Seven Zn(II) and Cd(II) 1D coordination polymers based on azine donor linkers and decorated with 2-thiophenecarboxylate: Syntheses, structural parallels, Hirshfeld surface analysis, and spectroscopic and inclusion properties. (15th September 2020)

• Record Type: Journal Article
• Authors: Lozovan, Vasile; Kravtsov, Victor Ch.; Coropceanu, Eduard B.; Siminel, Nikita; Kulikova, Olga V.; Costriucova, Natalia V.; Fonari, Marina S.
• Is Part Of: Polyhedron. Volume 188(2020)
• Publication Date: 2020-09-15
• Subjects: Azomethyne ligands -- Coordination polymers -- Crystal structure -- Spectroscopic studies -- Inclusion properties -- Luminescence; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2020.114702
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Of seven mixed-ligand 1D coordination polymers—[Zn2 (4-bphz)(2-tpc)4 ]n (1 ), [Zn2 (4-bpmhz)(2-tpc)4 ]n (2 ), [Cd(4-bphz)2 (2-tpc)2 ]n (3 ), [Zn(3-bphz)(2-tpc)2 ]n (4 ), [Zn(3-bpmhz)(2-tpc)2 ]n (5 ), [Cd(4-bpmhz)(2-tpc)2 ]n ·0.5n(4-bpmhz) (6 ), [Cd(3-bpmhz)(2-tpc)2 ]n · 0.5n(H2 O) (7 ) (where 2-tpc = 2-thiophenecarboxylate, 4-bphz = 1, 2-bis(pyridin-4-ylmethylene) hydrazine, 4-bpmhz = 1, 2-bis(1-(pyridin-4-yl)ethylidene)hydrazine, 3-bphz = 1, 2-bis(pyridin- 3-ylmethylene)hydrazine, and 3-bpmhz = 1, 2-bis(1-(pyridin-3-yl)ethylidene)hydrazine) the guest-free arrays 1 –5 pack in the parallel stacking modes, while the inclusion compounds 6 and 7 reveal criss-cross packing arrangements with large channels where guest molecules (4-bpmhz/water) serve as structure-directing templates. The distributions of intermolecular interactions in 1 –7 were quantified by Hirshfeld surface and fingerprint plots analysis. The guest-exchange properties for 6 and the solid state emissive properties for 1 –7 are reported. Highlights: Mixed-ligand strategy was used for the synthesis of 7 1D coordination polymers. Criss-cross crystal packing facilitates guest accommodation. Solvent-exchange was demonstrated. The weak intermolecular forces were confirmed by comprehensive Hirshfeld surface analysis. Emission properties were registered and discussed. Abstract: Seven mixed-ligand 1D coordination polymers [Zn2 (4-bphz)(2-tpc)4 ]n (1 ), [Zn2 (4-bpmhz)(2-tpc)4 ]n (2 ), [Cd(4-bphz)2 (2-tpc)2 ]n (3 ), [Zn(3-bphz)(2-tpc)2 ]n (4 ), [Zn(3-bpmhz)(2-tpc)2 ]n (5 ), [Cd(4-bpmhz)(2-tpc)2 ]n ·0.5n(4-bpmhz) (6 ), [Cd(3-bpmhz)(2-tpc)2 ]n ·0.5n(H2 O) (7 ) (where 2-tpc = 2-thiophenecarboxylate, 4-bphz = 1, 2-bis(pyridin-4-ylmethylene) hydrazine, 4-bpmhz = 1, 2-bis(1-(pyridin-4-yl)ethylidene)hydrazine, 3-bphz = 1, 2-bis(pyridin-3-ylmethylene)hydrazine, and 3-bpmhz = 1, 2-bis(1-(pyridin-3-yl)ethylidene)hydrazine) were prepared and studied using spectroscopic (FTIR, UV–Vis) and X-ray diffraction methods of analysis. Similarly, four bidentate-bridging azine ligands provide the polymers' extension, while the different mononuclear/binuclear metal nodes demonstrate the variable metals' coordination capacities that influence the crystal packing motifs and inclusion properties. The guest-free arrays 1 –5 pack in parallel stacking modes, while the inclusion compounds 6 and 7 reveal criss-cross packing arrangements with large channels where guest molecules (4-bpmhz/water) serve as structure-directing templates in the formation of crystal structures. The distributions of different types of intermolecular interactions with respect to the percentage of stacking interactions in 1 –7 were quantified by Hirshfeld surface and fingerprint plots analysis. The guest-exchange properties for 6 and the solid state emissive properties for 1 –7 are reported.