Incorporating Highly Anisotropic Four-Coordinate Co(II) Ions within One-Dimensional Coordination Chains

Long, Tao1; Yang, Jiong2; Moorthy, Shruti3; Shao, Dong1; Singh, Saurabh Kumar3; Zhang, Yuan-Zhu2

2023-03-01

10.1021/acs.cgd.3c00082

CRYSTAL GROWTH & DESIGN   影响因子和分区

1528-7483

1528-7505

Low-coordinate metallic ions have been well recognized for constructing good-performance single ion magnets (SIMs) due to their enhanced magnetic anisotropy; however, the incorporation of such specific ions into coordination polymers is still challenging. Here, we reported two new CoII coordination polymers, namely [Co(pdms)(bpe)]n (1) and {[Co(pdms)(tpb)]center dot H2O center dot tpb}n (2) (H2pdms = 1,2-bis(methanesulfonamido)benzene, bpe = 1,2-di(4-pyridyl)ethane, tpb = 1,2,4,5-tetra(4-pyridyl)benzene). Single crystal X-ray diffraction experiments indicated that the CoII centers in both 1 and 2 display a distorted tetrahedral geometry with quasi C2v symmetry and are linked into a one-dimensional (1D) zig-zag chain via the ditopic bridging ligand of bpe in 1 while a ribbon chain via the tetradentate linker of tpb in 2. Magnetic studies revealed the easy-axis magnetic anisotropy of the CoII ions with different zero -field splitting D of -19 cm-1 (1) and -33 cm-1 (2), likely due to the distinct changes in the Npy-Co-Npy bite angles (100.20 degrees (1) vs. 93.90 degrees (2)). Moreover, slow magnetic relaxation proceeded via different relaxation mechanisms under applied dc fields was observed, giving an effective energy barrier (Ueff) of 69.6 K for 1 and 76.6 K for 2, respectively. The ab initio calculations on both the polymers further confirmed the sign and magnitude of the ZFS parameters and nicely reproduced the experimental results. Our study demonstrated a great potential for applying the well-studied and highly anisotropic 4-coordinate metal ions within a coordination polymer, opening a viable means to tuning magnetic anisotropy via topological control.

SCI ; EI

英语

通讯

Huanggang Normal University["2042021033","202210204"] ; Young Talents Project of Department of Education of Hubei Province[Q20222904] ; Open Foundation of Hubei Key Laboratory of Novel Reactor and Green Chemical Technology[NRGC202210] ; Open Foundation of State Key Laboratory of Coordination Chemistry[SKLCC2208] ; Stable Support Plan Program of Shenzhen Natural Science Fund[20200925151834005] ; National Natural Science Foundation of China[22173043] ; Department of Science and Technology for the Start-up Research Grant[SRG/2020/001323]

Chemistry ; Crystallography ; Materials Science

Chemistry, Multidisciplinary ; Crystallography ; Materials Science, Multidisciplinary

WOS:000953439400001

AMER CHEMICAL SOC

20231113741397

Benzene ; Cobalt compounds ; Crystal symmetry ; Metal ions ; Microchannels ; Single crystals

Metallurgy:531.1 ; Magnetism: Basic Concepts and Phenomena:701.2 ; Organic Compounds:804.1 ; Physical Properties of Gases, Liquids and Solids:931.2 ; Crystalline Solids:933.1 ; Crystal Lattice:933.1.1

CHEMISTRY

Web of Science

1.Huanggang Normal Univ, Coll Chem & Chem Engn, Hubei Key Lab Proc & Applicat Catalyt Mat, Huanggang 438000, Peoples R China
2.Southern Univ Sci & Technol SUSTech, Dept Chem, Shenzhen 518055, Peoples R China
3.Indian Inst Technol Hyderabad, Dept Chem, Sangareddy 502285, Telangana, India

Long, Tao,Yang, Jiong,Moorthy, Shruti,et al. Incorporating Highly Anisotropic Four-Coordinate Co(II) Ions within One-Dimensional Coordination Chains[J]. CRYSTAL GROWTH & DESIGN,2023,23(4):2980-2987.

Long, Tao,Yang, Jiong,Moorthy, Shruti,Shao, Dong,Singh, Saurabh Kumar,&Zhang, Yuan-Zhu.(2023).Incorporating Highly Anisotropic Four-Coordinate Co(II) Ions within One-Dimensional Coordination Chains.CRYSTAL GROWTH & DESIGN,23(4),2980-2987.

Long, Tao,et al."Incorporating Highly Anisotropic Four-Coordinate Co(II) Ions within One-Dimensional Coordination Chains".CRYSTAL GROWTH & DESIGN 23.4(2023):2980-2987.