Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 130, Issue 51, Pages 17552-17562Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja8068038
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Funding
- ARC [DP0557000]
- Commonwealth of Australia
- U.S. Department of Energy [DE-AC02-06CH11357]
- Aquitaine Region
- French-Australia Science & Technology (FAST) [FR050129]
- Australian Research Council [DP0557000] Funding Source: Australian Research Council
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The nanoporous metal-organic framework, Fe(bpe)(2)(NCS)(2)center dot 3(acetone), SCOF-4(Ac) (where bpe is 1,2-bis(4'-pyridyl)ethane), displays a two-step spin crossover (SCO) transition (65-155 K) that is sensitive to the presence of acetone guest molecules. Structural analyses have revealed a structural phase transition, from tetragonal (P (4) over bar2(1)c) to orthorhombic (P2(1)2(1)2), associated with the spin transition that defines a checkerboard-like ordering of spin sites at the high-spin:low-spin plateau. The reversible desorption of the acetone guest species is accompanied by a complex series of structural phase transitions that describe a dramatic flexing of the structure. The thermal trapping of a metastable state with similar to 20-25% high-spin character was observed both magnetically and structurally upon rapid quenching of SCOF-4(Ac) to 10 and 25 K, respectively. The light-induced excited spin state trapping (LIESST) effects for SCOF-4(Ac) show a 55% excitation of a metastable HIS state at 10 K and a characteristic T(LIESST) value of 52 K.
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