photogeneration-n-heterocyclic-carbenes-application-photoinduced-ring

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes ...

Université de Haute-Alsace

université de strasbourg

We describe a novel solvent- and water-free sol-gel process for n-octadecyltriclorosilane (C(18)H(37)SiCl(3)) film catalyzed by photogenerated Brönsted acids. Driven by hydrophobic van der Waals interactions, a photoinduced self-assembly process occurs to afford a long-range ordered lamellar mesostructure, characterized by X-ray diffraction and transmission electron microscopy. Real-time Fourier transform IR spectroscopy was instrumental to probe the fast hydrolysis kinetics and assess the change of conformational behavior of the alkyl chains during UV irradiation. A unique combination of different solid-state NMR techniques ((29)Si, (13)C, (1)H) provided an insight into the supramolecular organization of this hybrid film.

Self-organized poly(n-octadecylsilsesquioxane) films via sol-gel photopolymerization.

Despite considerable achievements over the last two decades, nonporous organic-inorganic hybrid materials are mostly amorphous, especially in the absence of solvothermal processes. The organosilane self-assembly approach is one of the few opportunities for creating a regular assembly of organic and inorganic moieties. Additionally, well-established organosilicon chemistry enables the introduction of numerous organic functionalities. The synthesis of periodically ordered hybrids relies on mono-, bis-, or multisilylated organosilane building blocks self-assembling into hybrid mesostructures or superstructures, subsequently cross-linked by siloxane Si-O-Si condensation. The general synthesis procedure is template-free and one-step. However, three concurrent processes underlie the generation of self-organized hybrid networks: thermodynamics of amphiphilic aggregation, dynamic self-assembly, and kinetically controlled sol-gel chemistry. Hence, the set of experimental conditions and the precursor structure are of paramount importance in achieving long-range order. Since the first developments in the mid-1990s, the subject has seen considerable progress leading to many innovative advanced nanomaterials providing promising applications in membranes, pollutant remediation, catalysis, conductive coatings, and optoelectronics. This work reviews, comprehensively, the primary evolution of this expanding field of research. 

Abraham Chemtob

Institut de Science des Matériaux de Mulhouse (IS2M UMR 7361 CNRS)

Université de Haute-Alsace

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization