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

Click here to download Supporting Info material in PDF type

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

[1]	LI Haixia, WANG Jiwei, JIAO Lifang, TAO Zhanliang, LIANG Jing. Spherical Nano-SnSb/C Composite as a High-Performance Anode Material for Sodium Ion Batteries [J]. Acta Physico-Chimica Sinica, 0, (): 0-0.
[2]	Dan WANG,Xunlei DING,Henglu LIAO,Jiayu DAI. Methane Activation on (Au/Ag)₁-Doped Vanadium Oxide Clusters [J]. Acta Physico-Chimica Sinica, 2019, 35(9): 1005-1013.
[3]	JI Yi, LIANG Lixin, GUO Changmiao, BAO Xinhe, POLENOVA Tatyana, HOU Guangjin. Zero-Quantum Homonuclear Recoupling Symmetry Sequences in Solid-State Fast MAS NMR Spectroscopy [J]. Acta Physico-Chimica Sinica, 0, (): 0-0.
[4]	Yi Ren, Qing-Yu Liu, Yan-Xia Zhao, Qi Yang, Sheng-Gui He. C-C Coupling of Methane Mediated by Atomic Gold Cations under Multiple-Collision Conditions [J]. Acta Physico-Chimica Sinica, 0, (): 0-0.
[5]	Tao ZHANG,Yunguang QIU,Qichao LUO,Xi CHENG,Lifen ZHAO,Xin YAN,Bo PENG,Hualiang JIANG,Huaiyu YANG. Concentration Dependent Effects of Ca²⁺ and Mg²⁺ on the Phosphatidylethanolamine-Phosphatidylglycerol Bilayer [J]. Acta Physico-Chimica Sinica, 2019, 35(8): 840-849.
[6]	Mengru HAN,Yanan ZHOU,Xuan ZHOU,Wei CHU. Tunable Reactivity of MNi₁₂ (M = Fe, Co, Cu, Zn) Nanoparticles Supported on Graphitic Carbon Nitride in Methanation [J]. Acta Physico-Chimica Sinica, 2019, 35(8): 850-857.
[7]	SHI Feng, HU Lili, REN Jinjun, YANG Qiuhong. Structural Investigation of Alkaline-Earth Phosphosilicate Glasses Containing Six-Coordinated Silicon by Solid-State NMR [J]. Acta Physico-Chimica Sinica, 0, (): 0-0.
[8]	LI Shihan, ZHAO Zhenchao, LI Shikun, XING Youdong, ZHANG Weiping. Aluminum Distribution and Brønsted Acidity of Al-Rich SSZ-13 Zeolite: A Combined DFT Calculation and Solid-State NMR Study [J]. Acta Physico-Chimica Sinica, 0, (): 0-0.
[9]	LI Chao, SHEN Ming, HU Bingwen. Solid-State NMR and EPR Methods for Metal Ion Battery Research [J]. Acta Physico-Chimica Sinica, 0, (): 0-0.
[10]	Ze YU,Xiaohong LI,Yunchao LI,Mingfu YE. K⁺ Concentration-Dependent Conformational Change of Pb²⁺-Stabilized G-quadruplex [J]. Acta Phys. -Chim. Sin., 2018, 34(11): 1293-1298.
[11]	Qin WANG,Minmin XUE,Zhuhua ZHANG. Chemical Synthesis of Borophene: Progress and Prospective [J]. Acta Phys. -Chim. Sin., 2019, 35(6): 565-571.
[12]	Pingying LIU,Chunyan LIU,Qian LIU,Jing MA. Influence of Photoisomerization on Binding Energy and Conformation of Azobenzene-Containing Host-Guest Complex [J]. Acta Phys. -Chim. Sin., 2018, 34(10): 1171-1178.
[13]	Yasong ZHAO,Lijuan ZHANG,Jian QI,Quan JIN,Kaifeng LIN,Dan WANG. Graphdiyne with Enhanced Ability for Electron Transfer [J]. Acta Phys. -Chim. Sin., 2018, 34(9): 1048-1060.
[14]	Wenqiong CHEN,Yongji GUAN,Xiaoping ZHANG,Youquan DENG. Influence of External Electric Field on Vibrational Spectrum of Imidazolium-Based Ionic Liquids Probed by Molecular Dynamics Simulation [J]. Acta Phys. -Chim. Sin., 2018, 34(8): 912-919.
[15]	Xi HE,Xiaoyu LÜ,Xi FAN,Wenjun LIN,Haoran LI,Congmin WANG. Ultra-High SO₂ Capture by Anion-Functionalized Resins through Multiple-Site Adsorption [J]. Acta Phys. -Chim. Sin., 2018, 34(8): 896-903.

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

PDF (PC)

Like

Knowledge

Abstract

Supporting Info

Cite this article

share this article

References

Related Articles 15

Metrics

Comments

Recommended 10