Citation: Luo Shuchang, Sun Xiaoyuan, Zheng Pengfei, Liu Xiangyu, Huang Renyi. Magnetic Studies of Isomorphous Replacement of M^II Ions in {Gd^IIIM^II}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective[J]. Chemistry, ;2020, 83(5): 464-471. shu

Magnetic Studies of Isomorphous Replacement of M^II Ions in {Gd^IIIM^II}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective

1.
College of Chemical Engineering, Guizhou University of Engineering Science, Bijie, 551700
2.
College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan, 750021

Received Date: 13 November 2019
Accepted Date: 10 December 2019

Figures(5)

The magnetic properties was studied for a series of {Gd^IIIM^II}(M=Cu, Ni, Co, Fe, Mn) heterobinuclear complexes by the combination of DFT calculations, using the different functional methods and basis sets, with the broken-symmetry approach. The results showed that the calculated values at the level of PBE0/TZVP (Gd is SARC-ZDRA-TZVP) are consistent with the experimental values, and this method can be used to describe its magnetic properties. There is a strong orbital interaction between the paramagnetic centers Cu^II and Gd^III and bridged coordination oxygen atoms. The molecular magnetic orbital of the complex[Cu^IIGd^III{PyCO(OEt)Py C(OH)(OEt)Py}₃]²⁺ are mainly contributed by 4f_z³, 4f_z(x²-y²) orbitals of the paramagnetic center Gd^III, 3d_x²-y² orbital of Cu^II ion and p orbitals of the bridging oxygen atoms. Due to the compensation of spin delocalization from Cu^II ion and spin polarization from Gd^III ion, the effect of spin delocalization from Cu^II ion on bridged oxygen atoms is greater than the spin polarization effect of paramagnetic center Gd^III ion. Model calculations were used to examine the influence of the electronic configuration of the M^II ions on the magnetic coupling constants. As a result, the increase of unpaired electrons of M^II ions, the ρ_HS²-ρ_BS² of the paramagnetic centers Gd^III/M^IIincreases, the contribution of antiferromagnetic coupling increases, whereas the values of the magnetic coupling constant decreases.
- Gd^IIIM^II heterobinuclear complexes,
- M^II ions,
- Magnetic coupling constant,
- DFT-BS
1. [1]
  Dutt N K, Nag K. Inorg. Nucl. Chem., 1968, 30(9): 2493~2499.
2. [2]
  Bencini A, Benelli C, Caneschi A, et al. J. Am. Chem. Soc., 1985, 107(26): 8128~8136.
3. [3]
  Blagg R J, Ungur L, Tuna F, et al. Nat. Chem., 2013, 5: 673~678.
4. [4]
  Li Z Y, Zhang C, Zhai B, et al. CrystEngComm, 2017, 19(19): 2702~2708.
5. [5]
  Benelli C, Gatteschi D. Chem. Rev., 2002, 102(6): 2369~2387.
6. [6]
  Cremades E, Gómez-Coca S, Aravena D, et al. J. Am. Chem. Soc., 2012, 134(25): 10532~10542.
7. [7]
  Huang Y G, Jiang F L, Hong M C. Coord. Chem. Rev., 2009, 253(23/24): 2814~2834.
8. [8]
  Cancino P, Santibañez L, Fuentealba P, et al. Dalton Transac., 2018, 47(38): 13360~13367.
9. [9]
  Maity S, Mondal A, Konar S, et al. Dalton Transac., 2019, 48(40): 15170~15183.
10. [10]
  Andruh M. Chem. Commun., 2018, 54(29): 3559~3577.
11. [11]
  Escobedo-Cruz F V, Hughbanks T R. Dalton Transac., 2018, 47(19): 6831~6841.
12. [12]
  Ferbinteanu M, Stroppa A, Scarrozza M, et al. Inorg. Chem., 2017, 56(16): 9474~9485.
13. [13]
  Layfield R A, Murugesu M. Lanthanides and Actinides in Molecular Magnetism. John Wiley & Sons, 2015..
14. [14]
  Sieklucka B, Pinkowicz D. Molecular Magnetic Materials Concepts and Applications. John Wiley & Sons, 2017.
15. [15]
  Singh S K, Beg M F, Rajaraman G. Chem. Eur. J., 2016, 22(2): 672~680.
16. [16]
  Costes J P, Duhayon C, Mallet-Ladeira S, et al. Chem. Eur. J., 2016, 22(6): 2171~2180.
17. [17]
  Gupta T, Rajaraman G. Chem. Commun., 2016, 52(58): 8972~9008.
18. [18]
  Singh S K, Tibrewal N K, Rajaraman G. Dalton Transac., 2011, 40(41): 10897~10906.
19. [19]
  Paulovič J, Cimpoesu F, Ferbinteanu M, et al. J. Am. Chem. Soc., 2004, 126(10): 3321~3331.
20. [20]
21. [21]
  Singh S K, Rajaraman G. Dalton Transac., 2013, 42(10): 3623~3630.
22. [22]
  Rajaraman G, Totti F, Bencini A, et al. Dalton Transac., 2009(17): 3153~3161.
23. [23]
24. [24]
  Bar A K, Kalita P, Singh M K, et al. Coord. Chem. Rev., 2018, 367: 163~216.
25. [25]
  Georgopoulou A N, Adam R, Raptopoulou C P, et al. Dalton Transac., 2010, 39(20): 5020~5027.
26. [26]
  Bazhina E S, Aleksandrov G G, Kiskin M A, et al. Eur. J. Inorg. Chem., 2018, 2018(47): 5075~5090.
27. [27]
  Singh S K, Rajeshkumar T, Chandrasekhar V, et al. Polyhedron, 2013, 66: 81~86.
28. [28]
  Costes J P, Clemente-Juan J M, Dahan F, et al. Inorg. Chem., 2002, 41(11): 2886~2891.
29. [29]
  Shannon R D. Acta Cryst., 1976, A32, 751~767.
30. [30]
  Soda T, Kitagawa Y, Onishi T, et al. Chem. Phys. Lett., 2000, 319(3/4): 223~230.
31. [31]
  Adamo C, Barone V. J. Chem. Phys., 1999, 110(13): 6158~6170.
32. [32]
33. [33]
  Neese F. WIREs Comput. Mol. Sci., 2012, 2(1): 73~78.
34. [34]
  Neese F. WIREs Comput. Mol. Sci., 2018, 8(1): e1327.
35. [35]
  Humphrey W, Dalke A, Schulten K. J. Mol. Graph., 1996, 14(1): 33~38.
36. [36]
  Pantazis D A, Neese F. J. Chem. Theory Comput. 2009, 5(9): 2229~2238.
37. [37]
  Adamo C, Barone V. J. Chem. Phys., 1999, 110(13): 6158~6170.
38. [38]
  Feller D. J. Comp. Chem., 1996, 17(13): 1571~1586.
39. [39]
  Lawson D B, DeKock R L. J. Phys. Chem. A, 1999, 103(11): 1627~1633.
40. [40]
  Auer A A, Helgaker T, Klopper W. J. Comput. Chem., 2002, 23(3): 420~425.
41. [41]
  Cornell W D, Gould I R, Kollman P A. J. Mole. Struct: THEOCHEM, 1997, 392: 101~109.
42. [42]
  Costes J P, Dahan F, Dupuis A, et al. Inorg. Chem., 2000, 39(2): 169~173.
43. [43]
  Novitchi G, Costes J P, Donnadieu B. Eur. J. Inorg. Chem., 2004, 2004(9): 1808~1812.
44. [44]
  Costes J P, Dahan F, Dupuis A, et al. Inorg. Chem., 1996, 35(8): 2400~2402.
45. [45]
  Costes J P, Dahan F, Dupuis A, et al. Inorg. Chem., 1997, 36(19): 4284~4286.
46. [46]
  Chen Q Y, Luo Q H, Zheng L M, et al. Inorg. Chem., 2002, 41(3): 605~609.
47. [47]
  Costes J P, Dahan F, García-Tojal J. Chem. Eur. J., 2002, 8(23): 5430~5434.
48. [48]
  Costes J P, Dahan F, Donnadieu B, et al. Eur. J. Inorg. Chem., 2001, 2001(2): 363~365.
49. [49]
50. [50]
  Bian J Y, Chang Y F, Zhang J P. J. Phys. Chem. A, 2008, 112(14): 3186~3191.
51. [51]
52. [52]
  Illas F, Caballol R, Castell O, et al. J. Phys. Chem. A, 1997, 101(42): 7860~7866.
53. [53]
  Ruiz E, Cano J, Alvarez S, et al. J. Comp. Chem., 1999, 20(13): 1391~1400.
54. [54]
  Zhang Y Q, Luo C L. Eur. J. Inorg. Chem., 2008, 2008(13): 2199~2206.
1. [1]
  Ye Wang , Ruixiang Ge , Xiang Liu , Jing Li , Haohong Duan . An Anion Leaching Strategy towards Metal Oxyhydroxides Synthesis for Electrocatalytic Oxidation of Glycerol. Acta Physico-Chimica Sinica, 2024, 40(7): 2307019-0. doi: 10.3866/PKU.WHXB202307019
2. [2]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  Ying Xiong , Guangao Yu , Lin Wu , Qingwen Liu , Houjin Li , Shuanglian Cai , Zhanxiang Liu , Xingwen Sun , Yuan Zheng , Jie Han , Xin Du , Chengshan Yuan , Qihan Zhang , Jianrong Zhang , Shuyong Zhang . Basic Operations and Specification Suggestions for Determination of Physical Constants of Organic Compounds. University Chemistry, 2025, 40(5): 106-121. doi: 10.12461/PKU.DXHX202503079
6. [6]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
7. [7]
  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
8. [8]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts. Acta Physico-Chimica Sinica, 2025, 41(1): 100002-0. doi: 10.3866/PKU.WHXB202309002
9. [9]
  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
10. [10]
  Hong RAO , Yang HU , Yicong MA , Chunxin LÜ , Wei ZHONG , Lihua DU . Synthesis and in vitro anticancer activity of phenanthroline-functionalized nitrogen heterocyclic carbene homo- and heterobimetallic silver/gold complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2429-2437. doi: 10.11862/CJIC.20240275
11. [11]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
12. [12]
  Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce₄^ⅢCe₆^Ⅳ(μ₃-O)₄(μ₄-O)₄(acac)₁₄(CH₃O)₆]·2CH₃OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342
13. [13]
  Yichang Liu , Li An , Dan Qu , Zaicheng Sun . “双碳”背景下的综合设计实验——以PbCrO₄催化甲基蓝的光降解速率常数测定为例. University Chemistry, 2025, 40(6): 222-229. doi: 10.12461/PKU.DXHX202407105
14. [14]
  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
15. [15]
  Xin Feng , Kexin Guo , Chunguang Jia , Bowen Liu , Suqin Ci , Junxiang Chen , Zhenhai Wen . Hydrogen Generation Coupling with High-Selectivity Electrocatalytic Glycerol Valorization into Formate in an Acid-Alkali Dual-Electrolyte Flow Electrolyzer. Acta Physico-Chimica Sinica, 2024, 40(5): 2303050-0. doi: 10.3866/PKU.WHXB202303050
16. [16]
  Shuang Cao , Bo Zhong , Chuanbiao Bie , Bei Cheng , Feiyan Xu . Insights into Photocatalytic Mechanism of H₂ Production Integrated with Organic Transformation over WO₃/Zn_0.5Cd_0.5S S-Scheme Heterojunction. Acta Physico-Chimica Sinica, 2024, 40(5): 2307016-0. doi: 10.3866/PKU.WHXB202307016
17. [17]
  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
18. [18]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
19. [19]
  Jia-He Li , Yu-Ze Liu , Jia-Hui Ma , Qing-Xiao Tong , Jian-Ji Zhong , Jing-Xin Jian . 洛芬碱衍生物的合成、化学发光与重金属离子检测. University Chemistry, 2025, 40(6): 230-237. doi: 10.12461/PKU.DXHX202407080
20. [20]
  Cheng Zheng , Shiying Zheng , Yanping Zhang , Shoutian Zheng , Qiaohua Wei . Synthesis, Copper Content Analysis, and Luminescent Performance Study of Binuclear Copper (I) Complexes with Isomeric Luminescence Shift: A Comprehensive Chemical Experiment Recommendation. University Chemistry, 2024, 39(7): 322-329. doi: 10.3866/PKU.DXHX202310131

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(1357)
HTML views(213)

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

Magnetic Studies of Isomorphous Replacement of MII Ions in {GdIIIMII}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective

Metrics

通讯作者: 陈斌, bchen63@163.com

Magnetic Studies of Isomorphous Replacement of M^II Ions in {Gd^IIIM^II}(M=Cu, Ni, Co, Fe, Mn) Complexes: A Theoretical Perspective