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.
Highlights
One of the most active areas in materials chemistry in recent years involves the quest for novel organic solid-state luminescent materials for the development of organic light-emitting diodes (OLEDs) [1,2,3], bioimaging agents [4,5,6], chemosensors, detectors of microenvironmental changes [7,8,9,10], or dynamic functional materials [11,12,13]
We reported the synthesis of two new d10 metal supramolecular metal–organic frameworks (SMOFs) of general formula [ML2 (H2 O)2 ]n where M = Zn or Cd and L corresponds to the anionic
While aqueous solutions of the sodium salt of the ligand do barely emit, the two new SMOFs show a bright luminescence with a broad peak at about 440 nm
Summary
One of the most active areas in materials chemistry in recent years involves the quest for novel organic solid-state luminescent materials for the development of organic light-emitting diodes (OLEDs) [1,2,3], bioimaging agents [4,5,6], chemosensors, detectors of microenvironmental changes [7,8,9,10], or dynamic functional materials [11,12,13]. Several strategies have been developed to overcome this inconvenience which severely limits the application in solid-state devices of many materials which otherwise have superb luminescent properties in solution. Most of these efforts are basically aimed towards controlling the aggregation process to prevent excimer formation [14,15,16,17] that is thought to be at the origin of ACQ in many cases [18,19].
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