Toward an Iron(II) Spin-Crossover Grafted Phosphazene Polymer

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• 作者：Ross J. Davidson ; Eric W. Ainscough ; Andrew M. Brodie ; Geoffrey B. Jameson ; Mark R. Waterland ; Harry R. Allcock ; Mark D. Hindenlang ; Boujemaa Moubaraki ; Keith S. Murray ; Keith C. Gordon ; Raphael Horvath ; Guy N. L. Jameson
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：August 6, 2012
• 年：2012
• 卷：51
• 期：15
• 页码：8307-8316
• 全文大小：487K
• 年卷期：v.51,no.15(August 6, 2012)
• ISSN：1520-510X

文摘

Two new cyclotriphosphazene ligands with pendant 2,2鈥?6鈥?2鈥?terpyridine (Terpy) moieties, namely, (pentaphenoxy){4-[2,6-bis(2-pyridyl)]pyridoxy}cyclotriphosphazene (L¹), (pentaphenoxy){4-[2,6-terpyridin-4-yl]phenoxy}cyclotriphosphazene (L²), and their respective polymeric analogues, L^1P and L^2P, were synthesized. These ligands were used to form iron(II) complexes with an Fe^IITerpy₂ core. Variable-temperature resonance Raman, UV鈥搗isible, and M枚ssbauer spectroscopies with magnetic measurements aided by density functional theory calculations were used to understand the physical characteristics of the complexes. By a comparison of measurements, the polymers were shown to behave in the same way as the cyclotriphosphazene analogues. The results showed that spin crossover (SCO) can be induced to start at high temperatures by extending the spacer length of the ligand to that in L² and L^2P; this combination provides a route to forming a malleable SCO material.