A series of monoadducts of the β-bispyrazolato-copper(ii) one-dimensional coordination polymer is investigated with plane-wave density functional theory-dispersive interactions (DFT-D) calculations. It was found that weak Lewis bases, such as H2O and CH3OH, prefer a symmetric bridging coordination to the Cu(ii) ions, which in turn assume a highly distorted 4 + 2 octahedral configuration. Stronger Lewis bases, namely, NH3 and pyridine, prefer instead to bind to a single Cu(ii) ion, which adopts a 5-fold coordination in a square-pyramidal environment. A semi-bridging coordination, corresponding to a 5 + 1 distorted octahedral Cu(ii) environment, is finally predicted for molecules of intermediate Lewis basicity, such as CH3CN. The soundness of these results is corroborated by a good correlation found between the theoretical coordination number of the Cu(ii) ions, the computed spin-down fundamental band gap, and the experimentally observed vapochromic effects. This journal is © The Royal Society of Chemistry.

Vapochromic properties versus metal ion coordination of β-bispyrazolato–copper(II) coordination polymers: a first-principles investigation

PETTINARI, Claudio;
2015-01-01

Abstract

A series of monoadducts of the β-bispyrazolato-copper(ii) one-dimensional coordination polymer is investigated with plane-wave density functional theory-dispersive interactions (DFT-D) calculations. It was found that weak Lewis bases, such as H2O and CH3OH, prefer a symmetric bridging coordination to the Cu(ii) ions, which in turn assume a highly distorted 4 + 2 octahedral configuration. Stronger Lewis bases, namely, NH3 and pyridine, prefer instead to bind to a single Cu(ii) ion, which adopts a 5-fold coordination in a square-pyramidal environment. A semi-bridging coordination, corresponding to a 5 + 1 distorted octahedral Cu(ii) environment, is finally predicted for molecules of intermediate Lewis basicity, such as CH3CN. The soundness of these results is corroborated by a good correlation found between the theoretical coordination number of the Cu(ii) ions, the computed spin-down fundamental band gap, and the experimentally observed vapochromic effects. This journal is © The Royal Society of Chemistry.
2015
262
File in questo prodotto:
File Dimensione Formato  
304_CRYSTENGCOMM_2015_17_407_411.pdf

solo gestori di archivio

Tipologia: Versione Editoriale
Licenza: NON PUBBLICO - Accesso privato/ristretto
Dimensione 2.73 MB
Formato Adobe PDF
2.73 MB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11581/377382
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 6
  • ???jsp.display-item.citation.isi??? 6
social impact