Exploring and predicting intermolecular binding preferences in crystalline Cu(ii) coordination complexes. Issue 43 (9th October 2019)

• Record Type: Journal Article
• Authors: Kodrin, Ivan; Borovina, Mladen; Šmital, Luka; Valdés-Martínez, Jesús; Aakeröy, Christer B.; Đaković, Marijana
• Is Part Of: Dalton transactions. Volume 48:Issue 43(2019)
• Page Start: 16222
• Page End: 16232
• Publication Date: 2019-10-09
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt03346g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Molecular electrostatic potential values (MEP) at competing hydrogen-bond acceptor sites provided guidelines for predicting supramolecular connectivity in a set of Cu(ii ) acac-based complexes. Abstract : A simple model focusing on electrostatic contributions to interaction energies was found to be very effective for rationalizing the appearance of specific supramolecular interactions in a series of Cu(ii ) coordination compounds. The experimental space was provided by a combination of Cu(ii ) cations with acac-based anions (hexafluoracetylacetonato and trifluoracetylacetonato) and a series of pyridine-oxime ligands (3-pyridinealdoxime, methyl 3-pyridyl ketoxime, 4-pyridinealdoxime, methyl 4-pyridyl ketoxime, phenyl 4-pyridyl ketoxime). The calculated molecular electrostatic potential (MEP) values at competing hydrogen-bond acceptor sites, for ten structurally characterized complexes, provided guidelines for predicting supramolecular connectivity in cases when the MEP difference exceeded certain cut-off values, while two different and well-defined outcomes are possible within the so called 'grey zone', delineated by a range of MEP differences. It was also shown that the structural outcome within this region is determined by the influence of relatively weak, but distinct, auxillary interactions.