Citation: CHEN Rong, ZHOU Wo-Hua, WU Zi-Wen, XU Xuan, XU Zhi-Guang. Theoretical Study on the Structures and Magnetic Properties of Metal String Complexes [Ni₃(L)₄(NCS)₂] (L = dpa^-, mpta^-, mdpa^-, mppa^-)[J]. Acta Physico-Chimica Sinica, ;2015, 31(9): 1683-1689. doi: 10.3866/PKU.WHXB201506031 shu

Theoretical Study on the Structures and Magnetic Properties of Metal String Complexes [Ni₃(L)₄(NCS)₂] (L = dpa^-, mpta^-, mdpa^-, mppa^-)

CHEN Rong ¹ ,
ZHOU Wo-Hua ¹ ,
WU Zi-Wen ¹ ,
XU Xuan ^1,2,3, ,
XU Zhi-Guang ¹

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 Materials for Energy Conversion and Storage of Guangzhou, Guangzhou 510006, P. R. China

Received Date: 16 February 2015
Available Online: 3 June 2015
Fund Project: 广东省自然科学基金(S2012010008763) (S2012010008763) 广东省教育部产学研项目(2010B090400184) (2010B090400184)广州市科技攻关项目(2011J4300063)资助 (2011J4300063)

Density functional theory at the BP86 level and natural bond orbital theory were used to investigate the influence of bridging ligands on the Ni―Ni interactions and magnetic coupling properties of metal string complexes [Ni₃(L)₄(NCS)₂] (L = 1: dpa^- (dipyridylamine), 2: mpta^- (4-methylpyridyl-thiazolylamine), 3: mdpa^- (4-methyl-dipyridylamine), 4: mppa-(4-methylpyridyl-3H-pyrrolylamine)) with potential applications in molecular wires. The following conclusions can be drawn. (1) The ground states of the complexes are antiferromagnetic (AF) singlet states, which correspond to the quintet state (HS). The energy and structure of HS is similar to AF. There are three-center-four-electron σ bonds (σ₂σ_nb¹σ^*1) along the Ni₃⁶⁺ chains. (2) The Ni―Ni and Ni―N distances are unaffected by methyl substituents on the pyridine ring of dpa^- ligands. However, substitution of the 3H-pyrrole ring or thiazole ring by the pyridine ring in mdpa^- lengthens the N1―N2 and Ni―Ni distances but shortens the Ni2―N2 distance. These effects of the thiazole ring are weaker than those of the 3H-pyrrole ring. Therefore, the strength of the Ni―Ni interaction is 1 ≈ 3 > 2 > 4. (3) The predicted J_ab values of 3 and 4 are -103 and -88 cm^-1, respectively. The AF magnetic coupling effects of the complexes increase with increasing Ni―Ni interaction strength: the stronger the Ni―Ni interaction, the greater the direct magnetic coupling in the σ orbitals along the Ni₃⁶⁺ chains. In addition, the stronger the Ni2―N2 interaction, the larger the indirect magnetic coupling involving the bridging ligand. The direct magnetic coupling is stronger than the indirect magnetic coupling.
- Metal string complex,
- Bridging ligand,
- Density functional theory,
- Magnetic coupling,
- M olecular wire
1. [1]
  
  (1) Luo, K. G.; Tan, Y.; Xu, X.; Xu, Z. G. Inorg. Chim. Acta 2014, 421, 310. doi: 10.1016/j.ica.2014.06.003
2. [2]
  (2) Berry, J. F.; Cotton, F. A.; Murillo, C. A.; Roberts, B. K. Inorg. Chem. 2004, 43, 2277. doi: 10.1021/ic0354320
3. [3]
  (3) Chang, H. C.; Li, J. T.; Wang, C. C.; Lin, T. W.; Lee, H. C.; Lee, G. H.; Peng, S. M. Eur. J. Inorg. Chem. 1999, 1999 (8), 1243.
4. [4]
  (4) Lai, S. Y.; Wang, C. C.; Chen, Y. H.; Lee, C. C.; Liu, Y. H.; Peng, S. M. J. Chin. Chem. Soc. 1999, 46, 477. doi: 10.1002/jccs.v46.3
5. [5]
  (5) 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
6. [6]
  (6) 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
7. [7]
  (7) Hurley, T. J.; Robinson, M. A. Inorg. Chem. 1968, 7 (1), 33. doi: 10.1021/ic50059a007
8. [8]
  (8) Aduldecha, S.; Hathaway, B. J. Chem. Soc. Dalton Trans. 1991, 993.
9. [9]
  (9) 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
10. [10]
  (10) Shieh, S. J.; Chou, C. C.; Lee, G. H.; Wang, C. C.; Peng, S. M. Angew. Chem. Int. Edit. 1997, 36, 56.
11. [11]
  (11) Cheng, M. C.; Liu, I. P. C.; Hsu, C. H.; Lee, G. H.; Chen, C. H.; Peng, S. M. Dalton Trans. 2012, 41, 3166. doi: 10.1039/c2dt11246a
12. [12]
  (12) Clérac, R.; Cotton, F. A.; Dunbar, K. R.; Murillo, C. A.; Pascual, I.; Wang, X. P. Inorg. Chem. 1999, 38, 2655. doi: 10.1021/ic990006t
13. [13]
  (13) Berry, J. F.; Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Wang, X. P. Inorg. Chem. 2003, 42 (7), 2418. doi: 10.1021/ic0262740
14. [14]
  (14) Kiehl, P.; Rohmer, M. M.; Bénard, M. Inorg. Chem. 2004, 43 (10), 3151. doi: 10.1021/ic040011j
15. [15]
  (15) Cotton, F. A.; Lei, P.; Murillo, C. A. Inorg. Chim. Acta 2003, 351, 183. doi: 10.1016/S0020-1693(03)00112-9
16. [16]
  (16) Cotton, F. A.; Chao, H.; Murillo, C. A.; Wang, Q. S. Dalton Trans. 2006, No. 45, 5416.
17. [17]
  (17) Ismayilov, R. H.; Wang, W. Z.; Lee, G. H.; Wang, R. R.; Liu, I. P. C.; Yeh, C. Y.; Peng, S. M. Dalton Trans. 2007, 21 (27), 2898.
18. [18]
  (18) Yang, C. C.; Liu, I. P. C.; Hsu, Y. J.; Lee, G. H.; Chen, C. H.; Peng, S. M. Eur. J. Inorg. Chem. 2013, 2013 (2), 263. doi: 10.1002/ejic.201200934
19. [19]
  (19) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
20. [20]
  (20) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
21. [21]
  (21) Becke, A. D. Phys. Rev. A 1988, 38 (6), 3098. doi: 10.1103/PhysRevA.38.3098
22. [22]
  (22) Perdew, J. P. Phys. Rev. 1986, B33, 8882; 1986, B34, 7406.
23. [23]
  (23) Schwerdtfeger, P.; Dolg, M.; Schwarz, W. H. E.; Bowmaker, G. A.; Boyd, P. D. J. Chem. Phys. 1989, 91, 1762. doi: 10.1063/1.457082
24. [24]
  (24) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299. doi: 10.1063/1.448975
25. [25]
  (25) Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO, Version 3.1; Theoretical Chemistry Institute, University of Wisconsin: Madison, 1996.
26. [26]
  (26) Noodleman, L. J. Chem. Phys. 1981, 74 (10), 5737. doi: 10.1063/1.440939
27. [27]
  (27) Kitagawa, Y.; Matsui, T.; Nakanishi, Y.; Shigeta, Y.; Kawakami, T.; Okumura, M.; Yamaguchi, K. Dalton Trans. 2013, 42, 16200. doi: 10.1039/c3dt51466h
28. [28]
  (28) Lu, T. Multiwfn, Revision 3.3.5; Beijing Kein Research Center for Natural Sciences: Beijing, 2014.
29. [29]
  (29) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 09, Revision B.01; Gaussian Inc.: Pittsburgh, PA, 2009.
30. [30]
  (30) 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.]
31. [31]
  (31) L?pez, X.; Bénard, M.; Rohmer, M. M. J. Mol. Struct. 2006, 777, 53. doi: 10.1016/j.theochem.2006.08.040
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, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
2. [2]
  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
3. [3]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
4. [4]
  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
5. [5]
  Qilu DU , Li ZHAO , Peng NIE , Bo XU . Synthesis and characterization of osmium-germyl complexes stabilized by triphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1088-1094. doi: 10.11862/CJIC.20240006
6. [6]
  Jinfeng Chu , Yicheng Wang , Ji Qi , Yulin Liu , Yan Li , Lan Jin , Lei He , Yufei Song . Comprehensive Chemical Experiment Design: Convenient Preparation and Characterization of an Oxygen-Bridged Trinuclear Iron(III) Complex. University Chemistry, 2024, 39(7): 299-306. doi: 10.3866/PKU.DXHX202310105
7. [7]
  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
8. [8]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
9. [9]
  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
10. [10]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
11. [11]
  Zuozhong Liang , Lingling Wei , Yiwen Cao , Yunhan Wei , Haimei Shi , Haoquan Zheng , Shengli Gao . Exploring the Development of Undergraduate Scientific Research Ability in Basic Course Instruction: A Case Study of Alkali and Alkaline Earth Metal Complexes in Inorganic Chemistry. University Chemistry, 2024, 39(7): 247-263. doi: 10.3866/PKU.DXHX202310103
12. [12]
  Jia Yao , Xiaogang Peng . Theory of Macroscopic Molecular Systems: Theoretical Framework of the Physical Chemistry Course in the Chemistry “101 Plan”. University Chemistry, 2024, 39(10): 27-37. doi: 10.12461/PKU.DXHX202408117
13. [13]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
14. [14]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
15. [15]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
16. [16]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
17. [17]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
18. [18]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
19. [19]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
20. [20]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188

Get Citation

PDF

XML

Metrics

PDF Downloads(290)
Abstract views(597)
HTML views(28)

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

Theoretical Study on the Structures and Magnetic Properties of Metal String Complexes [Ni3(L)4(NCS)2] (L = dpa-, mpta-, mdpa-, mppa-)

Metrics

通讯作者: 陈斌, bchen63@163.com

Theoretical Study on the Structures and Magnetic Properties of Metal String Complexes [Ni₃(L)₄(NCS)₂] (L = dpa^-, mpta^-, mdpa^-, mppa^-)