Cobalt-Catalyzed Regiodivergent Double Hydrosilylation of Arylacetylenes.

Double hydrosilylation of alkynes represents a straightforward method to synthesize bis(silane)s, yet it is challenging if α-substituted vinylsilanes act as the intermediates. Here, a cobalt-catalyzed regiodivergent double hydrosilylation of arylacetylenes is reported for the first time involving this challenge, accessing both vicinal and geminal bis(silane)s with exclusive regioselectivity. Various novel bis(silane)s containing Si-H bonds can be easily obtained. The gram-scale reactions could be performed smoothly. Preliminarily mechanistic studies demonstrated that the reactions were initiated by cobalt-catalyzed α-hydrosilylation of alkynes, followed by cobalt-catalyzed ß-hydrosilylation of the α-vinylsilanes to deliver vicinal bis(silane)s, or hydride-catalyzed α-hydrosilylation to give geminal ones. Notably, these bis(silane)s can be used for the synthesis of high-refractive-index polymers (nd up to 1.83), demonstrating great potential utility in optical materials.

Aliphatic Polyesters with White-Light Clusteroluminescence.

Single-molecule white-light emission (SMWLE) has many advantages in practical applications; however, the fabrication of SMWLE from nonconjugated luminescent polymers, namely, clusteroluminogens (CLgens), is still a big challenge. Herein, the first example of linear nonconjugated polyesters with SMWLE is reported. Twenty-four kinds of nonconjugated aliphatic polyesters with tunable clusteroluminescence (CL) colors and efficiency were synthesized by the copolymerization of six epoxides and four anhydrides. Experimental and calculation results prove that, at the primary structure level, the balance of structural flexibility and rigidity via adjusting the side-chain length significantly enhances the efficiency of CL without wavelength change. However, altering the chemical structures of the monomer from succinic anhydride to trans-maleic anhydride (MA), cis-MA, and citraconic anhydride (CA), secondary structures of these polyesters change from helix to straight and folding sheet accompanied by gradually red-shifted CL from 460 to 570 nm due to the increase in through-space n-π* interactions, as demonstrated by the computational and experimental results. Then, pure SMWLE with CIE coordination (0.30, 0.32) based on overlapped short-wavelength and long-wavelength CL is achieved in CA-based polyesters. This work not only provides further insights into the emission mechanism of CL but also provides a new strategy to manipulate the properties of CL by regulating the hierarchical structures of CLgens.