Three-Dimensional Heterometallic Coordination Networks: Syntheses, Crystal Structures, Topologies, and Heterogeneous Catalysis

Abstract

This work presents the synthesis of {Co 3+ -Zn 2+ } and {Co 3+ -Cd 2+ } heterometallic coordination networks. These networks are originated from two unique Co 3+ -based metalloligands containing appended arylcarboxylic acid groups at the strategically placed positions. Such appended arylcarboxylate groups coordinate the secondary metal ions, Zn 2+ and Cd 2+ , to afford distinct three-dimensional networks. All four networks display orderly arrangement of secondary metal ions and unique network topologies including an unprecedented one. These networks have been shown to act as the heterogeneous and reusable catalysts for the Knoevenagel condensation reactions and cyanation reactions of assorted aldehydes. Cyanation reactions nicely demonstrate the substrate size-exclusion catalysis.

Design and synthesis of coordination polymers with chelated units and their application in nanomaterials science

“…In another interesting example, 3d-4d heterometallic Co(III)-Zn(II) and Co(III)-Cd(II) CPs are obtained from two Co(III)-based metalloligands containing appended groups of arylcarboxylic acids 5-(picolinamido)-isophthalic acid and 4-[(pyridine-2carbonyl)-amino]benzoic acid in different positions. 106 Arylcarboxylate groups coordinate secondary metal ions, Zn(II) and Cd(II), with production of different 3D networks (Fig. 7).…”

A Reusable Efficient Green Catalyst of 2D Cu-MOF for the Click and Knoevenagel Reaction

“…The heterometallic 3D networks containing [Co 3+ –Zn 2+ ] and [Co 3+ –Cd 2+ ] exhibit interesting network topologies including an unprecedented one. However, these networks act as the heterogeneous and reusable catalysts for the Knoevenagel condensation reactions as well as cyanation reactions of assorted aldehydes with good yields [ 54 ]. Copper is a non noble and inexpensive abundant metal.…”

Synthesis of Metallomacrocycle and Coordination Polymers with Pyridine‐Based Amidocarboxylate Ligands and Their Catalytic Activities towards the Henry and Knoevenagel Reactions

“…The reaction catalyzed by [Tb(BTATB)(dmf) 2 (H 2 O)] n {BTATB=4,4′,4′′‐[benzene‐1,3,5‐triyltris(azanediyl)]tribenzoate} produced 99 % yield by using 4 mol % of the catalyst at 60 °C for 24 h, that is, a longer time, a higher temperature, and a higher amount of catalyst than in our case (Table S7, entry 7) . With catalyst 1 at 50 °C, a 91 % yield was reached in only 1.5 h, and complete conversion was achieved in 3 h. However, a heterometallic Co/Zn MOF based on 5‐(picolinamido)isophthalate led to complete conversion at a lower temperature and a shorter time (Table S7, entry 10). Thus, and according to the above comparisons, catalyst 1 is usually more active than other reported catalysts.…”