Concentration Gradient-Induced Syntheses and Crystal Structures of Two Copper(II) Coordination Polymer Based on Phthalic Acid and 2,2′-Bipyridine

Concentration Gradient-Induced Syntheses and Crystal Structures of Two Copper(II) Coordination Polymer Based on Phthalic Acid and 2,2′-Bipyridine

The reaction of copper nitrate, phthalic acid (1,2-H<sub>2</sub>BDC), and bipyridine in ammonia/ethanol media affords two multi-copper (II) cluster-based coordination polymers, namely {[Cu<sub>4</sub>(bpy)<sub>4</sub>(OH)<sub>2</sub>(BDC)<sub>2&l...

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Bibliographic Details
Main Authors: Tao Zhou, Gengyi Zhang, Chunhong Tan, Yong Liu, Xiao-Feng Wang
Format: Article
Language:English
Published: MDPI AG 2025-04-01
Series:Molecules
Subjects:
multi-copper cluster
coordination polymer
gradient-induced
crystal structure
Online Access:https://www.mdpi.com/1420-3049/30/9/1953
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Summary:The reaction of copper nitrate, phthalic acid (1,2-H<sub>2</sub>BDC), and bipyridine in ammonia/ethanol media affords two multi-copper (II) cluster-based coordination polymers, namely {[Cu<sub>4</sub>(bpy)<sub>4</sub>(OH)<sub>2</sub>(BDC)<sub>2</sub>]·2OH·13H<sub>2</sub>O}<sub>n</sub> (<b>USC-CP-6</b>) and {[Cu<sub>2</sub>(BDC)<sub>2</sub>(bpy)<sub>2</sub>(H<sub>2</sub>O)]·3H<sub>2</sub>O}<sub>n</sub> (<b>USC-CP-7</b>), under ambient conditions, with <b>CP-6</b> forming at the bottom and <b>CP-7</b> at the upper edge of the same beaker. The single-crystal structures reveal that it is a rare case of gradient-induced formation of different multi-copper(II) cluster-based CPs within a single-solution chemical reaction. <b>CP-6</b> crystallizes in the monoclinic system, sp. gr. <i>P</i>2<sub>1</sub>/c, and is composed of chair-like tetranuclear [Cu<sub>4</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>(bpy)<sub>4</sub>(BDC)<sub>2</sub>]<sup>2+</sup> clusters as secondary building units, bridged by BDC<sup>2−</sup> ligands to form a two-dimensional layer framework, while <b>CP-7</b> crystallizes in the monoclinic system, sp. gr. <i>P</i>2<sub>1</sub>/n, with binuclear [Cu<sub>2</sub>(1,2-BDC)<sub>2</sub>(bpy)<sub>2</sub>(H<sub>2</sub>O)] clusters linked by bridging BDC<sup>2−</sup> ligands to form a one-dimensional looped double chain. Through intermolecular <i>π</i>–<i>π</i> stacking and hydrogen bonds between the coordination water, lattice water, and free oxygen atoms from carboxylate, both compounds yield a 3D supramolecular structure.
ISSN:1420-3049

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