Citation: Rui YANG, Shu-Ya ZHANG, Run-Guo WANG, Yin-Shan MENG, Tao LIU, Yuan-Yuan ZHU. Synthesis and Magnetic Properties of Mononuclear Cobalt(Ⅱ) Spin Crossover Complexes from Complementary Terpyridine Ligand Pairing[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(8): 1477-1486. doi: 10.11862/CJIC.2022.155 shu

Synthesis and Magnetic Properties of Mononuclear Cobalt(Ⅱ) Spin Crossover Complexes from Complementary Terpyridine Ligand Pairing

Rui YANG ¹ ,
Shu-Ya ZHANG ² ,
Run-Guo WANG ² ,
Yin-Shan MENG ¹ ,
Tao LIU ^1,, ,
Yuan-Yuan ZHU ^{1, 2,,}

1.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, Liaoning 116024, China
2.
Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, China

Corresponding author: Tao LIU, liutao@dlut.edu.cn Yuan-Yuan ZHU, yyzhu@hfut.edu.cn
Received Date: 7 April 2022
Revised Date: 22 April 2022

Figures(5)

The cobalt(Ⅱ) complexes containing terpyridine (terpy) and its derivatives compose a large family of Co(Ⅱ) SCO-active (SCO=spin-crossover) compounds and the reported cases are mainly built from homoleptic type terpy ligands. Herein we report the SCO properties in three mononuclear cobalt (Ⅱ) complexes constructed from complementary terpy ligand pairing. Their SCO behaviors are largely affected by the substituents of terpy at the 4-position. The archetypical complex 1 and its CF₃-substituted one 3 showed a gradual and incomplete spin transition from the low spin state of S=1/2 to the high spin state of S=3/2. The fluorine-substituted complex 2 exhibited a solventdependent spin transition phenomenon. The solvated form which contains three lattice water molecules showed a similar gradually incomplete spin transition. Whereas the entire removal of water molecules resulted in a repeatable thermal hysteresis loop with a width of ca. 50 K. Impressively, the adsorption and desorption of water molecules are reversible in structure and magnetism. In addition, absorption spectroscopy and cyclic voltammetry show that the substituent on the ligands can regulate the electronic structures of the central cobalt ion.
- spin-crossover,
- cobalt(Ⅱ) complexes,
- terpyridine,
- self-assembly
1. [1]
  Gütlich P, Goodwin H A. Spin Crossover—An Overall Perspective//Gütlich P, Goodwin H A. Spin Crossover in Transition Metal Compounds Ⅰ. Berlin: Springer Berlin, Heidelberg, 2004: 1-47
2. [2]
  Halcrow M A. Spin-Crossover Materials: Properties and Applications. Chichester: John Wiley & Sons, 2013.
3. [3]
  Nakaya M, Ohtani R, Hayami S. Guest Modulated Spin States of Metal Complex Assemblies[J]. Eur. J. Inorg. Chem., 2020(39):3709-3719.
4. [4]
  Olguin J. Unusual Metal Centres/Coordination Spheres in Spin Crossover Compounds[J]. Coord. Chem. Rev., 2020,407213148. doi: 10.1016/j.ccr.2019.213148
5. [5]
  Brooker S. Spin Crossover with Thermal Hysteresis: Practicalities and Lessons Learnt[J]. Chem. Soc. Rev., 2015,44(10):2880-2892. doi: 10.1039/C4CS00376D
6. [6]
  Halcrow M A. Structure: Function Relationships in Molecular Spin-Crossover Complexes[J]. Chem. Soc. Rev., 2011,40(7):4119-4142. doi: 10.1039/c1cs15046d
7. [7]
  Sciortino N F, Scherl-Gruenwald K R, Chastanet G, Halder G J, Chapman K W, Letard J F, Kepert C J. Hysteretic Three-Step Spin Crossover in a Thermo-and Photochromic 3D Pillared Hofmann-Type Metal-Organic Framework[J]. Angew. Chem. Int. Ed., 2012,51(40):10154-10158. doi: 10.1002/anie.201204387
8. [8]
  Cambi L, Szegö L. Über die Magnetische Susceptibilität der Komplexen Verbindungen. Ber. Dtsch. Chem. Ges. B, 1931, 64(10): 2591-2598
  Cambi L, Szegö L. The Magnetic Susceptibility of Complex Compounds. Ber. Dtsch. Chem. Ges. B, 1931, 64(10): 2591-2598
9. [9]
  Mathoniere C. Metal-To-Metal Electron Transfer: A Powerful Tool for the Design of Switchable Coordination Compounds[J]. Eur. J. Inorg. Chem., 2018(3/4):248-258.
10. [10]
  WANG Y Q, ZHANG H X, ZHANG S H, HE W, GE F Y, CHEN Y X, GU Z G. Synthesis and Gelation Ability of Spin-Crossover Iron(Ⅱ) Alkyl Imidazole Complexes[J]. Chinese J. Inorg. Chem., 2019,35(12):2260-2268. doi: 10.11862/CJIC.2019.254
11. [11]
  Gütlich P, Gaspar A B, Garcia Y. Spin State Switching in Iron Coordination Compounds[J]. Beilstein J. Org. Chem., 2013,9:342-391. doi: 10.3762/bjoc.9.39
12. [12]
  WANG K J, LI H Q, SUN Y C, WANG X Y. Synthesis and Properties of an Iron(Ⅲ) Spin Crossover Compound with 1D Chains Bridged by Hydrogen Bonds[J]. Chinese J. Inorg. Chem., 2020,36(6):1143-1148.
13. [13]
  Liu T, Liu Q, Hu J X, Meng Y S, Jiang W J, Wang J L, Wen W, Wu Q, Zhu H L, Zhao L. Asymmetric Coordination toward a Photoinduced Single-Chain Magnet Showing Large Coercivity[J]. Angew. Chem. Int. Ed., 2021,60(19):10537-10541. doi: 10.1002/anie.202017249
14. [14]
  Guo Y, Yang X L, Wei R J, Zheng L S, Tao J. Spin Transition and Structural Transformation in a Mononuclear Cobalt (Ⅱ) Complex[J]. Inorg. Chem., 2015,54(16):7670-7672. doi: 10.1021/acs.inorgchem.5b01344
15. [15]
  Xue S F, Guo Y N, Garcia Y. Spin Crossover Crystalline Materials Engineered via Single-Crystal-To-Single-Crystal Transformations[J]. CrystEngComm, 2021,23(45):7899-7915. doi: 10.1039/D1CE00234A
16. [16]
  Krivokapic I, Zerara M, Daku M L, Vargas A, Enachescu C, Ambrus C, Tregenna-Piggott P, Amstutz N, Krausz E, Hauser A. Spin-Crossover in Cobalt(Ⅱ) Imine Complexes[J]. Coord. Chem. Rev., 2007,251(3/4):364-378.
17. [17]
  Hayami S, Komatsu Y, Shimizu T, Kamihata H, Lee Y N. Spin-Crossover in Cobalt (Ⅱ) Compounds Containing Terpyridine and Its Derivatives[J]. Coord. Chem. Rev., 2011,255(17/18):1981-1990.
18. [18]
  Bersuke I B. Spin Crossover and Magnetic-Dielectric Bistability Induced by Hidden Pseudo-Jahn-Teller Effect[J]. Magnetochemistry, 2020,6(4)64. doi: 10.3390/magnetochemistry6040064
19. [19]
  Kilner C A, Halcrow M A. An Unusual Discontinuity in the Thermal Spin Transition in Co(terpy)₂[BF₄]₂[J]. Dalton Trans., 2010,39(38):9008-9012. doi: 10.1039/c0dt00295j
20. [20]
  Kou H Z, Sato O. New Oxalate-Bridged Cr^Ⅲ-Mn^Ⅱ Polymeric Network Incorporating a Spin-Crossover[Co(terpy)₂]²⁺ Cation[J]. Inorg. Chem., 2007,46(23):9513-9515. doi: 10.1021/ic701043f
21. [21]
  Zhang X, Wang Z X, Xie H, Li M X, Woods T J, Dunbar K R. A Cobalt (Ⅱ) Spin-Crossover Compound with Partially Charged TCNQ Radicals and an Anomalous Conducting Behavior[J]. Chem. Sci., 2016,7(2):1569-1574. doi: 10.1039/C5SC03547C
22. [22]
  Shao D, Shi L, Shen F X, Wei X Q, Sato O, Wang X Y. Reversible On-Off Switching of the Hysteretic Spin Crossover in a Cobalt (Ⅱ) Complex via Crystal to Crystal Transformation[J]. Inorg. Chem., 2019,58(17):11589-11598. doi: 10.1021/acs.inorgchem.9b01436
23. [23]
  Zenno H, Kobayashi F, Nakamura M, Sekine Y, Lindoy L F, Hayami S. Hydrogen Bond-Induced Abrupt Spin Crossover Behaviour in 1-D Cobalt (Ⅱ) Complexes—The Key Role of Solvate Water Molecules[J]. Dalton Trans., 2021,50(22):7843-7853. doi: 10.1039/D1DT01069G
24. [24]
  Sinha P, Kumari N, Singh K, Singh K, Mishra L. Homoleptic Bisterpyridyl Complexes: Synthesis, Characterization, DNA Binding, DNA Cleavage and Topoisomerase Ⅱ Inhibition Activity[J]. Inorg. Chim. Acta, 2015,432:71-80. doi: 10.1016/j.ica.2015.03.026
25. [25]
  Pankratova Y, Aleshin D, Nikovskiy I, Novikov V, Nelyubina Y. In Situ NMR Search for Spin-Crossover in Heteroleptic Cobalt(Ⅱ) Complexes[J]. Inorg. Chem., 2020,59(11):7700-7709. doi: 10.1021/acs.inorgchem.0c00716
26. [26]
  Wang S Y, Fu J H, Liang Y P, He Y J, Chen Y S, Chan Y T. Metallo-Supramolecular Self-Assembly of a Multicomponent Ditrigon Based on Complementary Terpyridine Ligand Pairing[J]. J. Am. Chem. Soc., 2016,138(11):3651-3654. doi: 10.1021/jacs.6b01005
27. [27]
  Wang S Y, Huang J Y, Liang Y P, He Y J, Chen Y S, Zhan Y Y, Hiraoka S, Liu Y H, Peng S M, Chan Y T. Multicomponent Self-Assembly of Metallo-Supramolecular Macrocycles and Cages through Dynamic Heteroleptic Terpyridine Complexation[J]. Chem. Eur. J., 2018,24(37):9274-9284. doi: 10.1002/chem.201801753
28. [28]
  Fu J H, Wang S Y, Chen Y S, Prusty S, Chan Y T. One-Pot Self-Assembly of Stellated Metallosupramolecules from Multivalent and Complementary Terpyridine-Based Ligands[J]. J. Am. Chem. Soc., 2019,141(41):16217-16221. doi: 10.1021/jacs.9b08731
29. [29]
  Mcpherson J N, Hogue R W, Akogun F S, Bondi L, Luis E T, Price J R, Garden A L, Brooker S, Colbran S B. Predictable Substituent Control of Co^Ⅲ/Ⅱ Redox Potential and Spin Crossover in Bis(dipyridylpyrrolide)cobalt Complexes[J]. Inorg. Chem., 2019,58(3):2218-2228. doi: 10.1021/acs.inorgchem.8b03457
30. [30]
  Kobayashi F, Iwaya K, Zenno H, Nakamura M, Li F, Hayami S. Spin State Modulation in Cobalt (Ⅱ) Terpyridine Complexes by Cocrystallization with 1, 3, 5-Triiodo-2, 4, 6-trifluorobenzene[J]. Bull. Chem. Soc. Jpn., 2021,94(1):158-163. doi: 10.1246/bcsj.20200246
31. [31]
  Karabulut F N H, Feltham H L C, Brooker S. Substituents Drive Ligand Rearrangements, Giving Dinuclear Rather than Mononuclear Complexes, and Tune Co^Ⅱ/Ⅲ Redox Potential[J]. Dalton Trans., 2018,47(34):11749-11759. doi: 10.1039/C8DT01502C
32. [32]
  Sil A, Ghosh U, Mishra V K, Mishra S, Patra S K. Synthesis, Structure, Electrochemical, and Spectroscopic Properties of Hetero-Bimetallic Ru(Ⅱ)/Fe(Ⅱ)-Alkynyl Organometallic Complexes[J]. Inorg. Chem., 2019,58(2):1155-1166. doi: 10.1021/acs.inorgchem.8b02440
33. [33]
  Dickenson J C, Haley M E, Hyde J T, Reid Z M, Tarring T J, Iovan D A, Harrison D P. Fine-Tuning Metal and Ligand-Centered Redox Potentials of Homoleptic Bis-terpyridine Complexes with 4′-Aryl Substituents[J]. Inorg. Chem., 2021,60(13):9956-9969. doi: 10.1021/acs.inorgchem.1c01233
34. [34]
  Holland J M, Mcallister J A, Lu Z B, Kilner C A, Thornton-Pett M, Halcrow M A. An Unusual Abrupt Thermal Spin-State Transition in [FeL₂][BF₄]₂[L=2, 6-Di(pyrazol-1-yl)pyridine][J]. Chem. Commun., 2001(6):577-578. doi: 10.1039/b100995h
35. [35]
  Mccusker J K, Rheingold A L, Hendrickson D N. Variable-Temperature Studies of Laser-Initiated ⁵T₂→¹A₁ Intersystem Crossing in Spin-Crossover Complexes: Empirical Correlations between Activation Parameters and Ligand Structure in a Series of Polypyridyl Ferrous Complexes[J]. Inorg. Chem., 1996,35(7):2100-2112. doi: 10.1021/ic9507880
36. [36]
  Alvarez S, Alemany P, Casanova D, Cirera J, Llunell M, Avnir D. Shape Maps and Polyhedral Interconversion Paths in Transition Metal Chemistry[J]. Coord. Chem. Rev., 2005,249(17):1693-1708.
37. [37]
  Ni Z P, Liu J L, Hogue N, Liu W, Li J Y, Chen Y C, Tong M L. Recent Advances in Guest Effects on Spin-Crossover Behavior in Hofmann-Type Metal-Organic Frameworks[J]. Coord. Chem. Rev., 2017,335:28-43. doi: 10.1016/j.ccr.2016.12.002
38. [38]
  Kobayashi F, Komatsumaru Y, Akiyoshi R, Nakamura M, Zhang Y, Lindoy L F, Hayami S. Water Molecule-Induced Reversible Magnetic Switching in a Bis-terpyridine Cobalt(Ⅱ) Complex Exhibiting Coexistence of Spin Crossover and Orbital Transition Behaviors[J]. Inorg. Chem., 2020,59(23):16843-16852. doi: 10.1021/acs.inorgchem.0c00818
39. [39]
  Tang J H, Sun T G, Shao J Y, Gong Z L, Zhong Y W. Resistive Memory Devices Based on a Triphenylamine-Decorated Non-precious Cobalt (Ⅱ) Bis-terpyridine Complex[J]. Chem. Commun., 2017,53(87):11925-11928. doi: 10.1039/C7CC05806C
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