title: Trinuclear copper(I) and silver(I) adducts of 4-chloro-3,5-bis(trifluoromethyl)pyrazolate and 4-bromo-3,5-bis(trifluoromethyl)pyrazolate.
abstract: Syntheses, structural, and photoluminescence properties of {[4-X-3,5-(CF3)2Pz]M}3 (X = Cl or Br, M = Cu or Ag) containing a heavier halide at the pyrazolyl ring 4-positions are reported. The Cu2O and Ag2O react with [4-Cl-3,5-(CF3)2Pz]H or [4-Br-3,5-(CF3)2Pz]H to form the corresponding metal pyrazolates, which are trinuclear adducts of the type {[4-X-3,5-(CF3)2Pz]M}3 with a nine-membered M3N6 metallacyclic core. They also feature relatively short M···Cl or M···Br intertrimer separations (∼ 3.6 Å) leading to supramolecular aggregates in the solid state. Distinct from the 4-H analogues {[3,5-(CF3)2Pz]M}3, none of the four complexes described herein exhibits short intertrimer metal-metal interactions (as closest such M···M separations are at a distance greater than 5.0 Å). The {[4-X-3,5-(CF3)2Pz]M}3 adducts exhibit bright photoluminescence even at room temperature. The photophysical data suggest that the {[4-X-3,5-(CF3)2Pz]Cu}3 complexes emit from an associative excited state, and the drastic Stokes shift suggests a significant change to the ground state structure of the trinuclear moiety and/or intermolecular interactions upon photoexcitation. The {[4-X-3,5-(CF3)2Pz]Ag}3 complexes emit from a ligand-centered excited state affected by silver and the heavier halogens. Thin films of {[4-X-3,5-(CF3)2Pz]Cu}3 trimers are promising for volatile organic compound (VOC) sensor applications as they exhibit luminescence color change upon exposure to vapors of benzene and its alkylated derivatives.
authors.affiliation: Department of Chemistry, Faculty of Science, University of Peradeniya , Peradeniya 20400, Sri Lanka.
authors.forename: Champika V
authors.initials: CV
authors.lastname: Hettiarachchi
authors.forename: Manal A
authors.initials: MA
authors.lastname: Rawashdeh-Omary
authors.forename: Daniel
authors.initials: D
authors.lastname: Korir
authors.forename: Jehan
authors.initials: J
authors.lastname: Kohistani
authors.forename: Muhammed
authors.initials: M
authors.lastname: Yousufuddin
authors.forename: H V Rasika
authors.initials: HV
authors.lastname: Dias