Abstract
The molecular orientation and dynamics were examined for 4-acetamido-2,2,6,6-tetramethyl-1-piperidinyloxyl (4-acetamido-TEMPO) radicals, which have a larger substituent group than many other TEMPO radicals, dispersed in the one-dimensional (1D) nanochannel of 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) with 4-substituted-2,2,6,6-tetramethylpiperidine (R-TEMP; R=OH or H). When TEMPOH (R=OH) was used as a spacer for dispersion in the CLPOT nanochannels, the molecular orientation of 4-acetamido-TEMPO in the CLPOT nanochannels was similar to that of other previously reported 4-substituted-TEMPO (4-X-TEMPO; X=OH, =O or OCH3) radicals. However, the activation energy for the rotational diffusion of 4-acetamido-TEMPO in the CLPOT nanochannels, estimated to be 11 kJ mol−1, was larger than that of other 4-X-TEMPO molecules (6–8 kJ mol−1). These results indicate that the molecular dynamics of 4-X-TEMPO in the CLPOT nanochannels can be controlled by the selection of a larger substituent X at the 4-position in 4-X-TEMPO (in this study, X=NHCOCH3), and also suggest an important concept for the design of new organic magnets.
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Acknowledgements
The authors wish to thank Professor T. Asaji of Nihon University for assistance with the ESR analyses and Prof. S. Stoll of the University of the Washington for assistance with the EasySpin calculations.
Funding
This work was supported in part by Common Research Funding from Showa University, 2017–2019 (17FY02).
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Kobayashi, H., Odanaka, Y. Molecular Orientation and Dynamics of a Derivative of 2,2,6,6-Tetramethyl-1-Piperidinyloxyl Radical with a Large Substituent Group Dispersed in 1D-Nanochannels of 2,4,6-Tris(4-Chlorophenoxy)-1,3,5-Triazine Crystal. Appl Magn Reson 51, 711–724 (2020). https://doi.org/10.1007/s00723-020-01218-w
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DOI: https://doi.org/10.1007/s00723-020-01218-w