电场对金属串配合物M3(dpa)4Cl2 (M=Co, Rh, Ir; dpa=dipyridylamide)结构的影响

引用本文: 黄燕, 黄晓, 许旋. 电场对金属串配合物M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)结构的影响[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201303181 shu

Citation: HUANG Yan, HUANG Xiao, XU Xuan. Effects of Electric Field on the Structures of Metal String Complexes M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201303181 shu

电场对金属串配合物M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)结构的影响

基金项目:
广东省自然科学基金项目(S2012010008763) (S2012010008763)

广东省教育部产学研结合项目(2010B090400184) (2010B090400184)

广东省人才引进专项资金(C10133) (C10133)

广州市科技攻关项目(2011J4300063)资助 (2011J4300063)

摘要:

应用密度泛函理论PBE0 方法研究具有分子导线潜在应用的金属串配合物M₃(dpa)₄Cl₂ (1: M=Co, 2: M=Rh, 3: M=Ir; dpa=dipyridylamide)在电场作用下的几何和电子结构. 结果表明: 配合物基态均是二重态. 1和2的M₃⁶⁺金属链形成三中心三电子σ键, 3 中M₃⁶⁺形成三中心四电子σ键且存在弱的δ键. 随金属原子周期数增大其M―M键增强、LUMO与HOMO能隙减小、金属原子的反铁磁耦合减弱以至消失且自旋密度向配体的离域增强. 在Cl4→Cl5 电场作用下, 低电势端的M3－Cl5 键缩短, 高电势端的M2―Cl4 键增长, M―M平均键长略为缩短, M―M键增强, 有利于分子线的电子传递; 分子能量降低, 偶极矩线性增大. 低电势端Cl5的负电荷向高电势端Cl4 转移, 且3 中金属原子的正电荷由高电势端向低电势端的转移较明显, 自旋电子由低电势端向高电势端金属原子移动, 但桥联配体dpa^-与M和Cl 所在的分子轴间没有电荷转移. 电场使LUMO与HOMO能隙减小, 有利于分子的电子输运. 随金属原子周期数增大, 电场作用下M―M平均键长变化减小, LUMO、HOMO的能级交错现象减少.

关键词:

English

Effects of Electric Field on the Structures of Metal String Complexes M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)

1.
1 School of Chemistry & Environment, South China Normal University, Guangzhou 510006, P. R. China;
2 Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Guangzhou 510006, P. R. China;
3 Key Laboratory of Electrochemical Technology on Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510006, P. R. China;
4 Engineering Research Center of Materials and Technology for Electrochemical Energy Storage, Ministry of Education, South China Normal University, Guangzhou 510006, P. R. China
Received Date: 16 November 2012
Available Online: 17 May 2013
Fund Project:
广东省自然科学基金项目(S2012010008763)

广东省教育部产学研结合项目(2010B090400184)

广东省人才引进专项资金(C10133)

广州市科技攻关项目(2011J4300063)资助

Abstract:

As potential molecular wire species, the geometrical and electronic structures of metal string complexes M₃(dpa)₄Cl₂ (1: M=Co, 2: M=Rh, 3: M=Ir; dpa=dipyridylamide) were investigated theoretically using density functional theory with the PBE0 functional by considering the interaction of an external electric field along the M₃⁶⁺ linear metal chain. The results show that the ground states of the complexes are all doublets. There is a 3-center-3-electron σ bond delocalized over the M₃⁶⁺ chain for 1 and 2, while there is a 3-center-4-electron σ bond and a weak δ bond among the Ir₃⁶⁺ chain in 3. Moving down the column of Co, Rh, and Ir elements in the periodic table, the complexes with the corresponding metals showed some regular trends, such as stronger M－M bonds, smaller LUMO-HOMO gaps, weaker anti-ferromagnetic spin coupling among the M₃⁶⁺ chains, and stronger spin delocalization from M₃⁶⁺ to ligands. In the external electric field along the Cl4→Cl5 direction, the M3 ― Cl5 bonds at the low potential side tend to be shortened, while the M2―Cl4 distances at the high potential side increase. With the increase of electric field, the average M―M distances slightly decrease, which is beneficial for electron transport. When the electric field increases, the molecular energy decreases and the dipole moment linearly increases. Moreover, the negative charge moves from Cl5 at the low potential end towards Cl4 at the high potential end, and the spin electron moves from M3 at the low potential end to M1 and M2 at the high potential end, while the positive charges transfer in the opposite direction along the M₃⁶⁺ chain of 3. However, there is no charge transfer between dpa^- ligands and M₃⁶⁺ chain or Cl^- ligands. The LUMO-HOMO gaps decrease with increasing electric field, which is beneficial for electron transfer. The sensitivity of the frontier orbitals to the electric field is different, which leads to the orbital level crossing for LUMO or HOMO. Moving down the column of metal elements in the periodic table, the complexes with the corresponding metals showed weaker orbital level crossing for LUMO or HOMO and smaller deviation of average M―M distances due to the effect of the electric field.

Key words:

1. [1]
  
  (1) Wu, L. P.; Field, P.; Morrissey, T.; Murphy, C.; Nagle, P.;Hathaway, B.; Simmons, C.; Thornton, P. J. Chem. Soc. DaltonTrans. 1990, 12, 3835.
  (1) Wu, L. P.; Field, P.; Morrissey, T.; Murphy, C.; Nagle, P.;Hathaway, B.; Simmons, C.; Thornton, P. J. Chem. Soc. DaltonTrans. 1990, 12, 3835.
2. [2]
  (2) Aduldecha, S.; Hathaway, B. J. Chem. Soc. Dalton Trans. 1991,4, 993.(2) Aduldecha, S.; Hathaway, B. J. Chem. Soc. Dalton Trans. 1991,4, 993.
3. [3]
  (3) Cotton, F. A.; Daniels, L. M.; Jordan, G. T.; Murillo, C. A.J. Am. Chem. Soc. 1997, 119, 10377. doi: 10.1021/ja971997h(3) Cotton, F. A.; Daniels, L. M.; Jordan, G. T.; Murillo, C. A.J. Am. Chem. Soc. 1997, 119, 10377. doi: 10.1021/ja971997h
4. [4]
  (4) Clérac, R.; Cotton, F. A.; Jeffery, S. P.; Murillo, C. A.;Wang, X.P. Inorg. Chem. 2001, 40, 1265. doi: 10.1021/ic001069a(4) Clérac, R.; Cotton, F. A.; Jeffery, S. P.; Murillo, C. A.;Wang, X.P. Inorg. Chem. 2001, 40, 1265. doi: 10.1021/ic001069a
5. [5]
  (5) Berry, J. F.; Cotton, F. A.; Murillo, C. A.; Roberts, B. K. Inorg.Chem. 2004, 43, 2277. doi: 10.1021/ic0354320(5) Berry, J. F.; Cotton, F. A.; Murillo, C. A.; Roberts, B. K. Inorg.Chem. 2004, 43, 2277. doi: 10.1021/ic0354320
6. [6]
  (6) Clérac, R.; Cotton, F. A.; Daniels, L. M.; Dunbar, K. R.;Kirschbaum, K.; Murillo, C. A.; Pinkerton, A. A.; Schultz, A. J.;Wang, X. P. J. Am. Chem. Soc. 2000, 122, 6226. doi: 10.1021/ja000515q(6) Clérac, R.; Cotton, F. A.; Daniels, L. M.; Dunbar, K. R.;Kirschbaum, K.; Murillo, C. A.; Pinkerton, A. A.; Schultz, A. J.;Wang, X. P. J. Am. Chem. Soc. 2000, 122, 6226. doi: 10.1021/ja000515q
7. [7]
  (7) Yang, E. C.; Cheng, M. C.; Tsai, M. S.; Peng, S. M. Chem.Commun. 1994, 2377.(7) Yang, E. C.; Cheng, M. C.; Tsai, M. S.; Peng, S. M. Chem.Commun. 1994, 2377.
8. [8]
  (8) Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Pascual, I. J. Am.Chem. Soc. 1997, 119, 10223. doi: 10.1021/ja971998+(8) Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Pascual, I. J. Am.Chem. Soc. 1997, 119, 10223. doi: 10.1021/ja971998+
9. [9]
  (9) Cotton, F. A.; Daniels, L. M.; Jordan, G. T. Chem. Commun.1997, 421.(9) Cotton, F. A.; Daniels, L. M.; Jordan, G. T. Chem. Commun.1997, 421.
10. [10]
  (10) Sheu, J. T.; Lin, C. C.; Chao, I.;Wang, C. C.; Peng, S. M. Chem.Commun. 1996, 315.(10) Sheu, J. T.; Lin, C. C.; Chao, I.;Wang, C. C.; Peng, S. M. Chem.Commun. 1996, 315.
11. [11]
  (11) Shieh, S. J.; Chou, C. C.; Lee, G. H.;Wang, C. C.; Peng, S. M.Angew. Chem. Int. Edit. 1997, 36, 56.(11) Shieh, S. J.; Chou, C. C.; Lee, G. H.;Wang, C. C.; Peng, S. M.Angew. Chem. Int. Edit. 1997, 36, 56.
12. [12]
  (12) Wang,W. Z.; Ismayilov, R. H.; Lee, G. H.; Yeh, C. Y.; Peng, S.M. Dalton Trans. 2007, 830.(12) Wang,W. Z.; Ismayilov, R. H.; Lee, G. H.; Yeh, C. Y.; Peng, S.M. Dalton Trans. 2007, 830.
13. [13]
  (13) Peng, S. M.;Wang, C. C.; Jang, Y. L.; Chen, Y. H.; Li, F. Y.;Mou, C. Y.; Leung, M. K. J. Mag. Mag. Mater. 2000, 209, 80.doi: 10.1016/S0304-8853(99)00650-2(13) Peng, S. M.;Wang, C. C.; Jang, Y. L.; Chen, Y. H.; Li, F. Y.;Mou, C. Y.; Leung, M. K. J. Mag. Mag. Mater. 2000, 209, 80.doi: 10.1016/S0304-8853(99)00650-2
14. [14]
  (14) Ismayilov, R. H.;Wang,W. Z.; Lee, G. H.; Yeh, C. Y.; Hua, S.A.; Song, Y.; Rohmer, M. M.; Bénard, M.; Peng, S. M. Angew.Chem. Int. Edit. 2011, 50, 2045. doi: 10.1002/anie.v50.9(14) Ismayilov, R. H.;Wang,W. Z.; Lee, G. H.; Yeh, C. Y.; Hua, S.A.; Song, Y.; Rohmer, M. M.; Bénard, M.; Peng, S. M. Angew.Chem. Int. Edit. 2011, 50, 2045. doi: 10.1002/anie.v50.9
15. [15]
  (15) Rohmer, M. M.; Bénard, M. J. Am. Chem. Soc. 1998, 120, 9372.doi: 10.1021/ja981400d(15) Rohmer, M. M.; Bénard, M. J. Am. Chem. Soc. 1998, 120, 9372.doi: 10.1021/ja981400d
16. [16]
  (16) Pantazis, D. A.; McGrady, J. E. J. Am. Chem. Soc. 2006, 128,4128. doi: 10.1021/ja0581402(16) Pantazis, D. A.; McGrady, J. E. J. Am. Chem. Soc. 2006, 128,4128. doi: 10.1021/ja0581402
17. [17]
  (17) Lin, S. Y.; Chen, I.W. P.; Chen, C. H.; Hsieh, M. H.; Yeh, C. Y.;Lin, T.W.; Chen, Y. H.; Peng, S. M. J. Phys. Chem. B 2004,108, 959. doi: 10.1021/jp035415w(17) Lin, S. Y.; Chen, I.W. P.; Chen, C. H.; Hsieh, M. H.; Yeh, C. Y.;Lin, T.W.; Chen, Y. H.; Peng, S. M. J. Phys. Chem. B 2004,108, 959. doi: 10.1021/jp035415w
18. [18]
  (18) Chen, I.W. P.; Fu, M. D.; Tseng,W. H.; Yu, J. Y.;Wu, S. H.; Ku,C. J.; Chen, C. H.; Peng, S. M. Angew. Chem. Int. Edit. 2006,118, 5946.(18) Chen, I.W. P.; Fu, M. D.; Tseng,W. H.; Yu, J. Y.;Wu, S. H.; Ku,C. J.; Chen, C. H.; Peng, S. M. Angew. Chem. Int. Edit. 2006,118, 5946.
19. [19]
  (19) Huang, G. C.; Liu, I. P. C.; Kuo, J. H.; Huang, Y. L.; Yeh, C. Y.;Lee, G. H.; Peng, S. M. Dalton Trans. 2009, 2623.(19) Huang, G. C.; Liu, I. P. C.; Kuo, J. H.; Huang, Y. L.; Yeh, C. Y.;Lee, G. H.; Peng, S. M. Dalton Trans. 2009, 2623.
20. [20]
  (20) Tsai, T.W.; Huang, Q. R.; Peng, S. M.; Jin, B. Y. J. Phys. Chem.C 2010, 114, 3641. doi: 10.1021/jp907893q(20) Tsai, T.W.; Huang, Q. R.; Peng, S. M.; Jin, B. Y. J. Phys. Chem.C 2010, 114, 3641. doi: 10.1021/jp907893q
21. [21]
  (21) Georgiev, V. P.; McGrady, J. E. Inorg. Chem. 2010, 49, 5591.doi: 10.1021/ic100493t(21) Georgiev, V. P.; McGrady, J. E. Inorg. Chem. 2010, 49, 5591.doi: 10.1021/ic100493t
22. [22]
  (22) Li, Y.W.; Zhang, Y.; Yin, G. P.; Zhao, J.W. Chem. J. Chin.Univ. 2006, 27, 292. [李延伟, 章岩, 尹鸽平, 赵健伟. 高等学校化学学报, 2006, 27, 292.](22) Li, Y.W.; Zhang, Y.; Yin, G. P.; Zhao, J.W. Chem. J. Chin.Univ. 2006, 27, 292. [李延伟, 章岩, 尹鸽平, 赵健伟. 高等学校化学学报, 2006, 27, 292.]
23. [23]
  (23) Yan, A. Y.; Song, X. S.; Jiang, M. Acta. Chim. Sin. 2009, 67 (16), 1875. [闫安英, 宋晓书, 姜明. 化学学报, 2009, 67 (16), 1875.](23) Yan, A. Y.; Song, X. S.; Jiang, M. Acta. Chim. Sin. 2009, 67 (16), 1875. [闫安英, 宋晓书, 姜明. 化学学报, 2009, 67 (16), 1875.]
24. [24]
  (24) Ye, Y. F.; Zhang, M. L.; Liu, H. M.; Zhao, J.W. Journal ofAtomic and Molecular Physics 2008, 25 (1), 6. [叶原丰, 张密林, 刘洪梅, 赵健伟. 原子与分子物理学报, 2008, 25 (1), 6.](24) Ye, Y. F.; Zhang, M. L.; Liu, H. M.; Zhao, J.W. Journal ofAtomic and Molecular Physics 2008, 25 (1), 6. [叶原丰, 张密林, 刘洪梅, 赵健伟. 原子与分子物理学报, 2008, 25 (1), 6.]
25. [25]
  (25) Tan, Y.; Huang, X.; Xu, X.; Xu, Z. G. Chem. J. Chin. Univ.2012, 33, 1278. [谭莹, 黄晓, 许旋, 徐志广. 高等学校化学学报, 2012, 33, 1278.](25) Tan, Y.; Huang, X.; Xu, X.; Xu, Z. G. Chem. J. Chin. Univ.2012, 33, 1278. [谭莹, 黄晓, 许旋, 徐志广. 高等学校化学学报, 2012, 33, 1278.]
26. [26]
  (26) Huang, X.; Tan, Y.; Xu, X.; Xu, Z. G. Acta Chim. Sin. 2012, 70 (18), 1979. [黄晓, 谭莹, 许旋, 徐志广. 化学学报,2012, 70 (18), 1979.] doi: 10.6023/A12030051(26) Huang, X.; Tan, Y.; Xu, X.; Xu, Z. G. Acta Chim. Sin. 2012, 70 (18), 1979. [黄晓, 谭莹, 许旋, 徐志广. 化学学报,2012, 70 (18), 1979.] doi: 10.6023/A12030051
27. [27]
  (27) Glendening, E. D.; Reed, A. E.; Carpenter, J. E. NBO Version3.1.(27) Glendening, E. D.; Reed, A. E.; Carpenter, J. E. NBO Version3.1.
28. [28]
  (28) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision D.02; Gaussian Inc.:Wallingford, CT, 2003.(28) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision D.02; Gaussian Inc.:Wallingford, CT, 2003.
29. [29]
  (29) Rohmer, M. M.; Strich, A.; Bénard, M.; Malrieu, J. P. J. Am.Chem. Soc. 2001, 123, 9126. doi: 10.1021/ja0103142(29) Rohmer, M. M.; Strich, A.; Bénard, M.; Malrieu, J. P. J. Am.Chem. Soc. 2001, 123, 9126. doi: 10.1021/ja0103142
30. [30]
  (30) Ma, H. X.; Zheng, Y. L.; Zhan, Y. S.; Tan, Y.; Huang, X.; Peng,Q.; Xu, X. Acta Phys. -Chim. Sin. 2012, 28 (7), 1637. [马华璇, 郑燕玲, 詹益仕, 谭莹, 黄晓, 彭琦, 许旋. 物理化学学报, 2012, 28 (7), 1637.] doi: 10.3866/PKU.WHXB201204111
  (30) Ma, H. X.; Zheng, Y. L.; Zhan, Y. S.; Tan, Y.; Huang, X.; Peng,Q.; Xu, X. Acta Phys. -Chim. Sin. 2012, 28 (7), 1637. [马华璇, 郑燕玲, 詹益仕, 谭莹, 黄晓, 彭琦, 许旋. 物理化学学报, 2012, 28 (7), 1637.] doi: 10.3866/PKU.WHXB201204111

扫一扫看文章

计量

PDF下载量: 612
文章访问数: 1162
HTML全文浏览量: 47

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

电场对金属串配合物M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)结构的影响

English

Effects of Electric Field on the Structures of Metal String Complexes M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处