Citation: ZHAO Jing, XU Zhi-Guang, XU Xuan. Coordination Structures of Metal String Complexes [MoMoCo(npo)₄(NCS)₂] and Relationship with External Electric Field[J]. Chinese Journal of Inorganic Chemistry, ;2020, 36(4): 666-672. doi: 10.11862/CJIC.2020.077 shu

Coordination Structures of Metal String Complexes [MoMoCo(npo)₄(NCS)₂] and Relationship with External Electric Field

ZHAO Jing ¹ ,
XU Zhi-Guang ¹ ,
XU Xuan ^1,2,3,,

1.
School of Chemistry, South China Normal University, Guangzhou 510006, China
2.
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, South China Normal University, Guangzhou 510006, China
3.
Key Laboratory of Materials Energy Conversion and Storage of Guangzhou, South China Normal University, Guangzhou 510006, China

Corresponding author: XU Xuan, xuxuan@scnu.edu.cn
Received Date: 29 August 2019
Revised Date: 31 December 2019

Figures(8)

Metal string complexes, with the structure of linear metal chain helically wrapped by four equatorial ligands, have attracted extensively attention due to their unique electronic, magnetic, and potential applications in molecular electronics. Some factors such as difference of metal atoms, axial ligands and equatorial ligands would affect the physical properties of conductance and magnetic properties of metal string complexes. The diversity of equatorial ligands provides more possibilities for such changes. The coordination structures of metal string complexes[MoMoCo(npo)₄(NCS)₂] (npo=1, 8-naphthyl-2-ketone) with potential applications as molecular wires have been investigated using the density functional theory B3LYP method by considering the effects of an external electric field (EF). The coordination mode is denoted as (n, m), where n and m represent the number of oxygen atoms coordinated with the Co3 and Mo1, respectively, and n=0, 1, 2, 3, 4; m=4, 3, 2, 1, 0. The energies and polarities of these molecules increase gradually as the coordination modes of four npo^- ligands become more and more consistent, but all of them can exist stably and compete with each other. The Mo-Mo quadruple bond exists in all molecules, and the bond length decreases with the decrease of the Z-direction dipole moment μ(Z). In addition, as the value of μ(Z) decreases, the orbital energy of π_NCS^*(1) decreases but that of π_NCS^*(2) increases. The geometric and electronic structures of the five coordination modes change regularly under the action of electric field. Under the electric field effect of Z direction, the Mo1-N8 bond lengths of all coordination modes except (0, 4) increase obviously, leading to structural instability. Moreover, the phenomenons of energy level interlacing in the frontier orbitals, and the reduction of LUMO-HOMO energy gap are related to the value of μ(Z). When μ(Z) is positive, the energy gaps of (0, 4) and (1, 3) decrease more significantly under the electric field effect of -Z direction. However, when μ(Z) is negative, the energy gaps of (2, 2), (3, 1) and (4, 0) decrease more obviously under the electric field effect of Z direction. Therefore, the complexes of (0, 4), (3, 1) and (4, 0) may have the rectification effect, but (3, 1) and (4, 0) are less stable.
- metal string complexes,
- coordination mode,
- density functional theory,
- electric field,
- molecular polarity
1. [1]
  Wu L P, Field P, Morrissey T, et al. J. Chem. Soc. Dalton Trans., 1990, 12:3835-3840
2. [2]
  Aduldecha S, Hathaway B. J. Chem. Soc. Dalton Trans., 1991, 4:993-998
3. [3]
  Yang E C, Cheng M C, Tsai M S, et al. Chem. Commun., 1994, 20:2377-2378
4. [4]
  Cotton F A, Daniels L M, Jordan G T, et al. J. Am. Chem., Soc., 1997, 119:10223-10224 doi: 10.1021/ja971998+
5. [5]
  Clérac R, Cotton F A, Jeffery S P, et al. Inorg. Chem., 2001, 40:1265-1270 doi: 10.1021/ic001069a
6. [6]
  Berry J F, Cotton F A, Murillo C A, et al. Inorg. Chem., 2004, 43(7):2277-2283 doi: 10.1021/ic0354320
7. [7]
  Clérac R, Cotton F A, Daniels L M, et al. J. Am. Chem. Soc., 2000, 122:6226-6236 doi: 10.1021/ja000515q
8. [8]
  Ismayilov R H, Wang W, Lee G H, et al. Dalton Trans., 2007, 21(27):2898-2907
9. [9]
  Nippe M, Berry J F. J. Am. Chem. Soc., 2007, 129(42):12684-12685 doi: 10.1021/ja076337j
10. [10]
  Nippe M, Turov Y, Berry J F. Inorg. Chem., 2011, 50(21):10592-10599 doi: 10.1021/ic2011309
11. [11]
  Clérac R, Cotton F A, Daniels L M, et al. Inorg. Chem., 2000, 39(4):752-756
12. [12]
  Cotton F A, Lei P, Murillo C A. Inorg. Chem. Acta, 2003, 349:173-181 doi: 10.1016/S0020-1693(03)00093-8
13. [13]
  Yu L C, Lee G H, Sigrist M, et al. Eur. J. Inorg. Chem., 2016, 26:4250-4256
14. [14]
  ZHI Sha-Sha, BAN Ying, XU Zhi-Guang, et al. Chem. J. Chinese Universities, 2019, 40(5):980-987
15. [15]
  Spivak M, Lopez X, Graaf C D. J. Phys. Chem. A, 2019, 123:1538-1547 doi: 10.1021/acs.jpca.8b10124
16. [16]
  Chipman J A, Berry J F. Inorg. Chem., 2018, 57:9354-9363 doi: 10.1021/acs.inorgchem.8b01331
17. [17]
  Chipman J A, Berry J F. Chem.-Eur. J., 2018, 24:1494-1499 doi: 10.1002/chem.201704588
18. [18]
  DeBrincat D, Keers O, McGrady J E. Chem. Commun., 2013, 49:9116-9118 doi: 10.1039/c3cc45063e
19. [19]
  Cotton F A, Lei P, Murillo C A, et al. Inorg. Chem. Acta, 2003, 349(5):165-172
20. [20]
  Liu I P C, Chen C H, Chen C F, et al. Chem. Commun., 2009, 7(5):577-579
21. [21]
  HUANG Yan, HUANG Xiao, XU Xuan. Acta Phys.-Chim. Sin., 2013, 29(6):1225-1232 doi: 10.3866/PKU.WHXB201303181
22. [22]
  Chang W C, Chang C W, Sigrist M, et al. Chem. Commun., 2017, 53:8886-8889 doi: 10.1039/C7CC05449A
23. [23]
  DING Dan-Dan, XU Xuan, XU Zhi-Guang. Acta Phys.-Chim. Sin., 2015, 31(7):1323-1330
24. [24]
  Becke A D. J. Chem. Phys., 1993, 98(7):5648-5652 doi: 10.1063/1.464913
25. [25]
  Becke A D. Phys. Rev. A, 1988, 38(6):3098-3100 doi: 10.1103/PhysRevA.38.3098
26. [26]
  Lee C, Yang W, Parr R G. Phys. Rev., 1988, 37:785-789 doi: 10.1103/PhysRevB.37.785
27. [27]
  Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 03, Revision D.02, Gaussian Inc.: Wallingford, CT, 2003.
28. [28]
  Pal K, Nakao K, Mashima K. Eur. J. Inorg. Chem., 2010, 36:5668-5674
29. [29]
  Holste G, Schäfer H. Z. Anorg. Allg. Chem., 1972, 391:263-270 doi: 10.1002/zaac.19723910307
30. [30]
  Cotton F A, Norman J G. J. Coord. Chem., 1972, 1:161-171 doi: 10.1080/00958977208070758
1. [1]
  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, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  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, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
3. [3]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
4. [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, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
5. [5]
  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, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
6. [6]
  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, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
7. [7]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
8. [8]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027
9. [9]
  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, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
10. [10]
  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, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
11. [11]
  Changjun You , Chunchun Wang , Mingjie Cai , Yanping Liu , Baikang Zhu , Shijie Li . 引入内建电场强化BiOBr/C₃N₅ S型异质结中光载流子分离以实现高效催化降解微污染物. Acta Physico-Chimica Sinica, 2024, 40(11): 2407014-. doi: 10.3866/PKU.WHXB202407014
12. [12]
  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, 2024, 39(5): 163-171. doi: 10.3866/PKU.DXHX202310084
13. [13]
  Ming Li , Zhaoyin Li , Mengzhu Liu , Shaoxiang Luo . Unveiling the Artistry of Mordant Dyeing: The Coordination Chemistry Beneath. University Chemistry, 2024, 39(5): 258-265. doi: 10.3866/PKU.DXHX202311085
14. [14]
  Quanguo Zhai , Peng Zhang , Wenyu Yuan , Ying Wang , Shu'ni Li , Mancheng Hu , Shengli Gao . Reconstructing the “Fundamentals of Coordination Chemistry” in Inorganic Chemistry Course. University Chemistry, 2024, 39(11): 117-130. doi: 10.12461/PKU.DXHX202403065
15. [15]
  Peipei Sun , Jinyuan Zhang , Yanhua Song , Zhao Mo , Zhigang Chen , Hui Xu . 引入内建电场增强光载流子分离以促进H₂的生产. Acta Physico-Chimica Sinica, 2024, 40(11): 2311001-. doi: 10.3866/PKU.WHXB202311001
16. [16]
  Zhi Zhou , Yu-E Lian , Yuqing Li , Hui Gao , Wei Yi . New Insights into the Molecular Mechanism Behind Clinical Tragedies of “Cephalosporin with Alcohol”. University Chemistry, 2025, 40(3): 42-51. doi: 10.12461/PKU.DXHX202403104
17. [17]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
18. [18]
  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, 2024, 40(12): 2356-2372. doi: 10.11862/CJIC.20240254
19. [19]
  Hong Wu , Yuxi Wang , Hongyan Feng , Xiaokui Wang , Bangkun Jin , Xuan Lei , Qianghua Wu , Hongchun Li . Application of Computational Chemistry in the Determination of Magnetic Susceptibility of Metal Complexes. University Chemistry, 2025, 40(3): 116-123. doi: 10.12461/PKU.DXHX202405141
20. [20]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(847)
HTML views(210)

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

Coordination Structures of Metal String Complexes [MoMoCo(npo)4(NCS)2] and Relationship with External Electric Field

Metrics

通讯作者: 陈斌, bchen63@163.com

Coordination Structures of Metal String Complexes [MoMoCo(npo)₄(NCS)₂] and Relationship with External Electric Field