Isomeric bis(pyrazolyl)sulfones based on bis(1,1-dihydropolyfluoroalkyl)sulfones. A new type of ligands for metal-polymer complexes with silver cation

The work is devoted to the methods of synthesis of bis(polyfluoroalkenyl)sulfones and bis(polyfluoromethoxyalkenyl)sulfones as well as to the study of their reactions with diazomethane, resulting in the formation of N-methylated bis(pyrazolyl)sulfones isomers. Methods for the preparation of bis(polyfluoromethoxyalkenyl)sulfones not described previously in the literature have been developed by the addition of triethylamine and trimethylchlorosilane to a solution of the respective bis(polyfluoroalkyl)sulfones and methanol in diethyl ether in an argon atmosphere. A new method for the preparation of a previously unknown bis(3,3-difluoro-2,2-dimethoxypropyl)sulfone was suggested. The reaction occurs at room temperature in methanol in the presence of lithium hydroxide monohydrate. It was found that different regioisomeric bis(polyfluoroalkylpyrazolyl)sulfones are formed when using different methoxy derivatives of bis(polyfluoroalkenyl)sulfones in reaction with diazomethane, depending on the length of the polyfluoroalkyl moiety. These experimental data suggest that the attack of the double bond of methoxy-derived bis(polyfluoroalkenyl)sulfones by a molecule of diazomethane is influenced not only by the presence of an alkoxyl group, but also by the length of the polyfluoroalkyl substituent. The obtained bis(pyrazolyl)sulfones were investigated for the possibility of their use as ligands in the chemistry of metal complexes. It was shown that 5,5'-sulfonylbis[4-(difluoromethyl)-1-methyl-1H-pyrazole] forms a polymeric metal complex with silver nitrate. The results of X-ray structural analysis of the prepared coordination compound are presented. According to these results, the silver atom coordinates with two nitrogen atoms of pyrazole cycles of different molecules in the crystal of the obtained metal-complex compound, forming a supramolecular structure. In our opinion, an important role in this arrangement is played by the nitrate group that is coordinated with two silver atoms. As a result, we observed a supramolecular structure in the crystal that had a spiral structure with some free space in the middle. The paper also presents the results of spectral and X-ray diffraction analysis of a new regioisomeric compound of bis(3-hexafluoropropyl-1-methylpyrazolyl)sulfone.

Effect on absorption and electron transfer by using Cd(ii) or Cu(ii) complexes with phenanthroline as auxiliary electron acceptors (A) in D–A–π–A motif sensitizers for dye-sensitized solar cells

Four new polymeric metal complex dyes (PBDTT-PhenCd, PBDTT-PhenCu, PPV-PhenCd and PPV-PhenCu) with donor–acceptor–π-bridge-acceptor (D–A–π–A) structure were designed and synthesized.

Poly[[(μ2-benzene-1,3-dicarboxylato){μ2-1,4-bis[(1H-imidazol-1-yl)methyl]benzene}cadmium] dimethylformamide monosolvate]

The title coordination polymer, {[Cd(C8H4O4)(C14H14N4)]·C3H7NO}n, was synthesized by solvothermal reaction of metallic cadmium with the semi-rigid neutral ligand 1,4-bis[(1H-imidazol-1-yl)methyl]benzene (bix) and the V-shaped benzene-1,3-dicarboxylic acid (m-H2bdc). The structure exhibits a pseudo-C-centring which is almost fulfilled by the polymeric metal complex but not by the solvent dimethylformamide (DMF) molecules. The asymmetric unit contains two independent CdIIions, twom-bdc2−ligands, one and two half bix ligands, and two solvent DMF molecules. The CdIIions are both five-coordinated by three O atoms from two differentm-bdc2−ligands and two N atoms from two different bix ligands in a distorted square-pyramidal geometry. Them-bdc2−ligands adopt a chelate-monodentate coordination mode, connecting neighboring CdIIions into a zigzag chain parallel to [110]. Adjacent chains are further cross-linked by bix ligands, giving rise to a puckered sheet nearly perpendicular to the chain direction. Thus, each CdIIion is connected to four neighboring CdIIions through twom-bdc2−anions and two bix ligands, giving rise to the final non-interpenetrating uninodal layer with sql (4,4) topology.