Crystallization Induced Enhanced Emission in Two New Zn(II) and Cd(II) Supramolecular Coordination Complexes with the 1-(3,4-Dimethylphenyl)-5-Methyl-1H-1,2,3-Triazole-4-Carboxylate Ligand

Abstract

Two new d10 metal supramolecular metal–organic frameworks (SMOFs) with general formula [ML2(H2O)2]n (M = Zn, Cd) have been synthetized using the sodium salt of the anionic 1-(3,4-dimethylphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate ligand (Na+L−). Both SMOFs have been structurally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The compounds are isostructural and form supramolecular aggregates via hydrogen bonds with the presence of less common dihydrogen bonds. Interestingly, they show ionic conductivity and porosity. The luminescent properties have been also studied by means of the excitation and emission spectra. Periodic DFT and molecular TD-DFT calculations have been used to unravel the emergence of luminescence in the otherwise non-emitting 1-(3,4-dimethylphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate ligand once incorporated in the SMOFs. Our results also illustrate the importance of considering the dielectric environment in the crystal when performing excited state calculations for isolated fragments to capture the correct electronic character of the low-lying states, a practice which is not commonly adopted in the community.

CuII-mediated DNA base pairing of a triazole-4-carboxylate nucleoside prepared by click chemistry

“…Triazole-4-carboxylate is known to form metal complexes with various transition metal ions via N, O-coordination, and the 2 : 1 Cu II complex is one such example. 38,39 The Taz C nucleoside was expected to form a Cu IImediated base pair when incorporated into a DNA duplex, similar to previously reported carboxypurine (Pur C ), 40 4-carboxyimidazole (Im C ), 17,41,42 and 2-oxo-carboxyimidazole (Im OC ) nucleosides. 26 In addition, the endocyclic nitrogen at the 2-position may function as a hydrogen bond acceptor for DNA polymerase recognition 43,44 and has the potential for future biotechnological applications.…”

Zinc(II) Carboxylate Coordination Polymers with Versatile Applications

“…Others CBCPs with benzenedi- or tricarboxylate and imidazole [ 10 , 29 , 30 , 31 , 32 , 33 ], triazole [ 34 , 35 , 36 , 37 ], thiazole [ 38 ], 2,2′-bipyridine (2,2′-bipy) [ 39 , 40 ], 1,10-phenanthroline (phen) [ 39 , 41 ] or 4,4′-bipyridine (4,4′-bipy) [ 39 , 42 , 43 , 44 , 45 , 46 ] derivatives were developed for the same purpose.…”

The Methylene Spacer Matters: The Structural and Luminescent Effects of Positional Isomerism of n-Methylpyridyltriazole Carboxylate Semi-Rigid Ligands in the Structure of Zn(II) Based Coordination Polymers

“…Luminescent Zn(II) complexes are used for the production of organic light-emitting diodes (OLED) [ 32 , 33 , 34 , 35 , 36 , 37 ]. Our previous studies show how the isomeric position of ethyl 5-methyl-1-(pyridin-3-yl)-1H-1,2,3-triazole-3-carboxylate/-4-carboxylate type organic ligands has allowed for the obtaining of monodimensional Cd(II) CPs to supramolecular 3D networks with the consequent modification of their emission [ 28 , 38 , 39 , 40 , 41 ]. We have now selected Zn(II) as the d 10 metal center and, as the flexible organic ligand, the tecton, 5-methyl-1-(pyridine-3-ylmethyl)-1 H -1,2,3-triazole -4-carboxylate (Na L1 ), and 5-methyl-1-(pyridin-4-ylmethyl)-1 H -1,2,3-triazole -4-carboxylate (Na L2 ) two positional isomers.…”