Citation: Guoshuai ZHANG, Peirong QI, Yaqi LI, Shengyuan CHANG. Solvent-regulated self-assembly of cobalt-p-sulfosulfonylcalix[4]arene frameworks with thiophene-2,5-dicarboxylic acid[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(10): 2245-2258. doi: 10.11862/CJIC.20260042 shu

Solvent-regulated self-assembly of cobalt-p-sulfosulfonylcalix[4]arene frameworks with thiophene-2,5-dicarboxylic acid

Guoshuai ZHANG ^{1, 2,,} ,
Peirong QI ¹ ,
Yaqi LI ¹ ,
Shengyuan CHANG ¹

1.
Department of Chemical and Materials Engineering, Lyuliang University, Lüliang, Shanxi 033001, China
2.
Institute of New Carbon-based Materials and Zero-carbon and Negative-carbon Technology, Lyuliang University, Lüliang, Shanxi 033001, China

Corresponding author: Guoshuai ZHANG, gszhang@llu.edu.cn
Received Date: 7 February 2026
Revised Date: 18 August 2026

Figures(7)

Two p-sulfosulfonylcalix^[4]arene supramolecular coordination complexes, namely, {[(CH₃)₄N]₄[Co₃(μ₃-O)(H₄TC4AS-SO₂)]₂(TDC)₂·2H₂O·67CH₃OH}_n (LLU-101) and {[(CH₃)₄N]₂[Co₃(μ₄-O)(H₄TC4AS-SO₂)_0.5(TDC)₂]·32DMF}_n (LLU-102) were obtained via solvothermal reactions involving a mixture of cobalt salt, p-sulfosulfonylcalix^[4]arene (H₈TC4AS-SO₂) and thiophene-2,5-dicarboxylic acid (H₂TDC) ligands under methanol or DMF solvents, respectively. Structural analysis revealed that solvent regulation has a significant impact on the formation of the structure. Complex LLU-101 exhibits a 2D layered structure, which can be viewed as a structure composed of trinuclear shuttlecock-like secondary building units (SBUs), {Co₃-H₄TC4AS-SO₂}, connected by the TDC^2- ligand via a single coordination mode. In this architecture, both the upper and lower rims of the main ligand coordinate to Co²⁺ centers. In sharp contrast, LLU-102 displays a 3D network architecture, which can be conceptualized as a structure formed by tetranuclear shuttlecock-like {Co₄-H₄TC4AS-SO₂} SBUs, which are connected through two different coordination modes of TDC^2- ligands. Within the LLU-102 framework, the main ligand exhibits two distinct coordination patterns: one involving only the lower rim attached to Co²⁺ ions, and the other engaging both the upper and lower rims simultaneously in coordination. Magnetic studies reveal that all the cobalt centers in both complexes exhibit antiferromagnetic interactions.
- p-sulfosulfonylcalix[4]arene,
- solvothermal reactions,
- cobalt ion,
- solvent regulation
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