title: Shedding light on the photochemistry of coinage-metal phosphorescent materials: a time-resolved Laue diffraction study of an Ag(I)-Cu(I) tetranuclear complex.
abstract: The triplet excited state of a new crystalline form of a tetranuclear coordination d(10)-d(10)-type complex, Ag2Cu2L4 (L = 2-diphenylphosphino-3-methylindole ligand), containing Ag(I) and Cu(I) metal centers has been explored using the Laue pump-probe technique with ≈80 ps time resolution. The relatively short lifetime of 1 μs is accompanied by significant photoinduced structural changes, as large as the Ag1···Cu2 distance shortening by 0.59(3) Å. The results show a pronounced strengthening of the argentophilic interactions and formation of new Ag···Cu bonds on excitation. Theoretical calculations indicate that the structural changes are due to a ligand-to-metal charge transfer (LMCT) strengthening the Ag···Ag interaction, mainly occurring from the methylindole ligands to the silver metal centers. QM/MM optimizations of the ground and excited states of the complex support the experimental results. Comparison with isolated molecule optimizations demonstrates the restricting effect of the crystalline matrix on photoinduced distortions. The work represents the first time-resolved Laue diffraction study of a heteronuclear coordination complex and provides new information on the nature of photoresponse of coinage metal complexes, which have been the subject of extensive studies.
authors.affiliation: Department of Chemistry, University at Buffalo, The State University of New York , Buffalo, New York 14260-3000, United States.
authors.forename: Katarzyna N
authors.initials: KN
authors.lastname: Jarzembska
authors.forename: Radosław
authors.initials: R
authors.lastname: Kamiński
authors.forename: Bertrand
authors.initials: B
authors.lastname: Fournier
authors.forename: Elżbieta
authors.initials: E
authors.lastname: Trzop
authors.forename: Jesse D
authors.initials: JD
authors.lastname: Sokolow
authors.forename: Robert
authors.initials: R
authors.lastname: Henning
authors.forename: Yang
authors.initials: Y
authors.lastname: Chen
authors.forename: Philip
authors.initials: P
authors.lastname: Coppens
mesh_terms: D003300:Copper / Q000737:chemistry*; D008027:Light; D049408:Luminescent Agents / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D055668:Photochemical Processes; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D013997:Time Factors
chemical_list: D049408:Luminescent Agents; D009942:Organometallic Compounds; D012834:Silver; D003300:Copper