title: Modulation of metallophilic bonds: solvent-induced isomerization and luminescence vapochromism of a polymorphic Au-Cu cluster.
abstract: We report a homoleptic Au-Cu alkynyl cluster that represents an unexplored class of luminescent materials with stimuli-responsive photophysical properties. The bimetallic complex formulated as [Au(2)Cu(2)(C(2)OHC(5)H(8))(4)](n) efficiently self-assembles from Au(SC(4)H(8))Cl, Cu(NCMe)(4)PF(6), and 1-ethynylcyclopentanol in the presence of NEt(3). This compound shows remarkably diverse polymorphism arising from the modulation of metallophilic interactions by organic solvents. Four crystalline forms, obtained from methanol (1a); ethanol, acetone, or choloroform (1b); toluene (1c); and diethyl ether or ethyl acetate (1d), demonstrate different photoluminescent characteristics. The solid-state quantum yields of phosphorescence (Φ) vary from 0.1% (1a) to 25% (1d), depending on the character of intermetallic bonding. The structures of 1b-d were determined by single-crystal X-ray diffraction. The ethanol (1b, Φ = 2%) and toluene (1c, Φ = 10%) solvates of [Au(2)Cu(2)(C(2)OHC(5)H(8))(4)](n) adopt octanuclear isomeric structures (n = 2), while 1d (Φ = 25%) is a solvent-free chain polymer built from two types of Au(4)Cu(4) units. Electronic structure calculations show that the dramatic enhancement of the emission intensity is correlated with the increasing role of metal-metal bonding. The latter makes the emission progressively more metal-centered in the order 1b < 1c < 1d. The metallophilic contacts in 1a-d show high sensitivity to the vapors of certain solvents, which effectively induce unusual solid-state isomerization and switching of the absorption and luminescence properties via non-covalent interactions. The reported polymorphic material is the first example of a gold(I) alkynyl compound demonstrating vapochromic behavior.
authors.affiliation: Department of Chemistry, University of Eastern Finland, Joensuu 80101, Finland. igor.koshevoy@uef.fi
authors.forename: Igor O
authors.initials: IO
authors.lastname: Koshevoy
authors.forename: Yuh-Chia
authors.initials: YC
authors.lastname: Chang
authors.forename: Antti J
authors.initials: AJ
authors.lastname: Karttunen
authors.forename: Matti
authors.initials: M
authors.lastname: Haukka
authors.forename: Tapani
authors.initials: T
authors.lastname: Pakkanen
authors.forename: Pi-Tai
authors.initials: PT
authors.lastname: Chou