Cu₆S₆ Clusters as a Building Block for the Stabilization of Coordination Polymers with NiAs, NaCl, and Related Structures: Synthesis, Structure, and Catalytic Studies

Abstract

Four new three-dimensional heterometallic coordination polymers (CPs), [{Zn 3 (Hen)(OH)}{Cu 6 (6-mna) 6 }·(H 2 O) 6 ] (I), [{Zn 2 (OH)(en)}{Cu 6 (6-mna) 6 } 0.5 ·(H 2 O) 2 ·EtOH] (II), [{Zn 3 (dap) 3 -(H 2 O)}{Cu 6 (6-mna) 6 }·(H 2 O) 4 ] (III), and [{Zn 2 (4,4′-bpy) 0.5 (OH)-(H 2 O)}{Cu 6 (6-mna) 6 } 0.5 ·(H 2 O)] (IV) (en = ethylenediamine, 6-H 2 mna = 6-mercaptonicotinic acid, dap = 1,2-diaminopropane, 4,4′-bpy = 4,4′-bipyridine), have been synthesized and their structures determined by single-crystal X-ray crystallography.[a]

Heterometallic coordination polymers as heterogeneous electrocatalysts

“…In the past decade, an increasing number of studies have been devoted to heterometallic CPs as promising heterogeneous catalysts for a variety of organic reactions, such as the cyanosilylation of aldehydes, 107 oxidation of cyclohexene, 108 olefin epoxidation, 109 the Knoevenagel condensation, 110 cyanation of aldehydes, 111 sulfoxidation, 112 imine formation from alcohols and amines, 113 regioselective halogenation of phenol, 114 hydrogenation, 115 desulfurization, 116 the Henry reaction, 117 C-S cross-coupling reactions, 118 organophosphate hydrolysis, 119 oxidative hydroxylation of phenylboronic acid, 120 nitroaldol reactions, 121 acetalization of benzaldehyde, 122 and reduction of nitrophenol. 123 The above catalytic reactions often involve redox reactions using chemical reagents (i.e., H 2 O 2 , O 2 , and NaBH 4 ), and their corresponding electrocatalytic reactions have not been reported to date.…”

Sequential Assembly and Stabilization of Cu6S6 Octahedral Clusters in NaCl-, NiAs-, and CdI2-Related Structures and Their Utility toward Thermochromism and Multicomponent Hantzsch Reaction

“…This approach appears to give precise and controllable M–X–M cluster units. In studies involving 2-mercaptonicotinic acid, it was established that the precise M 6 cluster (M = Cu + /Ag + ) can be stabilized both as individual units and also as an extended assembly. , The hard–soft acid–base (HSAB) principle provides rationalization toward the formation of these M 6 clusters . Thus, the softer −S – and the pyridine N connect with the Cu + /Ag + ions to form the M 6 clusters, followed by the use of the free −COOH group for linking with another metal ion.…”

Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests

“…Among them, paddlewheel-like hexanuclear Cu(I) and Ag(I) clusters with isomorphous structures [M 6 (Hmna) 6 ] or [M 6 (mna) 6 ] 6− (M = Cu and Ag, H 2 mna = 2-mercaptonicotininc acid) and their derivatives have gathered special attention recently [31][32][33][34][35][36][37][38][39][40][41]. The Molecules 2021, 26, 6731 2 of 15 clusters have been studied from various perspectives.…”