Photoluminescence and charge-transfer complexes of calixarenes grafted on TiO 2 nanoparticles

Justin M Notestein, Enrique Iglesia, Alexander Katz

Research output: Contribution to journalArticle

57 Citations (Scopus)

Abstract

Calix[4]arenes and thiacalix[4]arenes, cyclic tetramers of phenol, are synthesized with para position (upper rim) feri-butyl, Br, and NO 2 groups and grafted covalently onto surfaces of TiO 2 nanoparticles up to a geometrical maximum surface density of 0.30 nm -2. Grafted calixarenes are hydrolytically stable and are shown to exist in their 'cone' conformation from comparison with model materials synthesized by grafting preformed calixarene - Ti complexes. Individually, protonated calixarenes and TiO 2 absorb only UV light, but calixarene - TiO 2 hybrid organic - inorganic materials absorb light at significantly lower energies in the visible range (>2.2 eV, 2 nanoparticles. These absorption energies do not depend on the identity and electron-withdrawing properties of upper rim groups in calixarenes. However, the steady-state photoluminescence emission of the calixarene-TiO 2 hybrid material is weakened uniformly throughout the excitation spectrum when compared with the material before calixarene grafting, and these effects become stronger as calixarene upper rim substituents become more electron-withdrawing. The single-step synthesis protocols described here electronically couple calixarenes with surfaces of oxide semiconductors, leading to sensitization of TiO 2 for absorption in the visible region and provide a systematic method for controlling and understanding surface dipole-mediated electron-transfer phenomena relevant to the photocatalytic and optoelectronic properties of TiO 2.

Original languageEnglish
Pages (from-to)4998-5005
Number of pages8
JournalChemistry of Materials
Volume19
Issue number20
DOIs
Publication statusPublished - Oct 2 2007

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Calixarenes
Charge transfer
Photoluminescence
Nanoparticles
Electrons
Hybrid materials
Ultraviolet radiation
Optoelectronic devices
Phenols
Conformations
Cones
Phenol

ASJC Scopus subject areas

  • Materials Chemistry
  • Materials Science(all)

Cite this

Photoluminescence and charge-transfer complexes of calixarenes grafted on TiO 2 nanoparticles. / Notestein, Justin M; Iglesia, Enrique; Katz, Alexander.

In: Chemistry of Materials, Vol. 19, No. 20, 02.10.2007, p. 4998-5005.

Research output: Contribution to journalArticle

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