title: Reversible dimerization of [5,6]-C60O.
abstract: The recently discovered [5,6]-open isomer of C(60)O has been found to undergo facile dimerization to form a new C(2) symmetry isomer of C(120)O(2), which can be photodissociated with relatively high efficiency to regenerate monomeric [5,6]-C(60)O. High yield dimerization of [5,6]-C(60)O proceeds spontaneously in toluene solution near room temperature. On the basis of (13)C NMR spectroscopy, ab initio quantum computations, and HPLC retention patterns, the resulting C(120)O(2) product has been deduced to be a nonpolar dimer of C(2) symmetry in which the C(60)O moieties are linked by two single bonds between sp(3)-hybridized carbon atoms adjacent to oxygen atoms. Photophysical properties of this dimer have also been measured and compared to those of C(120), the [2 + 2]-dimer of C(60). The ground-state absorption spectrum of C(120)O(2) in toluene is slightly red-shifted relative to that of C(120), with a distinctive peak at 329 nm and an S(1)-S(0) origin band at 704 nm. Its fluorescence spectrum shows two major peaks at 718 and 793 nm. In room-temperature toluene, the measured triplet state intrinsic lifetime of this C(120)O(2) isomer is 34 +/- 2 micros, a value somewhat shorter than that of C(120) (44 micros). C(120)O(2) undergoes photodissociation from its triplet state to regenerate monomeric [5,6]-C(60)O with quantum yields of 2.5% at 24 degrees C and 43% at 70 degrees C. It can therefore serve as a stable reactant for photolytic production of [5,6]-C(60)O. As a simple fullerene adduct that reacts under mild conditions, [5,6]-C(60)O may prove useful in special synthetic applications. Solutions of [5,6]-C(60)O are also unique because they can provide mixtures of a fullerene monomer and its dimer in a dynamic balance controllable by adjustment of concentration, temperature, and optical irradiation.
authors.affiliation: Department of Chemistry, and Center for Nanoscale Science and Technology, Rice University, 6100 Main Street, Houston, Texas 77005, USA.
authors.forename: Dmitri
authors.initials: D
authors.lastname: Tsyboulski
authors.forename: Dieter
authors.initials: D
authors.lastname: Heymann
authors.forename: Sergei M
authors.initials: SM
authors.lastname: Bachilo
authors.forename: Lawrence B
authors.initials: LB
authors.lastname: Alemany
authors.forename: R Bruce
authors.initials: RB
authors.lastname: Weisman