Journal
INORGANIC CHEMISTRY
Volume 51, Issue 21, Pages 11769-11778Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic301719v
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Funding
- National Institute of General Medical Sciences of the National Institutes of Health [R01GM-038401]
- NSF [CHE-1026369]
- CAS Hundred Talent Program starting grant of UCAS
- U.S. DOE [DE-AC02-06CH11357]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1026369] Funding Source: National Science Foundation
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The low-frequency vibrational characterization of the spin-crossover complex, five-coordinate cyano(tetraphenylporphyrinato)iron(II), [Fe(TPP)(CN)](-), is reported. Nuclear resonance vibrational spectroscopy has been used to measure all low-frequency vibrations involving iron at several temperatures; this yields vibrational spectra of both the low- (S = 0) and high-spin (S = 2) states. Multitemperature oriented single-crystal measurements facilitate assignments of the vibrational character of all modes and are consistent with the DFT-predicted spectra. The availability of the entire iron vibrational spectrum allows for the complete correlation of the modes between the two spin states. These data demonstrate that not only do the frequencies of the vibrations shift to lower values for the high-spin species as would be expected owing to the weaker bonds in the high-spin state, but also the mixing of iron modes with ligand modes changes substantially. Diagrams illustrating the changing character of the modes and their correlation are given. The reduced iron-ligand frequencies are the primary factor in the entropic stabilization of the high-spin state responsible for the spin crossover.
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