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Issue 9, 2008
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ESR study of molecular dynamics and orientation of TEMPO included in organic 1-D nanochannel

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Abstract

A mixture of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical and 2,2,6,6-tetramethyl-1-piperidine (TEMP) was included into organic 1-D nanochannels of tris(o-phenylenedioxy)cyclotriphosphazene (TPP) crystal. Dilution of the paramagnetic TEMPO radical was achieved with excess TEMP, thereby isolating a TEMPO molecule in the nanochannel. For inclusion compounds of TPP with TEMPO and TEMP (TEMPO/all guest compounds = 0.017 (1), and 0.15 (2)), temperature-dependent electron spin resonance (ESR) spectra were observed to investigate their molecular dynamics and orientation. In the temperature range from 112 K to room temperature, the spectra depended remarkably on the temperature. Temperature dependence was well interpreted by uniaxial rotation, suggesting that TEMPO molecules undergo uniaxial rotation about a channel axis with a molecular orientation in which the N–O bond in the nitroxide group is perpendicular to the channel axis. The activation energy of uniaxial rotation was evaluated as 4.5 ± 0.3 kJ mol−1.

Graphical abstract: ESR study of molecular dynamics and orientation of TEMPO included in organic 1-D nanochannel

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Article information


Submitted
03 Jul 2007
Accepted
19 Nov 2007
First published
06 Dec 2007

Phys. Chem. Chem. Phys., 2008,10, 1263-1269
Article type
Paper

ESR study of molecular dynamics and orientation of TEMPO included in organic 1-D nanochannel

H. Kobayashi, T. Ueda, K. Miyakubo, T. Eguchi and A. Tani, Phys. Chem. Chem. Phys., 2008, 10, 1263
DOI: 10.1039/B710098A

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