Structural Diversity and Dimensionality of Three Cu(II)-dpds-C5O52– Coordination Polymers Controlled by the Coordination Sphere of Cu(II) Centers and the Coordination Modes of C5O52– (dpds = 4,4′-Dipyridyldisulfide)

• Published in: ACS omega 2024-09, Vol.9 (39), p.40920-40931
• Main Authors: Wang, Chih-Chieh, Liao, Pei-Juan, Chung, Yu-Chen, Shin, Chi-Yang, Wu, Yi-Chen, Lee, Gene-Hsiang, Chien, Su-Ying, Chen, Bo-Hao, Chuang, Yu-Chun
• Format: Article
• Language: English
• ISSN: 2470-1343
• DOI: 10.1021/acsomega.4c06176

Three supramolecular architectures, [Cu 2 (dpds) 2 (C 5 O 5 ) 2 (H 2 O) 4 ]·3H 2 O ( 1 ), [Cu(dpds)(C 5 O 5 )]·3H 2 O ( 2 ), and [Cu 2 (dpds) 2 (C 5 O 5 ) 2 ]·9H 2 O·C 2 H 5 OH ( 3 ) (dpds = 4,4′-dipyridyldisulfide and C 5 O 5 2– (croconate) = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione), have been synthesized and structurally characterized. Compound 1 contains two crystallographically independent Cu(II) ions, which are both distorted octahedral geometry with elongation along the croconate- and H 2 O-bound axial positions and bonded with two N atoms of two dpds, two O atoms of one C 5 O 5 2– , and two H 2 O molecules. Two crystallographically independent dpds ligands, both adopting the bis-monodentate bridging mode, connect two Cu(II) ions to form a one-dimensional zigzag chain-like coordination polymer. In 2 and 3 , there are two and three crystallographically independent Cu(II) ions, respectively, which are all distorted octahedral geometries with elongation along the croconate-bound axial positions six-coordinated and bonded with two N atoms of two dpds ligands in cis- or/and trans-forms and four O atoms of two C 5 O 5 2– ligands. The dpds ligands in 2 and 3 all adopt the bis-monodentate bridging mode, and the C 5 O 5 2– ligands act as bridging ligands with bridging bis-bidentate through three C 5 O 5 2– oxygen atoms in 2 and bridging bis-bidentate through four adjacent C 5 O 5 2– oxygen atoms in 3 , respectively, linking the Cu(II) ions to generate a two-dimensional layered and a three-dimensional metal–organic framework, respectively. The structural diversity and dimensionality observed in 1 – 3 may be attributed to the cis- or/and trans-coordination sphere of Cu(II) centers with two dpds ligands and the coordination modes of croconate ligands. Thermal stability and in situ temperature-dependent structural variations of 1 – 3 have been verified by thermogravimetric analysis and powder X-ray diffraction measurements. Compounds 1 and 3 both exhibit water vapor capture behaviors with hysteresis isotherms.