Buckminsterfulleride(1-) salts. Synthesis, EPR, and the Jahn-Teller distortion of C[sub 60][sup [minus]]

Journal Article · Wed Jun 16 04:00:00 EDT 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00065a037· OSTI ID:6235117

Stinchcombe, J; Penicaud, A; Bhyrappa, P; Reed, C A ^[1]; Boyd, P D.W. ^[2]

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1. Univ. of Southern California, Los Angeles (United States)
2. Univ. of Auckland (New Zealand)

Synthetic methods are reported for the isolation of a number of buckministerfulleride(1-) salts. Counterions include cobaltocenium ion, Na(dibenzo-18-crown-6)[sup +], and bis(N-methylimidazole)(tetraphenylporphinato)tin(IV[sup 2+]). The EPR spectrum of C[sub 60][sup [minus]] in frozen solution shows two unusual features. First, there is a counterion-dependent anisotropy observed at low temperatures. This is ascribed to an ellipsoidal distortion induced by ion pairing. It is consistent with, but not directly ascribable to, a static Jahn-Teller distortion. Second, there are two components to the high-temperature spectrum; the broad essentially isotropic, major signal and a narrower [open quotes]spike[close quotes]. The narrower signal is ascribed to thermal population of a low-lying excited state, a natural consequence of the distortion that splits the [sup 2]T[sub 1u] state into closely spaced [sup 2]E and [sup 2]A states. In contrast to intuition and to ab initio calculations, the [sup 2]E state is lowest in most systems studied to date. 43 refs., 4 figs.

• OSTI ID: 6235117
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:12; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
664100 -- Theory of Electronic Structure of Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ALKALI METAL COMPOUNDS
CARBON
COBALT COMPOUNDS
ELECTRON SPIN RESONANCE
ELECTRONIC STRUCTURE
ELEMENTS
FULLERENES
JAHN-TELLER EFFECT
MAGNETIC RESONANCE
NONMETALS
RESONANCE
SALTS
SODIUM COMPOUNDS
SPECTROSCOPY
SYNTHESIS
TIN COMPOUNDS
TRANSITION ELEMENT COMPOUNDS