Two variants of poly(dimethylsiloxane‐co‐methylhydrosiloxane) polymers were functionalized with three different phenol derivatives (3‐pentadecylphenol, 4‐tert‐octylphenol and phenol) to synthesize six new phenoxylated siloxane polymers using the Piers−Rubinsztajn process/chemistry. The new polymers ranged in physical appearance from waxy solids to liquids. It has been shown that the different phenoxy fragments directly influence the physical and thermal properties of the polymers in a predictable and rational way. The variant based on 3‐pentadecylphenol is of particular interest as it utilizes a naturally sourced and sustainable material from cashew nut shell oil. © 2017 Society of Chemical Industry

Tetrabenzotriazacorroles (Tbcs) are a family of molecules related to phthalocyanines but have the unique ability to intensely absorb both blue and red light. Here, we report the synthesis of four novel silicon tetrabenzotriazacorrole derivatives (SiTbcs) with varying sized axial ligands. SiTbcs are formed starting from bis(hydroxy) silicon phthalocyanine ((OH)-SiPc) via a simple in situ axial functionalization and reductive chemical process using magnesium metal and the respective chlorosilane in pyridine. Systematic probing of the reaction conditions revealed that the reaction is acid-promoted and that the formation of the Tbc macrocycle occurs at temperatures as low as 40 °C. Results imply this chemistry can be extended to SiTbcs with any axial ligands using pyridine hydrochloride as an acid source. Single crystals of all compounds were grown and showed significant π-π interactions between the macrocycles in the solid state. Optical, electrochemical, and thermal characterization of these materials is also described. The SiTbcs exhibit interesting highly oxidative electrochemistry as well as high thermal stability and tunable phase transition behavior.

Axial functionalization is one mode that enables the solubility of silicon phthalocyanines (SiPcs). Our group observed that the use of typical axial functionalization methodologies on reaction of Cl2SiPc with the chlorotriphenyl silane reagent unexpectedly resulted in the equal formation of triphenyl silyloxy silicon tetrabenzotriazacorrole ((3PS)-SiTbc) and the desired bis­(tri-phenyl siloxy)-silicon phthalocyanine ((3PS)2-SiPc). The formation of a (3PS)-SiTbc was unexpected, and the separation of (3PS)-SiTbc and (3PS)2-SiPc was difficult. Therefore, in this study, we investigated the use of Piers–Rubinsztajn (PR) chemistry as an alternative method to functionalize the axial position of a SiPc to avoid the generation of a Tbc derivative. PR chemistry is a novel method to form a Si–O bond starting with a Si–H-based reactant and a −OH-based nucleophile enabled by tris­(pentafluorophenyl)­borane as a catalyst. The PR chemistry was screened on several fronts on how it can be applied to SiPcs. It was found that the process needs to be run in nitrobenzene at a molar ratio and at a particular temperature. To this end, the triphenylsiloxy derivative (3PS)2-SiPc was produced and fully characterized, without the production of a Tbc derivative. In addition, we explored and outlined that the PR chemistry method can enable the formation of other SiPc derivatives that are inaccessible utilizing other established axial substitution chemistry methods such as (TM3)2-SiPc and (MDM)2-SiPc. These additional materials were also physically characterized. The main conclusion is that the PR chemistry method can be applied to SiPcs and yield several alternative derivatives and has the potential to apply to additional macrocyclic compounds for unique derivative formation.

Cross-linked triarylamine–siloxane hybrid thin film have been formed using Piers–Rubinsztajn chemistry. Key to this approach was the use of a ring-opening reaction to prevent the evolution of volatile small molecules. A representative cyclic ether containing biphenyl triarylamine compound was synthesized and on ring-opening was shown to form a smooth, glassy, and electroactive films by cross-linking with tetrakis(dimethylsiloxy)silane (QM*4). It was found that the films were electrochemically active with low glass transition temperatures. Cross-linked films were incorporated into organic light emitting diodes (OLEDs) under various conditions and functionality within OLEDs was confirmed. Finally, the resistance of the system to dissolution (orthogonality) was considered by casting F8T2, a p-type emitting polymer, from solution on top of the cross-linked film, which formed a working OLED.