非对称笼间电子迁移异构体与电场诱导电子迁移

doi:10.3866/PKU.WHXB201207302

Abstract

Abstract:

The asymmetrical, double-cage-shaped, single molecular solvated electron compounds e^-@C₂₄F₂₂(NH)₂C₂₀F₁₈ (1, 2, and 3) were investigated based on density functional theory (DFT). This work revealed a novel species of electromer consisting of asymmetrical inter-cage electron-transfer isomers. These inter-cage electron-transfer isomers belong to a new form of Robin-Day class II-III molecules. 1 and 3 are Robin-Day class II, with the excess electron inside the C₂₄F₂₂ and C₂₀F₁₈ cages respectively, while 2 is class III with the excess electron inside both cages. These electromers were found to exhibit significantly different dipole moments. The application of external electric fields of -0.0004 or -0.0008 a.u. in the y-axis direction of 1 resulted in either partial or whole transfer of the excess electron from C₂₄F₂₂ to C₂₀F₁₈, allowing conversion from 1 to 2 or 3. An E_c value of 0.0004 a.u. was determined, indicating that the excess electron can wholly transfer from the C₂₀F₁₈ cage to C₂₄F₂₂, resulting in conversion from 3 to 1 without going through 2.

Key words: Electric field inducement, Robin-Day molecule, Single molecular solvated electron, Electromer, Asymmetrical inter-cage electron transfer

MSC2000:

O641

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WANG Yin-Feng, HUANG Jian-Gen, ZHOU Guang-Pei, LI Zhi-Ru. Asymmetrical Inter-Cage Electron Transfer Electromers and Their Transfer Characteristics Under Electric Fields[J].Acta Phys. -Chim. Sin., 2012, 28(11): 2574-2580.

References

(1) Bally, T. Nat. Chem. 2010, 2, 165. doi: 10.1038/nchem.564
(2) Puschmann, H. F.; Harmer, J.; Stein, D.; Rüegger, H.; de Bruin,B.; Grützmacher, H. Angew. Chem. Int. Edit. 2010, 49, 385.doi: 10.1002/anie.200903201
(3) Gütlich, P.; Dei, A. Angew. Chem. Int. Edit. 1997, 36, 2734.doi: 10.1002/(ISSN)1521-3773
(4) Chaudhuri, P.; Hess, M.; Hildenbrand, K.; Bill, E.;Weyhermüller,T.;Wieghardt, K. Inorg. Chem. 1999, 38, 2781. doi: 10.1021/ic990003g
(5) de Visser, S. P.; Ogliaro, F.; Harris, N.; Shaik, S. J. Am. Chem. Soc. 2001, 123, 3037. doi: 10.1021/ja003544+
(6) Chen, D. L.; Tian,W. Q.; Feng, J. K.; Sun, C. C. J. Chem. Phys.2008, 128, 044318.
(7) Lu, X.; Chen, Z.; Thiel,W.; Schleyer, P. v. R.; Huang, R.;Zheng, L. J. Am. Chem. Soc. 2004, 126, 14871. doi: 10.1021/ja046725a
(8) Wang, Y. Y.; Shi, Q.; Zhang, F. X.; Shi, Q. Z. Chin. J. Inorg. Chem. 1999, 15, 557. [王尧宇, 时茜, 张逢星, 史启祯.无机化学学报, 1999, 15, 557.]
(9) Robin, M. N.; Day, P. Adv. Inorg. Chem. Radiochem. 1967, 10,247.
(10) Shriver, D. F.; Atkins, P.W.; Langford, C. H. Inorganic. Chemistry; Higher Education Press: Beijing, 1997; pp 553-555;translated by Gao, Y. C., Shi, Q. Z., Li, P. R. [Shriver, D. F.;Atkins, P.W.; Langford, C. H. 无机化学. 高忆慈, 史启祯,李丙瑞, 译. 北京: 高等教育出版社, 1997: 553-555.]
(11) Demadis, K. D.; Hartshorn, C. M.; Meyer, T. J. Chem. Rev.2001, 101, 2655. doi: 10.1021/cr990413m
(12) Lambert, C.; Nöll, G. J. Am. Chem. Soc. 1999, 121, 8434. doi: 10.1021/ja991264s
(13) Desfrançois, C.; Carles, S.; Schermann, J. P. Chem. Rev. 2000,100, 3943. doi: 10.1021/cr990061j
(14) Lee, H. M.; Lee, S.; Kim, K. S. J. Chem. Phys. 2003, 119, 187.doi: 10.1063/1.1576757
(15) Li, Y.; Li, Z. R.;Wu, D.; Li, R. Y.; Hao, X. Y.; Sun, C. C.J. Phys. Chem. B 2004, 108, 3145. doi: 10.1021/jp036808y
(16) Matsuishi, S.; Toda, Y.; Miyakawa, M.; Hayashi, K.; Kamiya,T.; Hirano, M.; Tanaka, I.; Hosono, H. Science 2003, 301, 626.doi: 10.1126/science.1083842
(17) Wang, Y. F.; Li, Z. R.;Wu, D.; Sun, C. C.; Gu, F. L. J. Comput. Chem. 2010, 31, 195. doi: 10.1002/jcc.v31:1
(18) Wang, Y. F.; Chen,W.; Yu, G. T.; Li, Z. R.;Wu, D.; Sun, C. C.J. Comput. Chem. 2010, 32, 2012.
(19) Wang, Y. F.; Li, Z. R.;Wu, D.; Li, Y.; Sun, C. C.; Gu, F. L.J. Phys. Chem. A 2010, 114, 11782. doi: 10.1021/jp1056557
(20) Wang, Y. F.; Li, Y.; Zhou, Z. J.; Li, Z. R.;Wu, D.; Huang, J.; Gu,F. L. ChemPhysChem 2012, 13, 756. doi: 10.1002/cphc.201100790
(21) Wang, X.; Ma, J. Phys. Chem. Chem. Phys. 2011, 13, 16134.
(22) Zhou, Z. J.; Li, X. P.; Liu, Z. B.; Li, Z. R.; Huang, X. R.; Sun,C. C. J. Phys. Chem. A 2010, 115, 1418.
(23) Jordan, K. D.; Luken,W. J. Chem. Phys. 1976, 64, 2760.doi: 10.1063/1.432599
(24) Skurski, P.; Gutowski, M.; Simons, J. Int. J. Quantum Chem.2000, 80, 1024. doi: 10.1002/(ISSN)1097-461X
(25) Rienstra-Kiracofe, J. C.; Tschumper, G. S.; Schaefer, H. F., III;Sreela, N.; Ellison, G. B. Chem. Rev. 2002, 102, 231. doi: 10.1021/cr990044u
(26) Pathak, A. K.; Mukherjee, T.; Maity, D. K. J. Chem. Phys. 2007,127, 044304. doi: 10.1063/1.2756535
(27) Khan, A. Chem. Phys. Lett. 2005, 401, 85. doi: 10.1016/j.cplett.2004.11.035
(28) Likura, H.; Tsuneda, T.; Yanai, T.; Hirao, K. J. Chem. Phys.2001, 115, 3540. doi: 10.1063/1.1383587
(29) Zhang, L.; Yan, S.; Cukier, R. I.; Bu, Y. J. Phys. Chem. B 2008,112, 3767.
(30) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09,Revision A.01; Gaussian Inc.:Wallingford, CT, 2009.
(31) Aihara, J. J. Phys. Chem. A 1999, 103, 7487. doi: 10.1021/jp990092i
(32) Simons, J. J. Phys. Chem. A 2008, 112, 6401. doi: 10.1021/jp711490b

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Asymmetrical Inter-Cage Electron Transfer Electromers and Their Transfer Characteristics Under Electric Fields

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