Coordinative self-assembly and solution-phase X-ray structural characterization of cavity-tailored porphyrin boxes

Joong Lee Suk, Karen L. Mulfort, Xiaobing Zuo, Andrew J. Goshe, Paul J. Wesson, Son Binh T. Nguyen, Joseph T. Hupp, David M. Tiede

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Combining linear Zn porphyrin trimers with orthogonally derivatized porphyrin dimers leads rapidly and spontaneously to the formation of monodisperse, torsionally constrained boxes comprising six components and a total of 16 metalloporphyrins. In situ X-ray scattering measurements confirm the formation of monodisperse assemblies of precisely the size expected from model box structures. While simple subunits yield highly symmetrical boxes, we find that sterically demanding subunits produce unusual twisted boxes. Previous studies of porphyrin-based box-like assemblies (squares) for selective catalysis and molecular sieving revealed two function-inhibiting structural problems: torsional motion along the metal-porphyrin-metal axis and ambiguous outside versus inside functionalization (via axial ligation of available Zn(II) sites). The new 16-porphyrin box assemblies eliminate both problems.

Original languageEnglish
Pages (from-to)836-838
Number of pages3
JournalJournal of the American Chemical Society
Issue number3
Publication statusPublished - Jan 23 2008


ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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