Pressure effects on the intervalence-transfer band of salts of mixed-valence 1',1'''-disubstituted biferrocenium cations

Journal Article · Wed Apr 13 04:00:00 EDT 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00216a021· OSTI ID:7247548

Sinha, U; Lowery, M D; Ley, W W; Drickamer, H G; Hendrickson, D N

The pressure dependence of the intervalence-transfer (IT) electronic absorption band has been determined for the mixed-valence biferrocenium and 1',1'''-diethylbiferrocenium cations intercalated into a clay and for the following eight microcrystalline compounds: biferrocenium triiodide (1); biferrocenium hexafluorophosphate (2); 1',1'''-diiodobiferrocenium triiodide (3); 1',1'''-diiodobiferrocenium dibromoiodate (4); 1',1'''-dibromobiferrocenium triiodide (5); 1',1'''-dichlorobiferrocenium triiodide hemiiodine (6); 1',1'''-diethylbiferrocenium triiodide (7); 1',1'''-di-n-butylbiferrocenium triiodide (8). Basically three different types of pressure dependencies of the energy of the IT band are seen. Compounds 3-5, which have a solid-state packing arrangement consisting of alternating stacks of cations and anions, exhibit one type of behavior. For these three compounds the IT band shifts blue initially with pressure, and above approx. 80 kbar there is the onset of a rather abrupt reversal where the IT band shifts red with increasing pressure.

• Research Organization: Univ. of Illinois, Urbana (USA)
• DOE Contract Number: AC02-76ER01198
• OSTI ID: 7247548
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:8; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CATIONS
CHARGED PARTICLES
COMPLEXES
DATA
DIENES
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
FERROCENE
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
IODIDES
IODINE COMPOUNDS
IONS
IRON COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
PRESSURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES
VALENCE