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
-
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.
-
-
-
[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.
-
[2]
(2) Aduldecha, S.; Hathaway, B. J. Chem. Soc. Dalton Trans. 1991,4, 993.
-
[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
-
[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
-
[5]
(5) Berry, J. F.; Cotton, F. A.; Murillo, C. A.; Roberts, B. K. Inorg.Chem. 2004, 43, 2277. doi: 10.1021/ic0354320
-
[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
-
[7]
(7) Yang, E. C.; Cheng, M. C.; Tsai, M. S.; Peng, S. M. Chem.Commun. 1994, 2377.
-
[8]
(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) Cotton, F. A.; Daniels, L. M.; Jordan, G. T. Chem. Commun.1997, 421.
-
[10]
(10) Sheu, J. T.; Lin, C. C.; Chao, I.;Wang, C. C.; Peng, S. M. Chem.Commun. 1996, 315.
-
[11]
(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) Wang,W. Z.; Ismayilov, R. H.; Lee, G. H.; Yeh, C. Y.; Peng, S.M. Dalton Trans. 2007, 830.
-
[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
-
[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
-
[15]
(15) Rohmer, M. M.; Bénard, M. J. Am. Chem. Soc. 1998, 120, 9372.doi: 10.1021/ja981400d
-
[16]
(16) Pantazis, D. A.; McGrady, J. E. J. Am. Chem. Soc. 2006, 128,4128. doi: 10.1021/ja0581402
-
[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
-
[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.
-
[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.
-
[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
-
[21]
(21) Georgiev, V. P.; McGrady, J. E. Inorg. Chem. 2010, 49, 5591.doi: 10.1021/ic100493t
-
[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.]
-
[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.]
-
[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.]
-
[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.]
-
[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
-
[27]
(27) Glendening, E. D.; Reed, A. E.; Carpenter, J. E. NBO Version3.1.
-
[28]
(28) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision D.02; Gaussian Inc.:Wallingford, CT, 2003.
-
[29]
(29) Rohmer, M. M.; Strich, A.; Bénard, M.; Malrieu, J. P. J. Am.Chem. Soc. 2001, 123, 9126. doi: 10.1021/ja0103142
-
[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
-
[1]
-
-
-
[1]
Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO2 by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20230385
-
[2]
Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N4 site: A density functional theory study. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240302
-
[3]
Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, doi: 10.12461/PKU.DXHX202404045
-
[4]
Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO2 capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240213
-
[5]
Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, doi: 10.12461/PKU.DXHX202405098
-
[6]
Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB202311026
-
[7]
Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, doi: 10.12461/PKU.DXHX202407022
-
[8]
Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, doi: 10.12461/PKU.DXHX202405166
-
[9]
Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB202408004
-
[10]
Huiying Xu , Minghui Liang , Zhi Zhou , Hui Gao , Wei Yi . Application of Quantum Chemistry Computation and Visual Analysis in Teaching of Weak Interactions. University Chemistry, doi: 10.12461/PKU.DXHX202407011
-
[11]
Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240192
-
[12]
Shuang Meng , Haixin Long , Zhou Zhou , Meizhu Rong . Inorganic Chemistry Curriculum Design and Implementation of Based on “Stepped-Task Driven + Multi-Dimensional Output” Model: A Case Study on Intermolecular Forces. University Chemistry, doi: 10.3866/PKU.DXHX202309008
-
[13]
Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240007
-
[14]
Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, doi: 10.3866/PKU.DXHX202402057
-
[15]
Keweiyang Zhang , Zihan Fan , Liyuan Xiao , Haitao Long , Jing Jing . Unveiling Crystal Field Theory: Preparation, Characterization, and Performance Assessment of Nickel Macrocyclic Complexes. University Chemistry, doi: 10.3866/PKU.DXHX202310084
-
[16]
Linhan Tian , Changsheng Lu . Discussion on Sextuple Bonding in Diatomic Motifs of Chromium Family Elements. University Chemistry, doi: 10.3866/PKU.DXHX202401056
-
[17]
Yanan Jiang , Yuchen Ma . Brief Discussion on the Electronic Exchange Interaction in Quantum Chemistry Computations. University Chemistry, doi: 10.12461/PKU.DXHX202402058
-
[18]
Zhanhui Yang , Jiaxi Xu . (m+n+…) or [m+n+…]cycloaddition?. University Chemistry, doi: 10.12461/PKU.DXHX202406032
-
[19]
Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, doi: 10.3866/PKU.DXHX202312017
-
[20]
Wenjing ZHANG , Xiaoqing WANG , Zhipeng LIU . Recent developments of inorganic metal complex-based photothermal materials and their applications in photothermal therapy. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240254
-
[1]
Metrics
- PDF Downloads(612)
- Abstract views(786)
- HTML views(16)