Akademik Veri Yönetim Sistemi
Synthetic Metals, cilt.319, 2026 (SCI-Expanded, Scopus)
In this work, the preparation and comprehensive electrochemical evaluation of α-substituted mononuclear CoPc ( 2 ), FePc ( 4 ), and Mn(OAc)Pc ( 6 ), as well as dinuclear ball-type Co₂Pc₂ ( 3 ), Fe₂Pc₂ ( 5 ), and Mn₂(OAc)₂Pc₂ ( 7 ) metallophthalocyanine complexes derived from 3,3′-((3,5-di-tert-butyl-1,2-phenylene)bis(oxy))diphthalonitrile under specific reaction conditions are presented. It aims to investigate the structure-property relationships of newly synthesized mono- and dinuclear metallophthalocyanines and to reveal how nuclearity and metal centers influence their structural features, electronic behavior, solubility, synthetic routes, and electrochemical redox behavior. Phthalocyanines were well dissolved in organic solvents and showed minimal aggregation, as expected, due to the presence of t-butyl groups. In contrast to previous works that primarily focused on β-substituted ball-type phthalocyanines, this study provides the first systematic investigation of the effect of α/β-substitution on redox behavior. Mononuclear complexes 2 , 4 , and 6 showed peripheral nitrile reduction processes that were absent in the dinuclear analogues, while ball-type complexes 3 , 5 , and 7 displayed richer electrochemistry due to mixed-valence interactions. By comparison, Mn(OAc)Pc ( 6 ) and Mn₂(OAc)₂Pc₂ ( 7 ) showed a broader redox behavior arising from Mn-based oxidation and reduction couples, specifically involving Mn(III)/Mn(IV) and Mn(III)/Mn(II) transitions. Mn2(OAc)2Pc2 ( 7 ) exhibited the richest redox profile, indicating its potential superiority for electrochemical applications. These findings highlighted the influence of molecular structure and nuclearity on electron-transfer characteristics. They provided a fundamental basis to support the development of future electrocatalytic and electrochromic materials due to their rich redox, spectral, and color properties.