title: Induced phosphorescence from Pt → Ag and Ag(i)...Ag(i) metallophilic interactions in benzenedithiolatodiimine-Pt2/Ag2 clusters: a combined experimental and theoretical investigation.
abstract: We report the synthesis and luminescence properties of a novel platinum(ii)-silver(i) cluster exhibiting supramolecular donor-acceptor dative Pt → Ag bonds as well as d(10)...d(10) argentophilic interactions. This compound was obtained by a self-assembly process upon mixing silver triflate with the [Pt(bdt)(bpy)] (1) building block. The new compound was characterized by infrared, NMR ((1)H, (13)C) and UV-vis spectroscopy. In addition, the molecular structure was unequivocally ascertained by a single-crystal X-ray diffraction study and shows that the assembly is identified as [(Pt2Ag2(o-bdt)2(bpy)2](CF3SO3)2 (2). Remarkably, the structure shows that complex 2 exists as two isomers I and II displaying different types of argentophilic interactions Ag...Ag as well as Pt → Ag dative bonds. These interactions are highly important and turn on phosphorescent emissions at low temperature depending on the nature of the isomer. The photophysical properties of both isomers were investigated and rationalized through TD-DFT calculations. This work paves the way to the synthesis of novel supramolecular assemblies displaying peculiar properties imparted from metallophilic as well as donor-acceptor metal-metal interactions.
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06, Université Pierre et Marie Curie, Institut Parisien de Chimie Moléculaire (IPCM) UMR 8232, 4 place Jussieu, 75252 Paris Cedex 05, France. jamal.moussa@upmc.fr.
authors.forename: Jamal
authors.initials: J
authors.lastname: Moussa
authors.forename: Lise Marie
authors.initials: LM
authors.lastname: Chamoreau
authors.forename: Maria Pia
authors.initials: MP
authors.lastname: Gullo
authors.forename: Alessandra
authors.initials: A
authors.lastname: Degli Esposti
authors.forename: Andrea
authors.initials: A
authors.lastname: Barbieri
authors.forename: Hani
authors.initials: H
authors.lastname: Amouri