Cation Exchange in Dynamic 3D Porous Magnets: Improvement of the Physical Properties

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• 作者：Thais Grancha ; Alvaro Acosta ; Joan Cano ; Jes煤s Ferrando-Soria ; Beatriz Seoane ; Jorge Gascon ; Jorge Pas谩n ; Donatella Armentano ; Emilio Pardo
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：November 16, 2015
• 年：2015
• 卷：54
• 期：22
• 页码：10834-10840
• 全文大小：592K
• ISSN：1520-510X

文摘

We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li₄{Mn₄[Cu₂(Me₃mpba)₂]₃}路68H₂O (2) and K₄{Mn₄[Cu₂(Me₃mpba)₂]₃}路69H₂O (3) obtained鈥攙ia alkali cation exchange in a single-crystal to single-crystal process鈥攆rom the earlier reported anionic manganese(II)鈥揷opper(II) PCP of formula Na₄{Mn₄[Cu₂(Me₃mpba)₂]₃}路60H₂O (1) [Me₃mpba^{4鈥?/sup> = N,N鈥?2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1鈥测€?b>3鈥? of 2.0 (1鈥?, 12.0 (2鈥?, and 20.0 K (3鈥?]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.}