Photophysical Properties and Adsorption Behaviors of Novel Tri-Cationic Boron(III) Subporphyrin on Anionic Clay Surface

Abstract

Two types of +3-charged subporphyrin derivatives with m- and p-methylpyridinium as the meso-aryl substituents were designed and synthesized. Their photophysical properties with and without anionic saponite clay were investigated. These cationic subporphyrins were suitably designed for adsorption on the saponite nanosheet surface with their photoactivity. Absorption and emission spectra of these subporphyrin-saponite complexes exhibited strong bathochromic shifts due to the flattening of the molecules on the nanosheet. This behavior was observed as drastic visual changes in their luminescence colors. Additionally, aggregation behaviors were not observed in the saponite complexes even at high dye loading levels for both subporphyrins. Moreover, under such condition, their fluorescence properties on the saponite surface were not only maintained but also enhanced without unexpected deactivations despite the dye molecules are densely introduced on the solid surface. These findings are beneficial for applications of the dye-clay complexes to photofunctional materials such as strongly luminescent materials, highly sensitive clay sensors and artificial photosynthesis systems.

Modification, hybridization and applications of saponite: An overview

“…Compared with Mt, Sap is more easy delaminated completely in water to form a transparent dispersion. Such optical transparency, together with high absorption capacity of Sap, make it a very good two-dimensional inorganic host for many organic dye molecules with optical functions (Tsukamoto et al, 2016b), in particular fluorescence. The interlayer space and the layer charge can provide a static confinement to the fluorescent dyes and is conducive to better distribution and assembly of the dye molecules, thereby preventing fluorescence from quenching.…”

“…Moreover, the chemical composition of natural Sap can be extremely variable, depending on the geological genesis process (Utracki et al, 2007). This defects limits the use of natural Sap in catalysis (Gómez-Sanz et al, 2017), adsorption (Franco et al, 2016a) and optics (Tsukamoto et al, 2016b). Hence, Sap-like solids with well-controlled chemical composition are synthesized and such solid products are often called synthetic Sap.…”

“…2). Strikingly, Sap has been used as a support for the immobilization of luminescent entities, rendering the resultant nanocomposites with particularities in optical imaging (Tsukamoto et al, 2016b) and optoelectronic applications (Nanan et al, 2015).…”

Fotoiniciadores baseados em quitosana/tioxantona e argila/tioxantona: síntese, caracterização e aplicação em reações de polimerização e formação de nanopartículas metálicas

“…Muitos grupos tem investigado o comportamento fotofísico de híbridos orgânico-inorgânico baseados em corantes orgânicos e argilas minerais (Bujdak, Iyi e Fujita, 2002;Bujdak, Iyi, Hrobarikova, et al, 2002;Martinez et al, 2004;Martinez et al, 2005;Yao et al, 2005;Bujdak e Iyi, 2008;Ferreira et al, 2013;Mallakpour et al, 2013;Tsukamoto et al, 2013;Bohac et al, 2016;Tsukamoto et al, 2016). A formação de híbridos de derivados de trifenilbenzeno/argila mostraram um aumento na intensidade de emissão de fluorescência comparados com a soluções do corante sem a presença da argila (Tsukamoto et al, 2013).…”

“…A formação de híbridos de derivados de trifenilbenzeno/argila mostraram um aumento na intensidade de emissão de fluorescência comparados com a soluções do corante sem a presença da argila (Tsukamoto et al, 2013). Materiais híbridos compostos de argila mineral e subporfirínas catiônicas também exibiram um aumento significativo nas propriedades luminescentes quando as moléculas orgânicas foram alinhadas nas superfície das lamelas de argila (Tsukamoto et al, 2016).…”