Morphology‐Controlled Self‐Assembly of an Organic/Inorganic Hybrid Porphyrin Derivative Containing Polyhedral Oligomeric Silsesquioxane (POSS)

Abstract

An organic/inorganic hybrid porphyrin derivative, namely, metal-free tetrakisphenyl porphyrin-polyhedral oligomeric silsesquioxanes (H2 TPP-POSS) was synthesized by azide-alkyne click chemistry. The self-assembly behavior of H2 TPP-POSS was systematically studied in CHCl3 at different concentrations and in solvents with different polarities. Novel nanovesicles could be obtained through the self-assembly of H2 TPP-POSS in CHCl3 at a concentration lower than 10(-4) m. Diffuse microrods formed at a concentration higher than 10(-4) M. Additionally, the polarity of the solvent also greatly influenced the assembled morphologies, and a series of assembled morphologies, including crescent-shaped micelles, spherical micelles, doughnut-shaped vesicles, and ordered square sheets, could form in solvents with different polarities.

Azides and Porphyrinoids: Synthetic Approaches and Applications. Part 1—Azides, Porphyrins and Corroles

“…The same research group, by following the LbL process and through a click approach, prepared other porphyrin-based molecular multilayer films (ITO-MP1-Zn) on indium tin oxide (ITO) electrodes for photovoltaic and photogalvanic devices [50]. Zhang and co-workers described the preparation of organic-inorganic hybrid porphyrin derivatives with a polyhedral oligomeric silsesquioxane (POSS) [51,52]. The authors followed two different synthetic approaches.…”

“…Firstly, POSS functionalized with an azido group (POSS-N 3 ) [53] was directly attached to the porphyrin-alkyne Zn(II) complex P67, under classical click chemistry conditions, with the formation of the expected triazole ring. Zn(II) porphyrin-POSS hybrid P68a was obtained at a 49% yield after 24 h at 40 • C (Scheme 21) [51].…”

“…HCl in chloroform and their self-assembly behavior was explored. The authors found that different morphologies, such as core-shell spherical micelles and ordered square sheets, can be obtained depending on the polarity of the solvent or solvent mixtures used [51]. The same group prepared the photosensitive organic-inorganic porphyrin-POSS hybrid P69 with an azobenzene bridge ( Figure 7) [52].…”

The controllable construction and properties characterization of organic–inorganic hybrid materials based on benzoxazine-bridged polysilsesquioxanes

“…[6][7][8] Recently, organic-inorganic hybrid materials constructed using this approach have gained great attention. [9][10][11][12] Composite nanomaterials with well-dened structures have been extensively explored to realize a combination of the respective properties of each component or achieve cooperatively enhanced performance. Structural control of organic bridged silsesquioxanes has been previously reported concerning self-assembly behaviour.…”

Preparation of polyhedral oligomeric silsesquioxane based cross-linked inorganic-organic nanohybrid as adsorbent for selective removal of acidic dyes from aqueous solution

“…Therefore, the development of novel adsorbents dominates the applications of adsorption approach for dye removal. Recently, huge amount of attentions have been paid to inorganic-organic hybrid materials which combine advantages of both inorganic and organic components through incorporation of inorganic molecules into organic materials [13]. Polyhedral oligomeric silsesquioxane (POSS), usually considering as a cornerstone or scaffold for construction of inorganic-organic hybrid materials, consists of a defined chemical composition of R 8 Si 8 O 12 .…”