Scripps VIVO scripps research logo

  • Index
  • Log in
  • Home
  • People
  • Organizations
  • Research
  • Events
Search form

Cavitand-porphyrins

Academic Article
uri icon
  • Overview
  • Identity
  • Additional Document Info
  • View All
scroll to property group menus

Overview

authors

  • Starnes, S. D.
  • Rudkevich, D. M.
  • Rebek Jr., Julius

publication date

  • May 2001

journal

  • Journal of the American Chemical Society  Journal

abstract

  • The synthesis and characterization of new nanoscale container molecules 7 and 8 are described. They are covalent hybrids of deepened, self-folding cavitands and metalloporphyrins. In receptor 7, the Zn-porphyrin wall is directly built onto the cavitand skeleton. Host 8 features a large unimolecular cavity containing two cavitands attached with the Zn-porphyrin wall. Its dimensions, approximately 10 x 25 A, place it among the largest synthetic hosts prepared to date. A series of adamantyl- and pyridyl-containing guests 14-20 of various lengths were prepared and used to determine the hosts' binding abilities in solution using UV/vis and (1)H NMR spectroscopy. Intramolecular hydrogen bonds at the upper rims of the cavitands resist the unfolding of the inner cavities and thereby increase the energetic barrier to guest exchange. The exchange is slow on the NMR time scale (at < or =300 K), and kinetically stable complexes result. When the cavities and metalloporphyrins participate simultaneously in the binding event, very high affinities for guests are found (-DeltaG295 up to 10 kcal x mol(-1) in toluene), to which the porphyrin fragments contribute significantly (-DeltaG295 up to 6 kcal x mol(-1)). The pairwise selection of two different guests by molecular container 8 is reported, and the termolecular complex formed raises the possibility of metal-catalyzed bimolecular reactions in these containers.

subject areas

  • Amides
  • Crystallography, X-Ray
  • Indicators and Reagents
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Conformation
  • Porphyrins
  • Spectrophotometry, Ultraviolet
  • Spectroscopy, Fourier Transform Infrared
scroll to property group menus

Identity

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/ja010038r

PubMed ID

  • 11457274
scroll to property group menus

Additional Document Info

start page

  • 4659

end page

  • 4669

volume

  • 123

issue

  • 20

©2021 The Scripps Research Institute | Terms of Use | Powered by VIVO

  • About
  • Contact Us
  • Support