Abstract
New coordination oligomers and polymers of Sn(IV)-tetra(4-sulfonatophenyl)porphyrin have been constructed by the chelation reaction of its diaxialphenolates with Cu2+. The structure and properties of the synthesized polyporphyrin arrays were investigated by 1H Nuclear Magnetic Resonance (1H NMR), Infra Red (IR), Ultra Violet - Visible (UV-Vis) and fluorescence spectroscopy, mass spectrometry, Powder X-Rays Diffraction (PXRD), Electron Paramagnetic Resonance (EPR), thermal gravimetric, elemental analysis, and quantum chemical calculations. The results show that the diaxial coordination of bidentate organic ligands (L-tyrazine and diaminohydroquinone) leads to the quenching of the tetrapyrrole chromophore fluorescence, while the chelation of the porphyrinate diaxial complexes with Cu2+ is accompanied by an increase in the fluorescence in the organo-inorganic hybrid polymers formed. The obtained results are of particular interest to those involved in creating new ‘chemo-responsive’ (i.e., selectively interacting with other chemical species as receptors, sensors, or photocatalysts) materials, the optoelectronic properties of which can be controlled by varying the number and connection type of monomeric fragments in the polyporphyrin arrays.
Highlights
Sn(IV)-porphyrindiaxial complexes (SnP(L)2 ) via Cu2+ cations is ensured by one copper of the Sn(IV)-porphyrindiaxial complexes (SnP(L)2) via Cu2+cations is ensured by one copcation forming two stable five-membered chelate rings, with the axial ligands belonging per cation forming two stable five-membered chelate rings, with the axial ligands belongto the neighboring porphyrinates. The result of this oligomerization is the formation of ing to the neighboring porphyrinates. The result of this oligomerization is the formation stable nanoparticles (in comparison with less stable oligomers, which can be formed by of stable nanoparticles, the sizes and properties of four- or six-membered chelate rings based on copper cations), the sizes and properties of which depend on the nature of the axial ligands and the concentration ratio of the Sn(IV)which depend on the nature of the axial ligands and the concentration ratio of the Sn(IV)porphyrin axial complexes and d-metal cations
The obtained porphyrin oligomers and polymers in solid state and in solution are compounds in which the porphyrin fragments with tyrosine and diaminoresorcinol axial ligands form stable coordination compounds with two five-membered square planar metallocycles
The obtained porphyrin oligomers formed by five-membered chelate rings with Cu2+ are stable compounds
Summary
The ordering of the components in three dimensions, the possibility to use tectons of different natures and sizes, and the dynamic properties of the frameworks provide coordination polymers with unique luminescent, nonlinear optical, redox, magnetic, sorption, catalytic, ion exchange, sensory, and other properties [3,4,5,6,7,8,9,10] Due to their structure and unique physicochemical and photophysical characteristics, particularlytheir photoactivity, optoelectronic, and electrochemical properties, tetrapyrrole molecules are extremely promising objects for the construction of metal-coordination polymers for various purposes [11,12,13,14,15,16,17,18,19].
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