Synthesis of 1,1,3,3,5,5-Hexamethyl-7,7-diorganocyclotetrasiloxanes and Its Copolymers

This paper reports a method for the synthesis of 1,1,3,3,5,5-hexamethyl-7,7-diorganocyclotetrasiloxanes by the interaction of 1,5-disodiumoxyhexamethylsiloxane with dichlorodiorganosilanes such as methyl-, methylvinyl-, methylphenyl-, diphenyl- and diethyl dichlorosilanes. Depending on the reaction conditions, the preparative yield of the target cyclotetrasiloxanes is 55–75%. Along with mixed cyclotetrasiloxanes, the proposed method leads to the formation of polymers with regular alternation of diorganosylil and dimethylsylil units. For example, in the case of dichlorodiethylsilane, 70% content of linear poly(diethyl)dimethylsiloxanes with regular alternation of units can be achieved in the reaction product. Using 7,7-diethyl-1,1,3,3,5,5-hexamethylcyclotetrasiloxane as an example, the prospects of the mixed cycle in copolymer preparation in comparison with the copolymerization of octamethyl- and octaethylcyclotetrasiloxanes are shown

Effects of electron-withdrawing group and electron-donating core combinations on physical properties and photovoltaic performance in D-pi-A star-shaped small molecules

The first representatives of star-shaped molecules having 3-alkylrhodanine (alkyl-Rh) electron-withdrawing groups, linked through bithiophene pi-spacer with electron-donating either triphenylamine (TPA) or tris(2-methoxyphenyl)amine (m-TPA) core were synthesized. The physical properties and photovoltaic performance of these novel molecules with 3-ethylrhodanine groups were comprehensively studied and compared to their full analogs having dicyanovinyl (DCV) units as the other type of well-known and frequently used acceptor groups. On one hand, the former demonstrate several advantages such as higher solubility and better photovoltaic performance in bulk-heterojunction (BHJ) organics solar cells (OSCs) as compared to the latter. Nevertheless, the former have slightly lower optical/electrochemical bandgaps and higher thermooxidation stability. On the other hand, molecules of both series based on m-TPA core along with higher solubility and higher position of HOMO energy levels have more pronounced tendency to crystalize as compared to the TPA-based molecules. Detailed investigation of the structure-property relationships for these series of molecules revealed that donor and acceptor unit combinations influence both charge generation and charge transport/recombination properties, as demonstrated by the ultrafast photoinduced absorption spectroscopy, space charge limited current measurements and transient photovoltage technique. These results give more insight how to fine-tune and predict physical properties and photovoltaic performance of small molecules having either alkyl-Rh or DCV units in their chemical structures and thus providing a molecular design guideline for the next generation of high-performance photovoltaic materials. (C) 2016 Elsevier B.V. All rights reserved