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    Ultra-small cobalt nanoparticles from molecularly-defined Co-salen complexes for catalytic synthesis of amines
    (Cambridge : RSC, 2020) Senthamarai, Thirusangumurugan; Chandrashekhar, Vishwas G.; Gawande, Manoj B.; Kalevaru, Narayana V.; Zbořil, Radek; Kamer, Paul C.J.; Jagadeesh, Rajenahally V.; Beller, Matthias
    We report the synthesis of in situ generated cobalt nanoparticles from molecularly defined complexes as efficient and selective catalysts for reductive amination reactions. In the presence of ammonia and hydrogen, cobalt-salen complexes such as cobalt(ii)-N,N′-bis(salicylidene)-1,2-phenylenediamine produce ultra-small (2-4 nm) cobalt-nanoparticles embedded in a carbon-nitrogen framework. The resulting materials constitute stable, reusable and magnetically separable catalysts, which enable the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds and ammonia. The isolated nanoparticles also represent excellent catalysts for the synthesis of primary, secondary as well as tertiary amines including biologically relevant N-methyl amines. This journal is © The Royal Society of Chemistry.
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    Mechanistic insight into the non-hydrolytic sol–gel process of tellurite glass films to attain a high transmission
    (Cambridge : RSC, 2020) Pan, Xuanzhao; Zhao, Jiangbo; Qian, Gujie; Zhang, Xiaozhou; Ruan, Yinlan; Abell, Andrew; Ebendorff-Heidepriem, Heike
    The development of amorphous films with a wide transmission window and high refractive index is of growing significance due to the strong demand of integrating functional nanoparticles for the next-generation hybrid optoelectronic films. High-index TeO2-based glass films made via the sol-gel process are particularly suitable as their low temperature preparation process promises high compatibility with a large variety of nanoparticles and substrates that suffer from low thermal stability. However, due to the lack of in-depth understanding of the mechanisms of the formation of undesired metallic-Te (highly absorbing species) in the films, the preparation of high-transmission TeO2-based sol-gel films has been severely hampered. Here, by gaining insight into the mechanistic chemistry of metallic-Te formation at different stages during the non-hydrolytic sol-gel process, we identify the chemical route to prevent the generation of metallic-Te in a TeO2-based film. The as-prepared TeO2-based film exhibits a high transmission that is close to the theoretical limit. This opens up a new avenue for advancing the performance of hybrid optoelectronic films via incorporating a large variety of unique nanoparticles. © 2020 The Royal Society of Chemistry.