Hierarchical Assembly of a {Mn(II)15Mn(III)4} Brucite Disc: Step-by-Step Formation and Ferrimagnetism

Journal of the American Chemical Society
Yong-Kai DengLan-Sun Zheng

Abstract

In search of functional molecular materials and the study of their formation mechanism, we report the elucidation of a hierarchical step-by-step formation from monomer (Mn) to heptamer (Mn7) to nonadecamer (Mn19) satisfying the relation 1 + Σn6n, where n is the ring number of the Brucite structure using high-resolution electrospray ionization mass spectrometry (HRESI-MS). Three intermediate clusters, Mn10, Mn12, and Mn14, were identified. Furthermore, the Mn19 disc remains intact when dissolved in acetonitrile with a well-resolved general formula of [Mn19(L)x(OH)y(N3)36-x-y](2+) (x = 18, 17, 16; y = 8, 7, 6; HL = 1-(hydroxymethyl)-3,5-dimethylpyrazole) indicating progressive exchange of N3(-) for OH(-). The high symmetry (R-3) Mn19 crystal structure consists of a well-ordered discotic motif where the peripheral organic ligands form a double calix housing the anions and solvent molecules. From the formula and valence bond sums, the charge state is mixed-valent, [Mn(II)15Mn(III)4]. Its magnetic properties and electrochemistry have been studied. It behaves as a ferrimagnet below 40 K and has a coercive field of 2.7 kOe at 1.8 K, which can be possible by either weak exchange between clusters through the anions and solvents or throu...Continue Reading

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Citations

Dec 13, 2016·Inorganic Chemistry·Xiu-Ying ZhengLan-Sun Zheng
Jan 18, 2017·Chemistry : a European Journal·Shan-Shan ZhangLan-Sun Zheng
Jan 26, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Ranran MaJianmin Dou
Jul 12, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Yang-Tian YanYao-Yu Wang
Sep 25, 2017·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Shi-Qiang BaiT S Andy Hor
Oct 25, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Zilu ChenFupei Liang
Oct 7, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Zilu ChenFupei Liang
May 12, 2018·Chemical Communications : Chem Comm·Chao ZhangJingyang Niu
Oct 20, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Hector W L FraserEuan K Brechin
Jan 12, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Mari E Slater-ParryLeigh F Jones
Jul 6, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiong-Feng MaFu-Pei Liang
Oct 30, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Kai-Qiang MoFu-Pei Liang
Oct 25, 2016·Chemistry : a European Journal·Hong-Xu NaMing-Hua Zeng
Mar 11, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Fei YuMohamedally Kurmoo
Jul 19, 2017·Angewandte Chemie·Xiu-Ying ZhengLan-Sun Zheng
Jan 15, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Hai-Ye LiFu-Pei Liang
Jul 8, 2021·Inorganic Chemistry·Hui-Jie LunLan-Sun Zheng
Oct 30, 2018·Langmuir : the ACS Journal of Surfaces and Colloids·Derek C PoppleJ Nathan Hohman
Sep 20, 2017·Journal of the American Chemical Society·Ling-Yu GuoLan-Sun Zheng

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