Issue 47, 2023

Fine-tuning synthesis of a novel CuI/CuII mixed-valence coordination polymer

Abstract

The chemistry of mixed-valence coordination polymers (CPs) and metal–organic frameworks (MOFs) is of great interest mainly due to their limited numbers and intriguing properties. The scarcity of these types of compounds can be attributed to the lack of effective methods for their synthesis. In this study, we report on the fine-tuning synthesis and structure of a novel CuI/CuII mixed-valence coordination polymer [Cu3Cl(4-ptz)2(OH)2]n (1), based on the reaction of a 5-(4-pyridyl)tetrazole (4-H-ptz) ligand and CuCl2·2H2O in a molar ratio of 1 : 3 under hydrothermal conditions. X-ray crystallography analysis of 1 and bond valence method calculations confirmed the mixed-valence characteristics of the MOF, where Cu(1) presents a +1 charge but Cu(2) presents a +2 charge. The structure is unique, in which the CuI center adopts a T-shaped geometry and CuII exists in a square-pyramidal arrangement. The CuI/CuII mixed-valence compound 1 was formed by the partial reduction of CuII salts in the presence of a 4-H-ptz ligand, which also serves as a reducing agent. In addition, the tetrazolate and pyridine groups of the deprotonated 4-ptz ligand in an appropriate spatial arrangement and coordination sites perfectly fit the requirements for the successful assembly of the final mixed-valence product. Furthermore, a univalence CuI-based compound [Cu2Cl(4-ptz)]n (2) was obtained by using a molar ratio of L : M = 1 : 2 (L = 4-H-ptz, M = CuCl2·2H2O) under 160 °C hydrothermal conditions. The isolation of this univalent 2 highlights the fact that the fine-tuning synthesis of the CuI/CuII mixed-valence compound 1 is possible. These results provide an excellent example of the design, synthesis, and crystal engineering of mixed-valence compounds.

Graphical abstract: Fine-tuning synthesis of a novel CuI/CuII mixed-valence coordination polymer

Supplementary files

Article information

Article type
Paper
Submitted
10 Oct 2023
Accepted
25 Oct 2023
First published
02 Nov 2023

CrystEngComm, 2023,25, 6635-6643

Fine-tuning synthesis of a novel CuI/CuII mixed-valence coordination polymer

S. Sie, S. Kamal, Z. Lu, L. Wei, T. Luo, Y. Liu, C. Chang, K. Chi and K. Lu, CrystEngComm, 2023, 25, 6635 DOI: 10.1039/D3CE01001E

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