Polyhedral-based nonlinear optical materials. 2. Theoretical investigation of some new high nonlinear optical response compounds involving polyhedral bridges with charged aromatic donors and acceptors

D. G. Allis, James T Spencer

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A theoretical study of several new classes of polyhedral-based molecules has shown that these species display large calculated nonlinear optical responses. These new classes of molecules are based on charged aromatic subunits connected through polyhedral cluster bridges, such as closo-[1-(C7H6)-12-(C5Me4) C2B10H10]. These compounds show calculated first hyperpolarizabilities (β) ranging from 6.5 to 8413.9 × 10-30 cm5 esu-1. A basis for understanding the origin of these large responses is proposed based on the two-state model and consideration of the orbital and electronic features of the molecules. In general, the highest occupied molecular orbitals for these species are localized on the aromatic donor rings, such as the cyclopentadienyl system, while the lowest unoccupied molecular orbitals are largely on the aromatic acceptor rings, such as the tropylium system. The electronic properties of these polyhedral-based systems appear to be significantly different from the analogous organic [5.6.7]quinarene system (tropyliumcyclopentadienylbenzene). The organic quinarene appears to behave as a completely electron-delocalized system over all three rings while the polyhedral-based compounds can best be described as consisting of two relatively independent, highly polarized regions.

Original languageEnglish (US)
Pages (from-to)3373-3380
Number of pages8
JournalInorganic Chemistry
Issue number14
StatePublished - Jul 2 2001


ASJC Scopus subject areas

  • Inorganic Chemistry

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