Guest Programmable Multistep Spin Crossover in a Porous 2-D Hofmann-Type Material

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• 作者：Michael J. Murphy ; Katrina A. Zenere ; Florence Ragon ; Peter D. Southon ; Cameron J. Kepert ; Suzanne M. Neville
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：January 25, 2017
• 年：2017
• 卷：139
• 期：3
• 页码：1330-1335
• 全文大小：401K
• ISSN：1520-5126

文摘

The spin crossover (SCO) phenomenon defines an elegant class of switchable materials that can show cooperative transitions when long-range elastic interactions are present. Such materials can show multistepped transitions, targeted both fundamentally and for expanded data storage applications, when antagonistic interactions (i.e., competing ferro- and antiferro-elastic interactions) drive concerted lattice distortions. To this end, a new SCO framework scaffold, [Fe^II(bztrz)₂(Pd^II(CN)₄)]·n(guest) (bztrz = (E)-1-phenyl-N-(1,2,4-triazol-4-yl)methanimine, 1·n(guest)), has been prepared that supports a variety of antagonistic solid state interactions alongside a distinct dual guest pore system. In this 2-D Hofmann-type material we find that inbuilt competition between ferro- and antiferro-elastic interactions provides a SCO behavior that is intrinsically frustrated. This frustration is harnessed by guest exchange to yield a very broad array of spin transition characters in the one framework lattice (one- (1·(H₂O,EtOH)), two- (1·3H₂O) and three-stepped (1·∼2H₂O) transitions and SCO-deactivation (1)). This variety of behaviors illustrates that the degree of elastic frustration can be manipulated by molecular guests, which suggests that the structural features that contribute to multistep switching may be more subtle than previously anticipated.