The pyridinedicarboxylate-Tb(III) complexes, TbPDC and Tb(PDC)3, as luminescent probes for ATP monitoring have been conveniently prepared and characterized by FT-IR, 1H-NMR, ESI-MS, UV-Vis, excitation, and emission spectroscopy. Interestingly, these two Tb(III) complexes were quenched by ATP by a similar mechanism via π-π stacking interaction between the chelating ligand and adenine moiety. The ability of luminescent probes applied for the determination of ATP in aqueous solution has been investigated. The dynamic ranges for the quantification of ATP are within 10−90 μM and 10−100 μM with detection limits of 7.62 and 11.20 μM for TbPDC and Tb(PDC)3, respectively. The results demonstrated that these luminescent probes would be a potential candidate assay for ATP monitoring in hygiene assessment.
Many experimental data show that bulky substituents on the molecules enhance solubility, catalytic activity, and photophysical properties due to the prevention of π-π stacking in metal salicylaldimines. In order to understand the effect of bulkiness of substituents on the properties of the obtained molecules, the author researched and synthesized two new pyrene-based salicylaldiminato-type ligands that were substituted at 7-position and functionalized on imine group with bulky substituents. After the introduction of the tert-butyl group at 7-position of pyrene by Friedel-Crafts reaction, the syntheses of new ligands 1-hydroxy-2-[((2,6-dimethylphenyl)-imino)methyl]-7-(tert-butyl)-pyrene 3, 2-hydroxy-1- [((2,6-dimethylphenyl)imino)methyl]-7-(tert-butyl)-pyrene 4 and corresponding platinum complexes 3(Pt), 4(Pt) were performed in the different ways with the synthetic processes of the complexes 1(Pt) and 2(Pt). The new ligands and complexes were characterized by 1H NMR, IR spectroscopy, mass spectroscopy, elemental analysis and X-ray diffraction, only for 3(Pt). In addition to measurements of the absorption and emission spectra, TDDFT calculations using the B3LYP functions were also performed. The complexes 3(Pt) and 4(Pt) exhibit good solubility and red-shift in absorption and emission spectra because of tert-butyl group at 7-position of pyrene and extension of the delocalized π-orbitals to the 2,6-dimethylphenyl on imine group. The change of functional groups also induces the upfield shift of the protons affected by ring currents of phenyl groups Ar-3, Ar-4 on imine groups. Introduction of t-butyl groups in pyrene moieties can stabilize radical forms in oxidation processes.
Molecules exhibiting cold crystallization, an exothermic phenomenon in heating following supercooling, can be used as a heat-storing material. On the other hand, examples in non-polymers are still few. To test metal complexes as potential compounds for heat-storage materials, a salicylaldiminato-typed copper(II) complex, bis[2-[(octylimino)methyl]-1-pyrenolato-N,O] copper(II) 1(Cu), which had two different coloured forms and a characteristic long alkyl chain, exhibited complicated thermal behaviour including cold crystallization. The long alkyl chain was a steric barrier to molecular stacking, leading to the supercooled state. Besides, the two polymorphs were characterized by IR spectra studies and magnetic susceptibility.
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