Hierarchical Assembly of a {Co24} Cluster from Two Vertex-Fused {Co13} Clusters and Their Single-Molecule Magnetism

Peng-Fei Yao; Yun-Kai Chen; Chao-Feng Lai; Hai-Ye Li; He-Dong Bian; Han-Fu Liu; Di Yao; Fu-Ping Huang

doi:10.1021/acs.inorgchem.8b01211

Hierarchical Assembly of a {Co₂₄} Cluster from Two Vertex-Fused {Co₁₃} Clusters and Their Single-Molecule Magnetism

Inorg Chem. 2018 Aug 6;57(15):9182-9189. doi: 10.1021/acs.inorgchem.8b01211. Epub 2018 Jul 9.

Authors

Peng-Fei Yao^{1

2}, Yun-Kai Chen¹, Chao-Feng Lai¹, Hai-Ye Li¹, He-Dong Bian^{1

3}, Han-Fu Liu¹, Di Yao¹, Fu-Ping Huang¹

Affiliations

¹ State Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmacy , Guangxi Normal University , Guilin , 541004 , People's Republic of China.
² Key Laboratory of Regional Ecological Environment Analysis and Pollution Control of West Guangxi, College of Chemistry and Environmental Engineering , Baise University , Baise , Guangxi 533000 , People's Republic of China.
³ School of Chemistry and Chemical Engineering , Guangxi University for Nationalities , Key Laboratory of Chemistry and Engineering of Forest Products, Nanning 530008 , People's Republic of China.

PMID: 29985614
DOI: 10.1021/acs.inorgchem.8b01211

Abstract

We present the synthesis, structural characterization, and magnetic properties of two high-nuclearity cobalt clusters formulated as [Co₁₃(μ₃-OH)₃(μ₃-Cl)(dpbt)₅(ptd)Cl₁₀][Co(H₂O)₂Cl₂]·(CH₃)₂CHOH (1) and [Co₂₄(μ₃-OH)₆(μ₃-Cl)₂(dpbt)₁₀(ptd)₂Cl₁₆]·2CH₃CH₂OH (2), respectively (H₂dpbt = 5,5'-bis(pyridin-2-yl)-3,3'-bis(1,2,4-triazole) and H₂ptd = 3-(pyridin-2-yl)-1,2,4-triazine-5,6-diol). Compound 1 is composed of an inner [Co₄(μ₃-OH)₃(μ₃-Cl)] cubane and an outer [Co₉(dpbt)₅(ptd)Cl₁₀] defective adamantane. Compound 2 reveals a giant {Co₂₄} cluster possessing a dual-[Co₁₂] skeleton from 1. The hierarchical assembly from 1 to 2 has been established and tracked through high-resolution electrospray ionization (HRESI-MS) analyses from the solvothermal reaction mother solution. Magnetic studies of 1 and 2 revealed the highly correlated spins, a glasslike magnetic phase transition at ca. 8 K, and slow relaxation behavior of SMM nature in the lower-temperature region (below 4 K).