On the Border between Low-Nuclearity and One-Dimensional Solids: A Unique Interplay of 1,2,4-Triazolyl-Based {Cu II 5 (OH) 2 } Clusters and Mo VI -Oxide Matrix

Lysenko, Andrey B.; Bondar, Oksana A.; Senchyk, Ganna A.; Rusanov, Eduard B.; Srebro-Hooper, Monika; Hooper, James; Prsa, Krunoslav; Krämer, Karl; Decurtins, Silvio; Waldmann, Oliver; Liu, Shi-Xia (2018). On the Border between Low-Nuclearity and One-Dimensional Solids: A Unique Interplay of 1,2,4-Triazolyl-Based {Cu II 5 (OH) 2 } Clusters and Mo VI -Oxide Matrix. Inorganic chemistry, 57(10), pp. 6076-6083. American Chemical Society 10.1021/acs.inorgchem.8b00616

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A pentanuclear CuII5-hydroxo cluster possessing an unusual linear-shaped configuration was formed and crystallized under hydrothermal conditions as a result of the unique cooperation of bridging 1,2,4-triazole ligand (trans-1,4-cyclohexanediyl-4,4′-bi(1,2,4-triazole) (tr2cy)), MoVI-oxide, and CuSO4. This structural motif can be rationalized by assuming in situ generation of {Cu2Mo6O22}4– anions, which represent heteroleptic derivatives of γ-type [Mo8O26]4– further interlinked by [Cu3(OH)2]4+ cations through [N−N] bridges. The framework structure of the resulting compound [Cu5(OH)2(tr2cy)2Mo6O22]·6H2O (1) is thus built up from neutral heterometallic {Cu5(OH)2Mo6O22}n layers pillared with tetradentate tr2cy. Quantum-chemical calculations demonstrate that the exclusive site of the parent γ-[Mo8O26]4– cluster into which CuII inserts corresponds with the site that has the lowest defect (“MoO2 vacancy”) formation energy, demonstrating how the local metal-polyoxomolybdate chemistry can express itself in the final crystal structure. Magnetic susceptibility measurements of 1 show strong antiferromagnetic coupling within the Cu5 chain with exchange parameters J1 = −500(40) K (−348(28) cm–1), J2 = −350(10) K (−243(7) cm–1) and g = 2.32(2), χ2 = 6.5 × 10–4. Periodic quantum-chemical calculations reproduce the antiferromagnetic character of 1 and connect it with an effective ligand-mediated spin coupling mechanism that comes about from the favorable structural arrangement between the Cu centers and the OH–, O2–, and tr2cy bridging ligands.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)
08 Faculty of Science > Other Institutions > Emeriti, Faculty of Science

UniBE Contributor:

Krämer, Karl, Decurtins, Silvio, Liu, Shi-Xia


500 Science > 540 Chemistry




American Chemical Society




Silvio Decurtins

Date Deposited:

15 May 2018 09:44

Last Modified:

05 Dec 2022 15:14

Publisher DOI:






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