Controllable assembly of three [Cu₂(COO)₄]-based complexes using two as-synthesized aromatic tetracarboxylate linkers

Abstract

Three new complexes, namely, [Cu₂(H₂bdcpb)₂(pyridine)₂] (1), [Cu₃(bdcpp)₂(CH₃NCH₃)(H₂O)] (2), and [Cu₂(H₂bdcpp)₂(H₂O)₂]·2H₂O (3), have been synthesized through the hydro/solvothermal reaction of cupric nitrate and lab-synthesized 1,3-bis(2′,4′-dicarboxylphenyl)benzene (H₄bdcpb) or 2,6-bis(2′,4′-dicarboxylphenyl)pyridine (H₄bdcpp) in the presence of different solvent systems. Isostructural complexes 1 and 3 show dinuclear [Cu₂(COO)₄] covalent modes with different coordinate solvent molecules. In complex 2, a two-dimensional covalent layer is generated from one-dimensional loop chains interconnected by [Cu₂(COO)₄] paddle-wheels. Structural analyses revealed that the framework stability of complexes 1–3 originated from molecular custom-designed [Cu₂(COO)₄] paddle-wheel units by symmetrical 2′,4′-dicarboxyl polyaromatic ligands.

Graphical Abstract

Three new complexes have been synthesized through the hydro/solvothermal reaction of cupric nitrate and two lab-synthesized polycarboxylates in the presence of different solvent systems. Among them, two isostructural complexes show dinuclear [Cu₂(COO)₄] covalent modes, while the other complex is a two-dimensional covalent layer. Structural analyses revealed that the framework stability of the complexes originated from molecular custom-designed [Cu₂(COO)₄] paddle-wheel units.

Keywords:

• 2EYWORDSwheel unitsecular custom-dCu(II) complexes
• paddle-wheel unit
• rational design

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant No. 21301062), the Key Natural Science Research Project of Anhui Provincial Colleges and Universities (Grant No. KJ2019A0691), Program for Innovative Research Team in Huainan Normal University, State Jiangsu Province Engineering Laboratory of High Efficient Energy Storage Technology and Equipments, China University of Mining and Technology (Grant No. 2019-2), and the Key Natural Science Research Project of Huainan Normal University (Grant No. 2019XJZD01).

Disclosure statement

There are no conflicts of interest to declare.

Additional information

Funding

This work was financially supported by the National Natural Science Foundation of China (Grant No. 21301062), the Key Natural Science Research Project of Anhui Provincial Colleges and Universities (Grant No. KJ2019A0691), Program for Innovative Research Team in Huainan Normal University, State Jiangsu Province Engineering Laboratory of High Efficient Energy Storage Technology and Equipments, China University of Mining and Technology (Grant No. 2019-2), and the Key Natural Science Research Project of Huainan Normal University (Grant No. 2019XJZD01).