Σ-Hole halogen bonding interactions in a mixed valence cobalt(iii/ii) complex and anti-electrostatic hydrogen bonding interaction in a cobalt(iii) complex: a theoretical insight. Issue 45 (31st October 2018)

• Record Type: Journal Article
• Authors: Ghosh, Kousik; Harms, Klaus; Bauzá, Antonio; Frontera, Antonio; Chattopadhyay, Shouvik
• Is Part Of: CrystEngComm. Volume 20:Issue 45(2018)
• Page Start: 7281
• Page End: 7292
• Publication Date: 2018-10-31
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c8ce01323c
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : Supramolecular interactions in the solid state structures of a mixed valence cobalt(ii /iii ) complex and a cobalt(iii ) complex have been studied using DFT calculations. Abstract : A mixed valence cobalt(iii /ii ) complex, [(μ1, 3 -OAc)2 {(SCN)Co III (L 1 )}2 Co II ]·H2 O (1 ), and an ionic coordination complex of cobalt(iii ), [Co III (L 2 )2 ][Co III (L 2 )(N3 )3 ] (2 ), have been synthesized and characterized {H2 L 1 = N, N ′-bis(5-bromosalicylidene)-2, 2-dimethyl-1, 3-propanediamine and HL 2 = N (5-bromosalicylidene)-2, 2-dimethyl-1, 3-propanediamine}. Energetic features of the supramolecular interactions involved in both complexes have been studied through DFT calculations, which indicate that the trinuclear structure of complex1 has been stabilized via σ-hole halogen bonding interactions in the solid state. On the other hand, counterintuitive anion⋯anion interactions are present in the solid state structure of complex2, which have been stabilized through anti-electrostatic H-bonds (AEHB). The dissociation scan plot for the AEHB dimer has showed the existence of a significantly high energetic barrier.