delayed fluorescence from the metal-to-ligand charge transfer excited state. Interestingly, by exposing the solid sample of THF-bound 1 to 4Mepy vapor, the emission intensity drastically increased and the emission color changed from blue to blue-green. Powder X-ray diffraction measurements revealed that the emission change of 1 is due to the vapor-induced ligand exchange of THF for 4Mepy, forming the strongly emissive complex 2. Further emission tuning was achieved by exposing 1 to pyrimidine or pyrazine vapors, forming green (λem= 510 nm) or orange (λem= 618 nm) emissive complexes, respectively. These results suggest that the vapor-induced ligand exchange is a promising method to control the emission color of luminescent Cu(I) complexes.
authors.affiliation: Department of Chemistry, Faculty of Science, Hokkaido University , North-10 West-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Hasegawa
authors.affiliation: Department of Chemistry, Faculty of Science, Hokkaido University , North-10 West-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
authors.forename: Atsushi
authors.identifier: http://orcid.org/0000-0002-1937-7698
authors.initials: A
authors.lastname: Kobayashi
authors.affiliation: Department of Chemistry, Faculty of Science, Hokkaido University , North-10 West-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
authors.forename: Hiroki
authors.initials: H
authors.lastname: Ohara
authors.affiliation: Department of Chemistry, Faculty of Science, Hokkaido University , North-10 West-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
authors.forename: Masaki
authors.initials: M
authors.lastname: Yoshida
authors.affiliation: Department of Chemistry, Faculty of Science, Hokkaido University , North-10 West-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
authors.forename: Masako
authors.initials: M
authors.lastname: Kato