Visible and Near‐IR Emissions from k2N‐ and k3N‐Terpyridine Rhenium(I) Assemblies Obtained by an [n×1] Head‐to‐Tail Bonding Strategy. Issue 26 (12th April 2017)

• Record Type: Journal Article
• Authors: Laramée‐Milette, Baptiste; Zaccheroni, Nelsi; Palomba, Francesco; Hanan, Garry S.
• Is Part Of: Chemistry. Volume 23:Issue 26(2017)
• Page Start: 6370
• Page End: 6379
• Publication Date: 2017-04-12
• Subjects: carbonyl ligands -- metallacycles -- NIR luminescence -- rhenium -- self-assembly; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201700077
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: An [ n ×1] head‐to‐tail bonding strategy has been used for the synthesis of Re I metallacycles. From a k 3 N ‐dicarbonyl precursor, a single discrete [4×1] square assembly was isolated and characterized, whereas a k 2 N ‐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 k 2 N 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 k 3 N ‐dicarbonyl species4 (935 nm) and7 (980 nm), as confirmed by density functional theory (DFT) and time‐dependent DFT (TD‐DFT) calculations. Abstract : Re‐naissance : Triangular and square Re I metallacycles have been assembled through an [ n ×1] head‐to‐tail bonding strategy. Among the latter, pronounced differences in luminescence for k 2 N‐ (563 nm) and k 3 N ‐ (980 nm) assemblies have been observed (see graphic), as well as enhanced electrochemical reversibility.