Cooperative influence of ligand frameworks in sustaining supramolecular architectures of Ni(II)/Pd(II) heteroleptic dithio-dipyrrin complexes via non-covalent interactions. (29th March 2015)

• Record Type: Journal Article
• Authors: Kumar, Vinod; Singh, Vikram; Gupta, Ajit N.; Singh, Santosh Kumar; Drew, Michael G.B.; Singh, Nanhai
• Is Part Of: Polyhedron. Volume 89(2015)
• Page Start: 304
• Page End: 312
• Publication Date: 2015-03-29
• Subjects: Xanthate -- Dithiocarbamate -- Dipyrromethene -- Photoluminescence -- Theoretical calculations; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2015.01.020
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Three new heteroleptic Ni(II)/Pd(II) dithio-dipyrrin complexes have been synthesized and structurally characterized. In3, a cyclic analog of benzene has been created via dimer formation between two C–H…N intermolecular hydrogen bonds; the dimers are subsequently held together by C–H…π (NiCS2, chelate) interactions to create a 2D supramolecular architecture. Abstract: The impact of the ligand frameworks on the crystal stabilization of the novel heteroleptic complexes [M(bzdpm)(xant)]( M = Ni(II)1, Pd(II)2, xant − = 4-methoxyphenylethylxanthate, bzdpmH = 5-benzyl dipyrromethene) and [Ni(dmbzdpm)(dtc)]3 (dmbzdpmH = 5-N, N-dimethylbenzyl dipyrromethene; dtc − = N-pyridyl-N-ferrocenylmethyl dithiocarbamate) has been investigated. In these planar complexes, the supramolecular structures of1 and2 are stabilized via C–H⋯O and CH⋯π interactions. The structure of3 revealed a centrosymmetric dimer formed by two C–H…N intermolecular hydrogen bonds between the nitrogen atom of the pyridyl group and a hydrogen atom on a neighboring molecule. The dimers thus formed are held together by C–H…π (NiCS2, chelate) interactions, sustaining a 2-D supramolecular architecture and constructing an unprecedented cyclic analog of benzene. The intermolecular interaction energies for the C–H…N and C–H…π (NiCS2, chelate) interactions have been estimated to assess their nature. The palladium complex2 shows luminescent characteristics in solution at room temperature.