Nonlinear optical dynamics of benzothiazole derivatized phthalocyanines in solution, thin films and when conjugated to nanoparticles

• Published in: Journal of photochemistry and photobiology. A, Chemistry. Chemistry., 2017-09, Vol.346, p.46-59
• Main Authors: Nwaji, Njemuwa, Jones, Benjamin, Mack, John, Oluwole, David O., Nyokong, Tebello
• Format: Article
• Language: English
• Subjects: Benzothiazole; Chlorides; Circular dichroism; Density functional theory; Dichroism; Gallium; Gold; Gold nanoparticles; Indium; Linkages; Nanoparticles; Nonlinear optics; Optics; Photophysics; Phthalocyanines; Silver; Silver nanoparticles; Spectroscopy; Sulfur; Thin films; Zinc
• ISSN: 1010-6030; 1873-2666
• DOI: 10.1016/j.jphotochem.2017.05.042

[Display omitted] Tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] complexes containing a sulphur bridge showed more enhanced optical limiting behaviour than the corresponding oxo bridged tetrakis[(benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] derivatives. •Ga, In and Zn benzothiazole phthalocynines are conjugated to Au and Ag nanoparticles.•The conjugates show improved nonlinear optical behaviour.•Au nanoparticles show more improved optical limiting compared to their Ag counterparts. Benzothiazole phthalocynines complexes: tetrakis[(benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] indium(III) chloride (1) and tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] indium(III) chloride (2) were synthesisized and their nanosecond nonlinear optical behaviours in solution, solid state and when conjugated to metallic nanoparticles were examined and compared to those of the corresponding ZnPc and GaPc which are designated as: tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] zinc(II) (3), tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] gallium(III) chloride (4), tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] zinc(II) (5) and tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] gallium(III) chloride (6). Trends in the electronic structures were identified through a comparison of the UV–vis absorption and magnetic circular dichroism (MCD) spectroscopy of the complexes and calculated spectra predicted by time dependent density functional theory (TD-DFT). Of all the complexes and nanoconjugates, complex 2 (containing sulphur linkages and In as a central metal) gave the best optical limiting behaviour.