title: Visible and Near-IR Emissions from k2N- and k3N-Terpyridine Rhenium(I) Assemblies Obtained by an [n×1] Head-to-Tail Bonding Strategy.
abstract: An [n×1] head-to-tail bonding strategy has been used for the synthesis of ReImetallacycles. From a k3N-dicarbonyl precursor, a single discrete [4×1] square assembly was isolated and characterized, whereas a k2N-tricarbonyl precursor led to two major species, a square and a [3×1] triangular assembly. Solid-state X-ray diffraction study has confirmed the high angular distortion (71° to 96°) of the k2N precursors. The electrochemical reversibility of the triangular (5) and square (6, 7) assemblies is increased with respect to that of their precursors. Photophysical investigation has confirmed pronounced red-shifts in the emissions of the k3N-dicarbonyl species 4 (935 nm) and 7 (980 nm), as confirmed by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations.
authors.affiliation: Département de Chimie, Université de Montréal, 5150 Ch. de la Rampe, Pavillon J.-A. Bombardier, Montréal, QC, H3T 2B1, Canada.
authors.forename: Baptiste
authors.identifier: http://orcid.org/0000-0002-3647-8570
authors.initials: B
authors.lastname: Laramée-Milette
authors.affiliation: Dipartimento di Chimica, "Giacomo Ciamician", Università di Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors.forename: Nelsi
authors.identifier: http://orcid.org/0000-0002-4517-6611
authors.initials: N
authors.lastname: Zaccheroni
authors.affiliation: Dipartimento di Chimica, "Giacomo Ciamician", Università di Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors.forename: Francesco
authors.initials: F
authors.lastname: Palomba
authors.affiliation: Département de Chimie, Université de Montréal, 5150 Ch. de la Rampe, Pavillon J.-A. Bombardier, Montréal, QC, H3T 2B1, Canada.
authors.forename: Garry S
authors.initials: GS
authors.lastname: Hanan
keywords: NIR luminescence; carbonyl ligands; metallacycles; rhenium; self-assembly