Premium
Vibrational–Structural Combined Study into Luminescent Mixed Copper(I)/Copper(II) Cyanide Coordination Polymers
Author(s) -
Grifasi Francesca,
Priola Emanuele,
Chierotti Michele R.,
Diana Eliano,
Garino Claudio,
Gobetto Roberto
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600124
Subject(s) - chemistry , luminescence , copper , crystallography , raman spectroscopy , supramolecular chemistry , cyanide , differential scanning calorimetry , thermogravimetric analysis , infrared spectroscopy , spectroscopy , crystal structure , inorganic chemistry , organic chemistry , materials science , physics , optoelectronics , quantum mechanics , optics , thermodynamics
Herein, we report the characterization of a series of CuCN‐based coordination polymers that display different crystal packing and electronic properties, namely, [Na 2 Cu(CN) 3 · 3H 2 O] n ( 1 ), [Cu 4 (CN) 5 (NH 3 ) 2 (H 2 O)] n ( 2 ), [Cu 3 (CN) 4 (NH 3 ) 3 ] n ( 3 ), [Cu 3 (CN) 3 (O) 0.25 (NH 3 )] n ( 4 ), [Cu 5 (CN) 6 (NH 3 ) 4 ] n ( 5 ), and [Cu 5 (CN) 6 (NH 3 ) 2 ] n ( 6 ). Spectroscopic evidence of the presence of ammonia molecules coordinated to the metal centers is provided, in particular for 4 , which is a new structure. The characterization has been performed by single‐crystal XRD (SCXRD), micro‐ IR spectroscopy, micro‐Raman spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The photophysical properties have been studied through solid‐state luminescence spectroscopy by acquiring the emission and excitation spectra and evaluating the emission quantum yields, which is an approach that has recently grown in importance in the solid‐state field. The goals of this work are (1) to elucidate the correlation between the luminescence properties and the presence of either Cu I or mixed Cu I /Cu II oxidation states, (2) to evaluate the presence of NH 3 , H 2 O, or both in the polymers through a combined crystallographic–spectroscopic study, and (3) to rationalize the supramolecular architecture and its influence on the resulting luminescence.