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

物理化学学报 >> 2012, Vol. 28 >> Issue (11): 2574-2580.doi: 10.3866/PKU.WHXB201207302

非对称笼间电子迁移异构体与电场诱导电子迁移

王银锋¹, 黄俭根¹, 周光培¹, 李志儒²

1 井冈山大学化学化工学院, 井冈山大学应用化学研究所, 江西省配位化学重点实验室,江西吉安 343009;
2 吉林大学理论化学研究所, 长春 130023

收稿日期:2012-06-08 修回日期:2012-07-30 发布日期:2012-10-17
通讯作者: 王银锋, 李志儒 E-mail:cyclont@yeah.net; lzr@jlu.edu.cn
基金资助:
江西省科技厅自然科学基金(20114BAB213007); 江西省教育厅自然科学基金(GJJ12486); 国家自然科学基金(21173098); 井冈山大学博士启动基金(JZ10045)及吉林大学理论计算化学国家重点实验室开放课题基金资助项目

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

WANG Yin-Feng¹, HUANG Jian-Gen¹, ZHOU Guang-Pei¹, LI Zhi-Ru²

1 School of Chemistry and Chemical Engineering, Institute of Applied Chemistry, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji’an 343009, Jiangxi Province, P. R. China;
2 State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P. R. China

Received:2012-06-08 Revised:2012-07-30 Published:2012-10-17
Supported by:
The project was supported by the Science and Technology Project of Jiangxi Provincial Department of Science & Technology, China (20114BAB213007), Science and Technology Project of Jiangxi Provincial Department of Education (GJJ12486), National Natural Science Foundation of China (21173098), DrStart-up Fund Research of Jinggangshan University (JZ10045), China, and Foundation of State Key Laboratory of Theoretical and Computational Chemistry of Jilin University, China.

摘要/Abstract

摘要：

基于密度泛函理论研究了非对称双笼型单分子溶剂化电子e^-@C₂₄F₂₂(NH)₂C₂₀F₁₈(1、2 和3), 进一步展示了我们提出的一种新型电子异构体——(非对称型的)笼间电子迁移异构体. 1、2 和3 具有显著不同的偶极矩. 由于都存在两个氧化还原中心, 它们属于一种非金属型的新型Robin-Day II-III 分子. 对于1 和3, 额外电子分别定域在C₂₄F₂₂和C₂₀F₁₈笼里(Robin-Day II); 对于2, 额外电子则离域于两个非对称的笼中(Robin-Day III). 值得注意的是, 在y 轴方向上外加-0.0004和-0.0008 a.u.的临界电场(E_c)时可分别使1 的额外电子从C₂₄F₂₂笼中部分和全部地迁移到C₂₀F₁₈笼中, 即实现从1 到2 再到3 的转化; 当E_c为0.0004 a.u.时, 3 的额外电子从C₂₀F₁₈笼中全部迁移到了C₂₄F₂₂笼中, 即3 未经过2 直接转化成了1.

关键词: 电场诱导, Robin-Day分子, 单分子溶剂化电子, 电子异构体, 不对称笼间电子迁移

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

点击下载补充材料PDF格式文件

王银锋, 黄俭根, 周光培, 李志儒. 非对称笼间电子迁移异构体与电场诱导电子迁移[J]. 物理化学学报, 2012, 28(11): 2574-2580.

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.

参考文献

(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]	李海霞, 王纪伟, 焦丽芳, 陶占良, 梁静. 碳包覆纳米SnSb合金作为高性能钠离子电池负极材料[J]. 物理化学学报, 0, (): 0-0.
[2]	王丹,丁迅雷,廖珩璐,戴佳钰. 单个金或银原子掺杂的氧化钒团簇上的甲烷活化反应[J]. 物理化学学报, 2019, 35(9): 1005-1013.
[3]	纪毅, 梁力鑫, GUO Changmiao, 包信和, POLENOVA Tatyana, 侯广进. 固体核磁共振高速魔角旋转条件下对称性脉冲零量子同核重耦技术[J]. 物理化学学报, 0, (): 0-0.
[4]	任熠, 刘清宇, 赵艳霞, 杨祁, 何圣贵. 多次碰撞条件下金阳离子诱导的甲烷碳-碳偶联[J]. 物理化学学报, 0, (): 0-0.
[5]	张涛,仇运广,罗启超,程曦,赵丽芬,严昕,彭浡,蒋华良,阳怀宇. 钙离子和镁离子浓度变化对磷脂酰乙醇胺-磷脂酰甘油双分子层膜的影响[J]. 物理化学学报, 2019, 35(8): 840-849.
[6]	韩萌茹,周亚男,周旋,储伟. 通过g-C₃N₄担载MNi₁₂ (Fe, Co, Cu, Zn)纳米团簇调节甲烷化[J]. 物理化学学报, 2019, 35(8): 850-857.
[7]	石峰, 胡丽丽, 任进军, 杨秋红. 固体核磁共振研究碱土金属磷硅酸盐玻璃的六配位硅结构[J]. 物理化学学报, 0, (): 0-0.
[8]	李诗涵, 赵侦超, 李世坤, 邢友东, 张维萍. DFT计算结合固体NMR研究富铝SSZ-13的铝分布和Brønsted酸性[J]. 物理化学学报, 0, (): 0-0.
[9]	李超, 沈明, 胡炳文. 面向金属离子电池研究的固体核磁共振和电子顺磁共振方法[J]. 物理化学学报, 0, (): 0-0.
[10]	于泽,李晓宏,李运超,叶明富. 钾离子浓度依赖的铅离子稳定G-四链体构型转化[J]. 物理化学学报, 2018, 34(11): 1293-1298.
[11]	王琴,薛珉敏,张助华. 硼烯化学合成进展与展望[J]. 物理化学学报, 2019, 35(6): 565-571.
[12]	柳平英,刘春艳,刘倩,马晶. 含偶氮苯主-客体复合物的光致异构化反应对结合能与几何构象的影响[J]. 物理化学学报, 2018, 34(10): 1171-1178.
[13]	赵亚松,张丽娟,齐健,金泉,林凯峰,王丹. 石墨二炔及其电子转移增强特性[J]. 物理化学学报, 2018, 34(9): 1048-1060.
[14]	陈文琼,关永吉,张晓萍,邓友全. 分子动力学模拟研究外电场对咪唑类离子液体振动谱的影响[J]. 物理化学学报, 2018, 34(8): 912-919.
[15]	贺熙,吕逍雨,樊喜,林文俊,李浩然,王从敏. 阴离子功能化大孔树脂用于二氧化硫的多位点高效捕集[J]. 物理化学学报, 2018, 34(8): 896-903.

非对称笼间电子迁移异构体与电场诱导电子迁移

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

PDF (PC)

赞

可视化

摘要/Abstract

支持信息

引用本文

使用本文

参考文献

相关文章 15

Metrics

本文评价

推荐阅读 10