Hydrosilylation for the synthesis of sequence‐controlled periodic copolymers

Abstract

Transition metal‐catalyzed addition of bis‐silyl hydride to bis‐alkyne is widely used for the synthesis of alt‐silylene‐divinyl‐linker copolymer. When the linker for connecting two silyl hydrides is different from that for two alkyne motifs, hydrosilylation reaction will give the corresponding AB‐type copolymer. The reactivity of alkynes can be manipulated by using different protective groups. This kind of strategy would enable us to assemble a range of linkers in regioregular manner or sequence‐controlled tactic. In this account, we summarize our synthetic endeavors on the use of rhodium‐catalyzed hydrosilylation reaction to incorporate different kinds and/or numbers of chromophores arranged regioselectively on the polymeric backbone. The photophysical properties such as those arising from the ground state interactions, fluorescence resonance energy transfer, photoinduced electron transfer, light‐harvesting, or a combination thereof have been systematically examined. These data may offer useful clues on the folding behavior of these silicon‐containing polymers.

A tribute to Professor Tien-Yau Luh

“…Fluorescence resonance energy transfer (FRET) 53 photoinduced electron transfer (PET) [54][55][56] can occur readily If the two acetylene moieties in 21 can be differentiated, this strategy could be extended towards oligomers having regioregular arrangements of multiple chromophores [57][58][59][60][61] and/or the sequence-controlled synthesis of polymers 34 without repeating units 30. 62 A silyl-substituted terphenylene-tetravinylene 31 has been shown to have the brightest blue emission in an electroluminescent device. 63…”

Sequence-controlled alternating block polychalcogenophenes: synthesis, structural characterization, molecular properties, and transistors for bromine detection

“…The recent advances in organometallic chemistry in organic synthesis have paved the way to access various types of sequence-controlled polymers with novel structural features. [1][2][3] The synthesis of sequence-controlled conjugated polymers (SCCPs) is one of the emerging and challenging topics in polymer science. [4][5][6][7][8][9] SCCPs with structural regularity are prone to self-assembly into ordered nanostructures, which is essential for realizing high-performance organic optoelectronics, such as organic photovoltaics (OPVs) 10,11 and eld-effect transistors (OFETs).…”