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Vibrational–Structural Combined Study into Luminescent Mixed Copper(I)/Copper(II) Cyanide Coordination Polymers

2016; Wiley; Volume: 2016; Issue: 18 Linguagem: Inglês

10.1002/ejic.201600124

1099-0682

Francesca Grifasi, Emanuele Priola, Michele R. Chierotti, Eliano Diana, Claudio Garino, Roberto Gobetto,

Lanthanide and Transition Metal Complexes

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.