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Time-resolved EPR and ENDOR study of the photoexcited triplet state of free-base tetraphenylchlorin in a crystalline toluene matrix

Kay, CWM; Di Valentin, M; Mobius, K; (1997) Time-resolved EPR and ENDOR study of the photoexcited triplet state of free-base tetraphenylchlorin in a crystalline toluene matrix. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 (12) 2563 - 2568.

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Abstract

A time-resolved EPR and ENDOR study of the photoexcited tripler state of the free-base tetraphenyl-chlorin has been made in a polycrystalline toluene matrix at 120 K. Crystallization of the toluene results in a partially aligned sample. The nature of the orientation of the solute molecules is investigated by time-resolved EPR spectroscopy using the anisotropy of the zero-field splitting tensor of the triplet state as the observable parameter. It is determined that 55% of the tripler molecules are oriented in a single crystal-like domain with the triplet z-axes oriented within 15 degrees of the magnetic field. In the ENDOR study selective excitation, of only those molecules which have their triplet z-axes parallel to the magnetic field, has permitted the measurement of the A(zz) component of the hyperfine coupling tensor of protons, in the reference frame of the zero-field splitting tenser. The sign and magnitude of the matrix couplings are also determined. The use of the partially oriented sample drastically enhanced the signal intensity over that achieved in a randomly oriented sample by increasing the number of molecules with their triplet z-axes parallel to the magnetic field. Additionally, time-resolved ENDOR spectroscopy allowed the hyperfine interactions to be determined at far higher temperatures than usual for the study of tripler states.

Type: Article
Title: Time-resolved EPR and ENDOR study of the photoexcited triplet state of free-base tetraphenylchlorin in a crystalline toluene matrix
Location: UNIV LANCASTER, LANCASTER, ENGLAND
Keywords: NUCLEAR DOUBLE-RESONANCE, ELECTRON-SPIN-RESONANCE, PHOTO-EXCITED TRIPLETS, N-OCTANE, COMPUTER-ANALYSIS, REACTION CENTERS, SINGLE-CRYSTAL, SPECTRA, PORPHYRINS, PORPHIN
UCL classification: UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > London Centre for Nanotechnology
URI: http://discovery.ucl.ac.uk/id/eprint/71639
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