Phosphorus-Nitrogen Compounds: Part 76. Design and Syntheses of Dispiro- and Trispiro(N/N)cyclotriphosphazenes: Conformational and Structural Analyses, Chirality, Electrochemical, Dye-Sensitized Solar Cells, and Bioactivity Studies

CEMALOĞLU R., ASMAFİLİZ N., Tumer Y., HÖKELEK T., Kilic Z., Celik N. N., ...More

INORGANIC CHEMISTRY, vol.63, no.39, pp.18389-18407, 2024 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 63 Issue: 39
  • Publication Date: 2024
  • Doi Number: 10.1021/acs.inorgchem.4c02206
  • Journal Name: INORGANIC CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Aquatic Science & Fisheries Abstracts (ASFA), Art Source, Chemical Abstracts Core, Chimica, Compendex, EMBASE, DIALNET
  • Page Numbers: pp.18389-18407
  • Hacettepe University Affiliated: Yes

Abstract

The reactions of monospirocyclotriphosphazenes (1 and 2) with N-methyl-1,3-diaminopropane gave unsymmetrical cis-(3 and 5) and trans-(4 and 6) dispirocyclotriphosphazenes. Trans-cis-trans (tct) (7 and 11), cis-cis-cis (ccc) (8 and 12), trans-trans-cis (ttc) (9 and 13), and cis-trans-trans (ctt) (14) trispirocyclotriphosphazenes were obtained from the reactions of 3 and 5 and 4 and 6 with N-methyl-1,3-diaminopropane. cis-Dispirocyclotriphosphazenes (3 and 5) exist as "pseudomesoracemates", while trans-dispirocyclotriphosphazenes (4 and 6) are in "racemates". The existences of cis-3 and trans-4 as "pseudomesoracemate" and "racemate" were confirmed by P-31 NMR spectra recorded by the addition of "chiral solvating agent (CSA)". X-ray crystallography proved that the absolute configurations of each enantiomer of cis-5 and trans-6 are SS ' and RS '. Trispirocyclotriphosphazenes tct, ttc, ccc, and ctt exist as racemates, pseudomesoracemate, and meso forms. Furthermore, Hirshfeld surface analysis of the crystal structures of cis-5 and trans-6 revealed that the most significant contribution to crystal packing comes from HH (58.2 and 57.6%, respectively). An oxidation-reduction wave was detected in the reversible cyclic voltammograms of the phosphazenes. The highest power conversion efficiency in dye-sensitized solar cell studies was obtained with cis-5. Additionally, trans-6 exhibited the lowest minimal inhibitory concentration value (78.1 mu M) against Candida tropicalis, and it was observed to cleave pBR322 plasmid DNA.