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Bis[(E)-2,6-bis(1H-pyrazol-1-yl)-4-styrylpyridine]iron(II) Complex: Relationship between Thermal Spin Crossover and Crystal Solvent.
MedLine Citation:
PMID:  23347048     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The crystal structures and thermal spin-crossover (SCO) behavior of [Fe(E-dpsp)(2)](BF(4))(2)·X [E-dpsp = (E)-2,6-bis(1H-pyrazol-1-yl)-4-styrylpyridine; X = crystal solvent] are investigated. The titled iron(II) complex features polymorphology induced by crystal solvents, which is identified by means of single-crystal X-ray diffraction analysis: For [Fe(E-dpsp)(2)](BF(4))(2)·acetone and [Fe(E-dpsp)(2)](BF(4))(2)·4MeNO(2), detailed analyses at various temperatures are conducted. The magnetic properties of bulk microcrystalline samples of [Fe(E-dpsp)(2)](BF(4))(2)·X are assessed using a SQUID magnetometer. Among the series, only [Fe(E-dpsp)(2)](BF(4))(2)·acetone undergoes peculiar thermal SCO, such as a precipitous and hysteretic spin-state change (T(1/2↑) = 179 K, T(1/2↓) = 164 K, and ΔT(1/2) = 15 K) and frozen-in effect. All single crystals of [Fe(E-dpsp)(2)](BF(4))(2)·X are free from intermolecular interaction except for [Fe(E-dpsp)(2)](BF(4))(2)·acetone: One of the phenyl rings in [Fe(E-dpsp)(2)](BF(4))(2)·acetone is twisted appreciably and features an intermolecular H-H short contact with one of the neighboring complexes to form a one-dimensional network. The twisted phenyl group also participates in π-π stacking with one of the pyrazolyl rings of another neighboring molecule, constructing a dimeric couple. These intermolecular interactions would induce cooperative effects, which leads to the good thermal SCO phenomenon of [Fe(E-dpsp)(2)](BF(4))(2)·acetone.
Authors:
Yuta Hasegawa; Ryota Sakamoto; Kazuhiro Takahashi; Hiroshi Nishihara
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-24
Journal Detail:
Title:  Inorganic chemistry     Volume:  -     ISSN:  1520-510X     ISO Abbreviation:  Inorg Chem     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-25     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0366543     Medline TA:  Inorg Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
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