The Charge-Transfer Motif in Crystal Engineering. Self-Assembly of Acentric (Diamondoid) Networks from Halide Salts and Carbon Tetrabromide as Electron-Donor/Acceptor Synthons

Document Type

Article

Language

eng

Publication Date

2003

Publisher

American Chemical Society

Source Publication

Journal of the American Chemical Society

Source ISSN

0002-7863

Original Item ID

doi:10.1021/ja030299w

Abstract

Unusual strength and directionality for the charge-transfer motif (established in solution) are shown to carry over into the solid state by the facile synthesis of a series of robust crystals of the [1:1] donor/acceptor complexes of carbon tetrabromide with the electron-rich halide anions (chloride, bromide, and iodide). X-ray crystallographic analyses identify the consistent formation of diamondoid networks, the dimensionality of which is dictated by the size of the tetraalkylammonium counterion. For the tetraethylammonium bromide/carbon tetrabromide dyad, the three-dimensional (diamondoid) network consists of donor (bromide) and acceptor (CBr4) nodes alternately populated to result in the effective annihilation of centers of symmetry in agreement with the sphaleroid structural subclass. Such inherently acentric networks exhibit intensive nonlinear optical properties in which the second harmonics generation in the extended charge-transfer system is augmented by the effective electronic (HOMO−LUMO) coupling between contiguous CBr4/halide centers.

Comments

Accepted version. Journal of the American Chemical Society, Vol. 125, No. 38 (2003): 11597-11606. DOI. © 2003 American Chemical Society. Used with permission.

Sergey V. Lindeman was affiliated with the University of Houston at the time of publication.

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