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Cis/Trans Isomeric Valence Tautomeric Compounds with Guest-Driven Conformational Adaptation in Pillar[5]arene
Ling-Tai Yue1, Jie-Sheng Hu1, Yu-Meng Zhao1
1Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Liangxiang Campus, Beijing Institute of Technology, Beijing 102488, PR China.
Inorganic Chemistry
|March 4, 2025
Summary
This study synthesized novel cobalt-based valence tautomeric (VT) complexes using pillar[5]arene ligands, achieving both trans and rare cis isomers for the first time. These findings demonstrate host-guest interactions
Area of Science:
- Coordination Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Valence tautomeric (VT) complexes are crucial for developing advanced materials.
- Designing effective ancillary ligands is key to synthesizing new VT complexes.
- Pillar[5]arene derivatives offer adaptable conformations for ligand design.
Purpose of the Study:
- To synthesize novel cobalt-based VT complexes using phenylpyridine- and alkynylpyridine-containing pillar[5]arene ligands.
- To investigate the structural diversity and isomeric configurations of the synthesized VT complexes.
- To explore the influence of host-guest interactions on VT behavior and material properties.
Main Methods:
- Synthesis of cobalt-based VT complexes incorporating pillar[5]arene derivatives (pyphp[5] and pyetp[5]).
- Single-crystal X-ray diffraction analysis to determine the one-dimensional structures and configurations.
- Characterization of host-guest interactions and their impact on pore conformation and stacking patterns.
Main Results:
- Successful synthesis of four cobalt-based VT complexes: [CoIII(Sq•-)(Cat2-)(pyphp[5])] and [CoIII(Sq•-)(Cat2-)(pyetp[5])].
- Complexes 1a· and 1b· adopted the common trans configuration, while 2a· and 2b· exhibited a rare C2h-symmetric cis configuration.
- Distinct pore conformations and stacking patterns were observed, influenced by guest molecule size and host-guest interactions within the pillar[5]arene cavity.
- This work marks the first instance of synthesizing both trans and C2h-symmetric cis isomers of the cobalt-dioxolene-pyridine moiety.
Conclusions:
- Pillar[5]arene ligands enable the synthesis of VT isomers with controllable configurations.
- Host-guest interactions within pillar[5]arenes play a critical role in modulating VT behavior.
- This research provides valuable insights for designing multifunctional materials with tunable magnetic properties.
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