Akademik Veri Yönetim Sistemi
Inorganica Chimica Acta, cilt.600, 2026 (SCI-Expanded, Scopus)
This study covers the syntheses, spectroscopic and electrochemical characterizations, and dye-sensitized solar cell (DSSC) performances of novel unsymmetrical dichlorobis(ferrocenylspiro-N2/N2 and N2/NO) cyclotriphosphazenes. Herein, nucleophilic exchange reactions of monoferrocenylspirocyclotriphosphazenes (1, 2 and 3) and N-methyl-N′-ferrocenyl-1,3-diaminopropane afford unsymmetrical trans-(1a, 2a and 3a) and cis-(1b, 2b and 3b) dichlorobis(ferrocenyl) dispirocyclotriphosphazenes. The crystal and molecular structures of trans-1a, trans-2a and cis-2b were elucidated crystallographically. In addition, Hirshfeld surface (HS) analyses were carried out. Crystallographic data also confirmed their cis and trans configurations. The total puckering amplitudes (QTs) of the six-membered P3N3 rings indicate that they are in the flattened boat conformations with the QT values of 0.0680 (24) Å (for trans-1a), 0.2034 (16) Å (for trans-2a), and 0.1767 (20) Å (for cis-2b). These phosphazenes have two different chiral P-centers. Trans- and cis-dispirocyclotriphosphazenes are expected to exist as “racemates (racemate I, RR’/SS’; racemate II, RS’/SR’) and pseudomesoracemate (pseudomesoracemate I, RS’/SR’; pseudomesoracemate II, RR’/SS’), respectively. 31P NMR spectra with the added chiral resolving agent [R)-(−)-1-(9′-anthryl)-2,2,2-trifluoroethanol, CSA] confirm these chiralities. All dispirophosphazenes were characterized using FTIR, Q-TOFMS, and NMR spectroscopy. Additionally, the reversible cyclic voltammograms of unsymmetrical dispiroferrocenylphosphazenes show only an oxidation-reduction wave. Based on studies of DSSCs, the highest power conversion efficiency (η = 0.48%) is observed in trans-3a. Trans 3a demonstrated the best DSSC performance, with a power conversion efficiency of 0.65%, a current density (JSC) of 1.25 mA cm−2 and an open-circuit voltage (VOC) of 740 mV.