Supramolecular materials: molecular packing of tetranitrotetrapropoxycalix[4]arene in highly stable films with second-order nonlinear optical properties

Paul J.A. Kenis, Oscar F.J. Noordman, Holger Schönherr, Esther G. Kerver, Bianca H.M. Snellink‐Ruël, Gerrit J. van Hummel, Sybolt Harkema, Cornelis P.J.M. van der Vorst, Jeff Hare, Stephen J. Picken, Johan F.J. Engbersen, Niek F. van Hulst, G. Julius Vancso, David N. Reinhoudt

Research output: Contribution to journalArticleAcademicpeer-review

37 Citations (Scopus)


Highly stable films of tetranitrotetrapropoxycalix[4]arene (9) with second-order nonlinear optical (NLO) properties and a noncentrosymmetric structure were obtained by a novel crystallization process at 130-140 degrees C in a de electric field. The packing of 9 in these films was elucidated by a combination of X-ray diffraction, angle-dependent second- harmonic generation, and scanning force microscopy (SFM). The experimental results agree well with solid-state molecular dynamics calculations for these films. No crystalline phase was observed for nitrocalix[4]arene derivatives with longer or branched alkyl chains; this explains the limited NLO stability of films of these calixarenes. Scanning force microscopy o­n the aligned films of 9 showed two distinct surface lattice structures: a rectangular lattice (a = 9.3, b = 11.7 Angstrom) and a pseudohexagonal lattice (d approximate to 11.4 Angstrom). The combination of these data with the interlayer distance of 8.9 Angstrom (X-ray diffraction) allowed the packing of molecules of 9 in these structures to be fully elucidated at the molecular level.
Original languageEnglish
Pages (from-to)1225-1234
JournalChemistry: a European journal
Issue number7
Publication statusPublished - 1998



  • Calixarenes
  • Supramolecular Chemistry
  • Structure elucidation
  • Nonlinear optics

Cite this