Ion‐Directed Coordinative Polymerization of Copper(II) Pyridyl‐Alcohol Complexes Through Thiane Functionalities

Abstract

A mononuclear complex [Cu(HL·S)2(NO3)2] (1) and a one‐ dimensional coordination polymer [Cu(HL·S)Cl2]n (2) [HL·S = 4‐(pyridin‐2‐ylmethyl)tetrahydro‐2H‐thiopyran‐4‐ol] showcase the structure‐directing role of the counterions in their formation reaction: monodentate ligation of NO3– and Cl– induces an octahedral (with two HL·S per Cu in 1) or trigonal‐bipyramidal (with one HL·S per Cu in 2) CuII coordination environment. In contrast to 1 exhibiting no coordinative metal–sulfur bonds in the crystal lattice (space group P21/c), 2 (P21/c) features intermolecular Cu–S contacts of 2.3188(7) Å. The coordination compounds are thermally stable up to ca. 160 °C. Whereas 1 demonstrates the spin‐like behavior of an isolated central CuII ion, compound 2 exhibits weak antiferromagnetic intra‐chain coupling with J ≈ –2.1 cm–1 between neighboring CuII ions.

Conductive Self-Assembled Monolayers of Paramagnetic {CoIICo4III} and {Co4IICo2III} Coordination Clusters on Gold Surfaces

“…The augmentation of our polynuclear complexes with ancillary groups like thioethers (Dreiser et al, 2015; Schmitz et al, 2018c) aims to contribute to their conformational and charge stabilization on metallic surfaces and, furthermore, to reduce their possible agglomeration due to steric repulsion between the structurally exposed –SR anchor points. It is however noteworthy that metal complexes derivatized by thiane functionalities as, for example, mononuclear copper(II) pyridyl–alcohol complexes are capable of featuring close intermolecular S···S contacts in the crystal lattice (Schmitz et al, 2019).…”