Authors: Chih‐Chieh Wang | Pei-Juan Liao | Yu‐Chen Chung | Chi-Yang Shin | Yichen Wu | Gene‐Hsiang Lee | Su‐Ying Chien | Bo‐Hao Chen | Yu‐Chun Chuang
Source: ACS Omega (article, 2024-09-17)
Field: Chemistry — Inorganic Chemistry

Structural Diversity and Dimensionality of Three Cu(II)-dpds-C<sub>5</sub>O<sub>5</sub><sup>2–</sup> Coordination Polymers Controlled by the Coordination Sphere of Cu(II) Centers and the Coordination Modes of C<sub>5</sub>O<sub>5</sub><sup>2–</sup> (dpds = 4,4′-Dipyridyldisulfide) Three supramolecular architectures, [Cu<sub>2</sub>(dpds)<sub>2</sub>(C<sub>5</sub>O<sub>5</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·3H<sub>2</sub>O (<b>1</b>), [Cu(dpds)(C<sub>5</sub>O<sub>5</sub>)]·3H<sub>2</sub>O (<b>2</b>), and [Cu<sub>2</sub>(dpds)<sub>2</sub>(C<sub>5</sub>O<sub>5</sub>)<sub>2</sub>]·9H<sub>2</sub>O·C<sub>2</sub>H<sub>5</sub>OH (<b>3</b>) (dpds = 4,4'-dipyridyldisulfide and C<sub>5</sub>O<sub>5</sub> <sup>2-</sup> (croconate) = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione), have been synthesized and structurally characterized. Compound <b>1</b> contains two crystallographically independent Cu(II) ions, which are both distorted octahedral geometry with elongation along the croconate- and H<sub>2</sub>O-bound axial positions and bonded with two N atoms of two dpds, two O atoms of one C<sub>5</sub>O<sub>5</sub> <sup>2-</sup>, and two H<sub>2</sub>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 <b>2</b> and <b>3</b>, 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<sub>5</sub>O<sub>5</sub> <sup>2-</sup> ligands. The dpds ligands in <b>2</b> and <b>3</b> all adopt the bis-monodentate bridging mode, and the C<sub>5</sub>O<sub>5</sub> <sup>2-</sup> ligands act as bridging ligands with bridging bis-bidentate through three C<sub>5</sub>O<sub>5</sub> <sup>2-</sup> oxygen atoms in <b>2</b> and bridging bis-bidentate through four adjacent C<sub>5</sub>O<sub>5</sub> <sup>2-</sup> oxygen atoms in <b>3</b>, 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 <b>1</b>-<b>3</b> 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 <b>1</b>-<b>3</b> have been verified by thermogravimetric analysis and powder X-ray diffraction measurements. Compounds <b>1</b> and <b>3</b> both exhibit water vapor capture behaviors with hysteresis isotherms. Polymer ; Curse of dimensionality ; Crystallography ; Materials science ; Chemistry ; Physics ; Computer science ; Organic chemistry Metal-Organic Frameworks: Synthesis and Applications ; Crystal structures of chemical compounds ; Organometallic Compounds Synthesis and Characterization