Ordered and amorphous microporous polytriazine networks have been obtained from the trimerization of nitriles in a ZnCl2 melt at 400 °C (see structure of the polymer formed from 1,4‐dicyanobenzene; C gray, N blue). The materials are high‐performance polymers with very large surface areas and could find applications in gas storage, as sensors, or catalyst supports.

High surface area organic materials featuring both micro- and mesopores were synthesized under ionothermal conditions via the formation of polyaryltriazine networks. While the polytrimerization of nitriles in zinc chloride at 400 degrees C produces microporous polymers, higher reaction temperatures induce the formation of additional spherical mesopores with a narrow dispersity. The nitrogen-rich carbonaceous polymer materials thus obtained present surface areas and porosities up to 3300 m(2) g(-1) and 2.4 cm(3) g(-1), respectively. The key point of this synthesis relies on the occurrence of several high temperature polymerization reactions, where irreversible carbonization reactions coupled with the reversible trimerization of nitriles allow the reorganization of the dynamic triazine network. The ZnCl2 molten salt fulfills the requirement of a high temperature solvent, but is also required as catalyst. Thus, this dynamic polymerization system provides not only highly micro- and mesoporous materials, but also allows controlling the pore structure in amorphous organic materials.

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Triazine-based polymer scaffolds with controllable porosity were prepared through a dynamic polymerization scheme based on a broad variety of aromatic nitriles, upon polytrimerization of the latter from ZnCl 2 salt melts at high temperatures. In the present study, the reaction parameters such as the temperature and monomer concentration as well as the geometry and functionality of the monomers were systematically varied. A comprehensive overview of the influences of these parameters on the outcome of the polymerization reaction in terms of chemical nature and porous properties of the materials is proposed. Rather than the variation of the monomer size and/or geometry, the reaction parameters were found to play a crucial role for tuning the porosity of the materials and especially the reaction temperature. Finally, the use of functional aromatic bridging units allowed the formation of functional polymer scaffolds with the ability to coordinate metal salts, introducing the possibility to design new metallo-organic materials.

For over 30 years complexes with the general formula [NiPh(P,O)L] (L = tertiary phosphine; P,O = chelating phosphanylenolato ligand) have been used as highly efficient oligomerisation catalysts suitable for the production of linear alpha-olefins. The same complexes, which are usually referred to as SHOP-type catalysts (SHOP = Shell Higher Olefin Process) can also be used as ethylene polymerisation catalysts, provided they are treated with a phosphine scavenger that selectively removes the tertiary phosphine ligand (L). This Perspective examines the impact of various parameters (influence of the substituents, backbone size, solvent, use of co-catalysts, etc.) on the catalytic outcome of the complexes. Overall, this review shows that the selectivity and activity of the catalyst may be tuned efficiently through directed modification of the P,O chelator.

A new generation of porous polymers was made for various energy-related applications, e.g., as fuel cell membranes, as electrode materials for batteries, for gas storage, partly from renewable resources. This review intends to catch this emerging field by reporting on a variety of different approaches to make high performing polymers porous. This includes template techniques, polymers with inherent microporosity, polymer frameworks by ionothermal polymerization, and the polymerization of carbon from appropriate precursors and by hydrothermal polymerization. In this process, we try to not only identify the current status of the field, but also point to open question and tasks to identify the potentially relevant progress.

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