Theoretical study on the electronic structures and related properties of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and its cationic lipid derivates in the charge/discharge processes has been carried out using the density functional theory (DFT) at the (U)B3LYP/6-31G(d,p) or 6-31+G(d,p) level. The changes and regularities of geometric and electronic properties of these compounds in the charge/discharge processes were revealed in detail. The computational results show that the substitute group plays a very important role in the electronic structures and related properties of TEMPOs during the charge/discharge processes. It is very interesting to find that after getting an electron, TEMPO is more stable in singlet state but the lipid is more stable in triplet state. For TEMPO, both the charge and the discharge processes greatly influence the electronic properties of N and O atoms of the radical part. For the cationic lipid, the discharge process mainly influences the pyridinium head and the charge process mainly influences the free radical head. Moreover, the solvent effect plays an important role in some bond lengths and the charge population of the free radical head. In addition, the UV-Vis absorption spectra of TEMPO and the lipid were calculated and simulated using TDDFT at the 6-31G(d,p) or 6-31+G(d,p) level, in satisfying agreement with the experimental ones.

r1
R. Numa, M. Baron, R. Kohen and R. Yaka
Eur. J. Pharmacol.
,
650
,
157
(
2011
).
r2
Y. Taguchi, Y. Ishida, S. Tsuge, H. Ohtani, K. Kimura, T. Yoshikawa and H. Matsubara
Polym. Degrad. Stabil.
,
83
,
221
(
2004
).
r3
K. Pietrasik, O. Swiatkowska and A. Kaim
Polymer.
,
55
,
812
(
2010
).
r4
P. Ding, D. Wunnicke, H. J. Steinhoff and F. Seela
Chem. Eur. J.
,
16
,
14385
(
2010
).
r5
J. S. Yadav, K. V. R. Rao, K. Ravindar and B. V. S. Reddy
Eur. J. Org. Chem.
,
58
,
2011
(
2011
).
r6
X. Li, J. Han, M. L. Pang, Y. Chen, J. X. Zhang, H. Ma, Z. J. He and J. B. Meng
Tetrahedron. Lett.
,
48
,
6044
(
2007
).
r7
L. Zhu, K. L. Yao and Z. L. Liu
J. Magn. Magn. Mater.
,
301
,
301
(
2006
).
r8
M. Y. Zheng, Y. S. Wei, Z. W. An and S. Wang
Chin. Chem. Lett.
,
20
,
549
(
2009
).
r9
Z. Zhang, P. Chen, T. N. Murakami, S. M. Zakeeruddin and M. Gråtzel
Adv. Funct. Mater.
,
18
,
341
(
2008
).
r10
H. Nishide, S. Iwasa, Y. J. Pu, T. Suga, K. Nakahara and M. Satoh
Electrochim. Acta
,
50
,
827
(
2004
).
r11
K. Koshika, N. Chikushi, K. Sano, K. Oyaizu and H. Nishide
Green Chem.
,
12
,
1573
(
2010
).
r12
J. Qu, T. Katsumata, M. Satoh, J. Wada, F. Terakura, F. Mizoguchi, N. Ogata and T. Masuda
Chem. Eur. J.
,
13
,
7965
(
2007
).
r13
K. Oyaizu, Y. Ando, H. Konishi and H. Nishide
J. Am. Chem. Soc.
,
130
,
14459
(
2008
).
r14
J. Qu, F. Z. Khan, M. Satoh, J. Wada, H. Hayashi, K. Mizoguchi and T. Masuda
Polymer.
,
49
,
1490
(
2008
).
r15
J. Qu, R. Morita, M. Satoh, J. Wada, F. Terakura, K. Mizoguchi, N. Ogata and T. Masuda
Chem. Eur. J.
,
14
,
3250
(
2008
).
r16
R. Andreu, J. Garin and J. Orduna
Tetrahedron.
,
57
,
7883
(
2001
).
r17
R. I. J. Amos, J. A. Smith, B. F. Yates and C. H. Schiesser
Tetrahedron.
,
66
,
7600
(
2010
).
r18
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez and J. A. Pople
Gaussian 03, Revision D.01
(
Wallingford CT: Gaussian Inc.
) (
2005
).
r19
I. Novak and B. Kovac
Spectrochimi. Acta A
,
62
,
915
(
2005
).
r20
B. Rahmana, H. Akutsua, J. Yamadaa, K. Ohara and S. Nakatsuji
Synthetic Met.
,
159
,
1123
(
2009
).
r21
D. R. Lide
CRC Handbook of Chemistry and Physics
83th Edn. (
London: CRC Press LLC
) p
9
(
2002
).
r22
Y. K. Wang and J. A. Lei
J. Xi'an Petroleum Institute
,
17
,
49
(
2002
).
r23
J. Li, L. C. Xu, J. C. Chen, K. C. Zheng and L. N. Ji
J. Phys. Chem. A
,
110
,
8174
(
2006
).
r24
F. Pointillart, T. Cauchy, Y. L. Gal, S. Golhen, O. Cador and L. Ouahab
Inorg. Chem.
,
49
,
1947
(
2010
).
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