Role of anions in preparing silver(i) complexes with a new multidentate ligand: polymorphs, structures and nonlinear optical properties

Abstract

A new multidentate ligand containing pyridyl and pyrazolyl groups, 6-phenyl-4-(4-(1H-pyrazolyl)phenyl)-2,29-bipyridine (L) was designed and synthesized. By self-assembly of L with silver(I) salts, three new complexes containing disilver(I) metallocycles, namely [TsOAgL] 3), were obtained. Polymorph (II) of L was obtained unexpectedly when AgSCN complex was prepared. In complexes 1 and 2, two ligands in a head-to-tail mode bridge two Ag(I) ions via pyridyl and pyrazolyl N atoms to generate binuclear [AgL] 2 unit. While, in complex 3, the asymmetric unit contains two kinds of crystallographically and conformationally independent molecules with completely different structures and coordination environments of Ag(I) ions. The structure of one kind of molecule is similar to that of complex 1. However, the other kind has a uninuclear structure, and the Ag(I) center is coordinated by four pyridyl nitrogen atoms from two ligands. Different anions have shown a great influence on both the molecular structures and the packing structures of the complexes. The nonlinear optical (NLO) properties of L and the complexes were measured through Z-scan technique. The results show that they may be good candidates for non-linear optical materials.

Novel metal-organic hybrid materials constructed by ferrocenyl terpyridine derivatives and ZnIIX2 (X = Cl−, Br−, I−, SCN− and CH3COO−)

“…Presently, although the coordination effect between the ligands and the metal ions in the MOMs can be predicted, it is impossible to control the overall packing structures of the molecules because of the multiple weak intermolecular interactions which affect the molecular packing mostly [15,16]. As a result, the variation of backbone flexibility, substituent groups, molecular size and experimental conditions, such as solvents, metal-to-ligand ratio, and symmetry of organic linkers, can also affect the structures and properties of the MOMs [1,16].…”

Diverse Structural Ag(I) Supramolecular Complexes Constructed from Multidentate Dicyanoisophorone-Based Ligands: Structures and Enhanced Luminescence

“…In recent years, the design and synthesis of supramolecular complexes have become one of the most active fields in coordination chemistry and crystal engineering due to not only their novel topologies and fascinating structural diversities but also their special chemical and physical properties as well as their potential applications as functional materials. − The simple association of ligand with metal salt through the coordination and noncovalent interactions can be used to assemble new coordination complexes exhibiting properties that are not displayed by either of the components alone . Up to now, a number of supramolecular complexes with specific topologies and excellent properties have been synthesized by assembly of metal salts and organic ligands.…”

Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling

“…Data were collected using phi and omega scans of 0.5 • per frame, and a full sphere of data was obtained. Cell parameters were retrieved using Bruker SMART [37] software and refined using Bruker SAINT [37] on all the observed reflections. Absorption corrections were applied using SADABS [38].…”