Introduction of Bulky Perfluoroalkyl Groups at the Periphery of Zinc Perfluorophthalocyanine: Chemical, Structural, Electronic, and Preliminary Photophysical and Biological Effects

Abstract

Hohe Antitumor‐Aktivität zeigt das erste sterisch gehinderte (nichtplanare), perhalogenierte Zink‐Phthalocyanin (Pc), [F64PcZn(Aceton)2], im Vergleich zu planarem Zinkperfluorphthalocyanin (siehe Struktur: F grün, N blau, O rot, C grau). Die Perfluorisopropyl‐Substituenten erhöhen die Löslichkeit, stabilisieren die axialen Liganden (wie die koordinierten Acetonmoleküle in der abgebildeten Struktur), verkleinern die HOMO‐LUMO‐Lücke, verändern die Redoxpotentiale und verlängern die Lebenszeit des angeregten Triplettzustandes des neuen Komplexes.

Growth and characterization of thin films prepared from perfluoro-isopropyl-substituted perfluorophthalocyanines

“…Semiempirical calculations (Parameterized Model number 3) also reveal a 1.0 eV energetic stabilization of the frontier orbitals of F 64 PcZn relative to those of F 16 PcZn [26]. This difference between F and R f groups can be rationalized [30,31], by the absence of π back-bonding of R f groups, which results in their overall higher electron-withdrawing capability. The calculated energy stabilization of the frontier orbitals is reflected by the positive 0.6 V shift of the electrochemical redox potential of the first ring-centered reduction in F 64 PcZn compared to F 16 PcZn [30], and the suppression of oxidation.…”

“…In particular, F 16 Pc materials are interesting candidates for n-type channels in organic field effect transistors, being relatively stable even under ambient conditions [27,28]. A further step in the direction of orbital stabilization is represented by the introduction of perfluorinated alkyl groups as Pc ring substituents [29][30][31][32]. 1,4,8,11,15,18,22,25-octakisfluoro-2,3,9,10,16,17,23,24- [23,24].…”

Photophysical, photochemical and aggregation behavior of novel peripherally tetra-substituted phthalocyanine derivatives

“…Furthermore, owing to their extensively planar aromatic system, phthalocyanines exhibit a high aggregation tendency which leads to insolubility in the case of unsubstituted parent derivatives or hinders purification and characterization of compounds in many respects together with a lower efficiency in their use in PDT [16,17]. PDT is a binary therapy that involves the combination of visible light and a photosensitizer [18].…”

Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(m-methoxyphenyl)coumarin groups

“…They play a major role in many fields of modern technology such as data storage, photoelectronic generation, and catalyst [11][12]. Their use as photosensitizers in photodynamic therapy (PDT) is the most attractive application of phthalocyanines because of their ability to generate highly singlet oxygen ( 1 O 2 ), which is toxic for tumor cells [13][14][15].…”