Design and molecular structure of new homo- and heterofunctionalized polyazole derivatives of 1,1’-dinaphthylmethane and resorcincalix[4]arenes

• Published in: Journal of molecular structure 2025-04, Vol.1328, p.141294, Article 141294
• Main Authors: Glushko, Valentina V., Serkova, Olga S., Levina, Irina I., Toropygin, Ilya Yu, Maslennikova, Vera I.
• Format: Article
• Language: English
• Subjects: 1,1′-dinaphthylmethanes; Complex formation; Resorcincalixarenes; Tetrazoles; Triazoles
• ISSN: 0022-2860
• DOI: 10.1016/j.molstruc.2024.141294

•Azole systems based on 1,1’-dinaphthylmethane and rccc, rctt calix[4]resorcinarenes platforms were synthesized.•The obtained conjugates contain 2, 4 or 8 tetrazole or triazolyl-tetrazole moieties.•Hybrid rctt resorcinarene with phosphate and triazolyl-tetrazole groups in different plane was formed.•By UV spectroscopy primary evaluation of an ionophore abilities of olygotetrazole systems towards Cu2+, Ag+, Tb3+, Yb3+ was carried out.•All tetrazole ligands accept Cu2+ cations. Approaches to the design of new homo- and heterofunctionalized derivatives of 1,1’-dinaphthylmethane and resorcincalix[4]arenes that differ in the number, nature and spatial orientation of azole rings conjugated with polycyclic platform were found. Developed methods of synthesis were based on varying the combination of O-alkylation, nitrile-azide and alkyne-azide cycloaddition reactions. As a result following new compounds were synthesized, isolated with high yields and characterized: 2,2’-di- and 2,2’,7,7’-tetra-tetrazolyl-1,1’-dinaphthylmetanes, 2,2’-di- and 2,2’,7,7’-tetra-triazoletetrazolyl-1,1’-dinaphthylmethanes; rccc octa-tetrazolyl- and octa-triazoletetrazolyl-tetra-C-phenethylresorcincalix[4]arenes; rctt octa-tetrazolyl- and octa-triazoletetrazolyl-tetra-C-naphthylresorcincalix[4]arenes containing azole fragments located on horizontal and vertical benzene rings of macrocycle; rctt tetra-triazoletetrazolyl-tetra-phosphato-tetra-C-naphthylresorcincalix[4]arenes, in which azole groups are linked only to vertically oriented benzene rings of macrocycle, and phosphate moieties are immobilized on horizontally arranged benzene rigs. Using UV-spectroscopic method, the ionophore abilities of obtained polyazole systems towards some cations of d- (Cu2+, Ag+) and f- (Tb3+, Yb3+) elements were evaluated. It was shown that all examined compounds accepted Cu2+ cations, affinity to Ag+ cations was characteristic only of dinaphthylmethane derivatives, and ability to bind Tb3+, Yb3+ cations was exhibited by 2,2’,7,7’-tetra-triazoletetrazolyl-1,1’-dinaphthylmethane and rctt octa-triazoletetrazolyl-tetra-C-naphthylresorcincalix[4]arenes with the most spatially separated heterotopic functional branches. [Display omitted]