Dimensional Structures and Electrocatalytic Activities of Platinum(II)–Palladium(II)–Manganese(II) Coordination Polymers Controlled by Chloride versus Bromide

Abstract

Here we report the synthesis and structural characterization of heterotrimetallic (Pt II 2 Pd II 2 Mn II 2 ) n coordination polymers that show different dimensionalities and electrocatalytic activities depending on chloride and bromide employed in the system. The reaction of the Pt II 2 Pd II 2 tetranuclear complex [Pd 2 Pt 2 (NH 3 ) 4 (D-pen) 4 ] (1), bearing free carboxylate groups, with Mn 2+ in the presence of chloride produced the (Pt II 2 Pd II 2 Mn II 2 ) n coordination polymer [Mn 2 Cl 2 (H 2 O) 6 (1)]Cl 2 (2 Cl ), in which the Pt II 2 Pd II 2 units of 1 are linked by [MnCl(H 2 O) 3 ] + moieties in a 1:2 ratio to form a 2D sheetlike structure. The corresponding reaction in the presence of bromide also gave the (Pt II 2 Pd II 2 Mn II 2 ) n coordination polymer [Mn 2 (H 2 O) 6 (1)]Br 4 (3 Br ), but 3 Br adopted a 3D network structure via a 1:1 linkage of the Pt II 2 Pd II 2 units with [Mn 2 (H 2 O) 6 ] 4+ moieties. These complexes showed appreciably different electrocatalytic activities for H 2 evolution.

In Situ Conversion of Ligand to a Coordination Polymer via a Core@Shell Crystal: A Multi-Step Phase-Dependent Structural Transformation

“…In recent years, research in the field of coordination polymers (CPs) has focused on discovering new and smart materials with a variety of compositions and architectures. , In fact, coordination polymers have attracted the attention of chemists because of their brilliant potential in magnetism, − catalysis, − sensing, − gas adsorption − /separation, − and drug delivery. , Various factors such as anion, − temperature, − and metal-to-ligand ratio have a significant impact on coordination polymers and ultimately affect their structures and functions. In addition, a solvent system is another influential factor in designing the coordination polymers. , According to previous reports, the solvent can directly participate in the crystal structure or indirectly affect the formation of the final structural framework. − On the other side, noncovalent interactions play an essential role in the self-assembly process of coordination polymers, ,− and among the types of noncovalent interactions, the anion-π interaction is particularly highlighted. − During the past decade, scientists have done considerable theoretical and experimental research to investigate this type of interaction, − and with widespread progress in this field, the anion-π interaction is considered an important interaction for the identification of anionic species. − The discussion on joint experimental/theoretical is limited, and Frontera and co-workers presented valuable pape...…”