Porous materials provide great oportunities for the construction of architectures with linear polymers. The chains can be generated in situ starting from the absorbed monomers, co-assembled or diffused from a fluid phase. The influence of the porous framework surrounding the included polymers allows for the control on the conformational arrangement, which, in turn, determines extended chain morphology and conductive properties. On higher hierarchical scales it was feasible to build integrated constructions among single-chains or nanobundles and the 3D networks. Thermal transformation of the polymer chains into graphitic fibers, semiconductive and conductive polyaromatic chains was performed starting from polyacrylonitrile generatied in the nanospaces. In some cases we could achieve the participation of the chains in the network by copolymerization reactions with the formation of covalent bonds between the framework and the polymer. The porous materials were chosen among crystalline molecular materials (PMCs), metal organic (MOFs), porous organic frameworks (POFs) and hybrid organosiloxane mesoporus matrices (PMOs). If desired, the host can be removed from the polymer in distinct ways depending on the easiness of subliming and dissolving as in PMCs, digesting the metal-organic bonds in MOFs, or dissociating carbon-silicon bonds in PMOs. On the contrary, reactive elements were inserted into the porous material in such a way to connect adjacent chains. Distinct cross-section pores (from 0.5 - 4 nm) allow for an individual or a limited number of polymer chains to be collected.Therefore, it was demonstrated that a variety of solutions may be designed to optimize the couple framework/linear-polymer, with the goal in mind to orient the nanocomposite structure and properties. The generation of multiple heterogeneous intaractions in the sophisticated architecctures was an ideal playground for solid state multinuclear NMR, which could recognize specific interactions and nanometric intimacy among the constituents. References 1. Chem. Eur. J. 2016, 21, 18209; Nature Chem. 2013, 5, 335; Angew. Chem. Int. Ed. 2016, 55, 1378.
Sozzani, P., Comotti, A., Bracco, S., Perego, J., Piga, D. (2018). Porous Materials: the Interplay with Linear Polymers. Intervento presentato a: 2nd PoMoS, Meeting on Porous Molecular Solids (Vietri sul Mare, Italy, 6 - 8 June 2018)., Vietri sul Mare, Italy.
Porous Materials: the Interplay with Linear Polymers
Sozzani, P
Membro del Collaboration Group
;Comotti, A;Bracco, SMembro del Collaboration Group
;Perego, J;Piga, D
2018
Abstract
Porous materials provide great oportunities for the construction of architectures with linear polymers. The chains can be generated in situ starting from the absorbed monomers, co-assembled or diffused from a fluid phase. The influence of the porous framework surrounding the included polymers allows for the control on the conformational arrangement, which, in turn, determines extended chain morphology and conductive properties. On higher hierarchical scales it was feasible to build integrated constructions among single-chains or nanobundles and the 3D networks. Thermal transformation of the polymer chains into graphitic fibers, semiconductive and conductive polyaromatic chains was performed starting from polyacrylonitrile generatied in the nanospaces. In some cases we could achieve the participation of the chains in the network by copolymerization reactions with the formation of covalent bonds between the framework and the polymer. The porous materials were chosen among crystalline molecular materials (PMCs), metal organic (MOFs), porous organic frameworks (POFs) and hybrid organosiloxane mesoporus matrices (PMOs). If desired, the host can be removed from the polymer in distinct ways depending on the easiness of subliming and dissolving as in PMCs, digesting the metal-organic bonds in MOFs, or dissociating carbon-silicon bonds in PMOs. On the contrary, reactive elements were inserted into the porous material in such a way to connect adjacent chains. Distinct cross-section pores (from 0.5 - 4 nm) allow for an individual or a limited number of polymer chains to be collected.Therefore, it was demonstrated that a variety of solutions may be designed to optimize the couple framework/linear-polymer, with the goal in mind to orient the nanocomposite structure and properties. The generation of multiple heterogeneous intaractions in the sophisticated architecctures was an ideal playground for solid state multinuclear NMR, which could recognize specific interactions and nanometric intimacy among the constituents. References 1. Chem. Eur. J. 2016, 21, 18209; Nature Chem. 2013, 5, 335; Angew. Chem. Int. Ed. 2016, 55, 1378.
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