Advances and Properties of Silanol‐Based Materials

Trifunctional Silyl Groups as Anchoring Units in the Preparation of Luminescent Phosphole–Silica Hybrids

“…Because hydrosilanes are suitable to react with surface silanol units as well, we explored the possibility of obtaining the corresponding primary hydrosilane 4, which can be obtained in a straightforward manner from 3 using LiAlH 4 . One might envision conversion of hydrosilane 4 to the corresponding silanetriol; 42,43 however, the latter turned out to be unstable against self-condensation given the insufficient steric protection similar to related cases. 45 In total, the set of new functional β-silylphospholes with alkoxy, chloro, and hydrosilyl units outlined above offers a variety of gradual reactivity for immobilization on silica surfaces.…”

“…The β-silylphospholes reported so far are limited to relatively unreactive TMS units. − Because trifunctional silyl units are well established as anchoring sites for the attachment of silica surfaces, − we wondered whether β-silylphospholes with functional trialkoxysilyl or trichlorosilyl units would be accessible and suitable for immobilization on such surfaces. To this end, we prepared phospholes via the established lithiophosphanation of diynes employing lithiosilylphosphanides with suitably functionalized silyl groups (Scheme ).…”

Cobalt-catalyzed highly selective hydroxylation of organohydrosilanes and hydrosiloxanes

“…[7][8][9] Materials science, on the other hand, is also benefited from the usages of organosilanols and siloxanols in polymerization, sol-gel processes, supramolecular chemistry, room-temperature-vulcanizing silicone compositions, and so on. [10][11][12] Retro-synthetically, hydrolysis of chloro-and alkoxy-silanes constitutes the most classical approach, which unfortunately requires vigorous control of the pH medium to avoid the formation of siloxanes. 13,14 To this end, catalytic oxidation of hydrosilanes has been emerging as a much more greener and sustainable alternative solution (Scheme 1A).…”

“…7–9 Materials science, on the other hand, is also benefited from the usages of organosilanols and siloxanols in polymerization, sol–gel processes, supramolecular chemistry, room-temperature-vulcanizing silicone compositions, and so on. 10–12…”

Structural Modularity of Unique Multicomponent Hydrogen-Bonded Organic Frameworks Based on Organosilanetriols and Silanediols as Molecular Building Blocks

“…Notwithstanding the versatility of organosilanetriols, their extended use as molecular building blocks to produce crystalline supramolecular arrangements has been limited due to low stability of Si­(OH) 3 groups toward self-condensation reactions. − In fact, to prevent the formation of polycondensation byproducts during the synthesis of organo-mono­(silanetriols), it is mandatory to use kinetically stabilizing groups such as bulky organic substituents. ,, Nevertheless, it was also demonstrated that an alternative way to achieve the stabilization of N- and C-bonded organo-mono­(silanetriols) consists of the formation of diamin-silanol adducts, where the diamine molecules are trapped between adjacent Si­(OH) 3 moieties, reducing the kinetic tendency of silanetriols to self-condensation. − On the other hand, Corriu et al reported the first synthesis of C-bonded organo-bis­(silanetriols), where the Si–C bonds lower the acidity of the Si–OH groups improving the stability of the compounds. − Nevertheless, these organo-bis­(silanetriols) were not characterized by SCXRD analysis, because the presence of more than one Si­(OH) 3 moiety per molecule enhances the probability of their polymerization via the formation of Si–O–Si bridges after longer periods of time in solution hindering the growth of suitable monocrystals. , Given all these considerations, our research group reported a sustainable synthetic method for stable organo-mono­(silanetriols) and organo-bis­(silanetriols) were the silicon atom binds to four oxygen atoms as in silica materials, which enhances the acidity of the OH groups . Moreover, in this work we also showed the first example of a multicomponent hydrogen-bonded supramolecular network ( 1a ) obtained by the cocrystallization of bridged organo-bis­(silanetriol) ( 1 ) and 2 equiv of 1,4-diazabicyclo[2.2.2]­octane (DABCO) ( a ) .…”