Guanidinium Para-Substituted Benzenesulfonates: Competitive Hydrogen Bonding in Layered Structures and the Design of Nonlinear Optical Materials

Victoria A. Russell, Margaret C. Etter, Michael D. Ward

Research output: Contribution to journalArticle

Abstract

X-ray crystal structures of six guanidinium para-substituted benzenesulfonates, [C(NH2)3]+(p-XC6H4SO3] (X = −CH3, −NH2, −OCH3, −NO2, −OH, and −CO2H), are reported. Molecular packing in these salts is directed predominantly by hydrogen-bonding and Coulombic interactions. The planar guanidinium-sulfonate hydrogen-bonded sheet motif that is generally observed for these compounds is disrupted when the substituent X has hydrogen-bonding character. Consequently, the sheets “pucker” about guanidinium-sulfonate hydrogen-bonded ribbons, the puckering increasing with increasing hydrogen-bonding ability of X. For X = −CH3, −NH2, and −OCH3 the typical nearly planar sheet motif is observed. For X = −NO2 and −OH, the puckering of the hydrogen-bonded sheets is severe, and the ribbons assemble into noncentrosymmetric crystalline phases (Ama2 and Ima2, respectively) which exhibit second harmonic generation. For X = −CO2H, the sheet motif is completely disrupted due to competitive hydrogen bonding of X for guanidinium and sulfonate hydrogen-bonding sites. However, guanidinium-sulfonate hydrogen-bonded ribbons are observed in all salts. These studies suggest that the highly directing hydrogen-bonding and ionic character of the guanidinium-sulfonate networks provide a sound strategy for materials design, particularly for low-dimensional electronic properties and second harmonic generation.

Original languageEnglish (US)
Pages (from-to)1206-1217
Number of pages12
JournalChemistry of Materials
Volume6
Issue number8
DOIs
StatePublished - Aug 1 1994

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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