A modified one-pot Sonogashira cross-coupling reaction based on a copper-free methodology has been applied for the synthesis of conjugated microporous poly(aryleneethynylene) networks (CMPs) from readily available iodoarylenes and 1,3,5-triethynylbenzene. The polymerization reactions were carried out by using equimolar amounts of halogen and terminal alkyne moieties with extremely small loadings of palladium catalyst as low as 0.65 mol %. For the first time, CMPs with rigorously controlled structures were obtained without any indications of side reactions, as proven by FTIR and solid-state NMR spectroscopy, while showing Brunauer–Emmett–Teller (BET) surface areas higher than any poly(aryleneethynylene) network reported before, reaching up to 2552 m² g⁻¹.

Supported NiO nanoparticles (NPs) were prepared by impregnation of mesoporous silica SBA-15 with a molecular, metalorganic [Ni₄O₄] cubane cluster as precursor. By using this ligand-stabilized Ni cluster, deposition of four Ni ions in close proximity on the silica support was achieved; this resulted in the formation of small and highly dispersed NiO NPs after heat treatment. These clusters were shown to have a significant influence on the formation of NiO NPs compared to a conventional Ni(OAc)₂ precursor. After a further reduction step, the materials were used as catalysts for the dry reforming of methane, which showed that preorganization of the Ni atoms on the support surface had a beneficial effect on the methane conversion rate.

Conjugated microporous polymer networks have been prepared from the strong electron donor tetrathiafulvalene (TTF) and 1,3,5-triethynylbenzene (TEB) by using the Sonogashira–Hagihara cross-coupling reaction. Optimization of reaction conditions yields polymers with surface areas of up to 434 m² g⁻¹. The strong electron-donating properties of the network can be proven by iodine exposure. Structural and electronic changes due to formation of the charge-transfer salt from TTFs in the porous network and iodine within the pores are investigated.

Graphitic carbon nitride (g-CN) is a promising heterogeneous metal-free catalyst for organic photosynthesis, solar energy conversion, and photodegradation of pollutants. Its catalytic performance is easily adjustable by modifying texture, optical, and electronic properties via nanocasting, doping, and copolymerization. However, simultaneous optimization has yet to be achieved. Here, a facile synthesis of mesoporous g-CN using molecular cooperative assembly between triazine molecules is reported. Flower-like, layered spherical aggregates of melamine cyanuric acid complex (MCA) are formed by precipitation from equimolecular mixtures in dimethyl sulfoxide (DMSO). Thermal polycondensation of MCA under nitrogen at 550 °C produces mesoporous hollow spheres comprised of tri-s-triazine based g-CN nanosheets (MCA-CN) with the composition of C₃N_4.14H_1.98. The layered structure succeeded from MCA induces stronger optical absorption, widens the bandgap by 0.16 eV, and increases the lifetime of photoexcited charge carriers by twice compared to that of the bulk g-CN, while the chemical structure remains similar to that of the bulk g-CN. As a result of these simultaneous modifications, the photodegradation kinetics of rhodamine B on the catalyst surface can be improved by 10 times.

Dieser Aufsatz soll einen Überblick über die jüngsten Entwicklungen auf dem Gebiet der porösen organisch-anorganischen oder rein organischen Funktionsmaterialien geben. Verschiedene Möglichkeiten zum Einbau organischer Gruppen, die eine chemische oder physikalische Funktion aufweisen, in poröse Netzwerke werden diskutiert. Speziell sollen hier Materialien besprochen werden, bei denen die organischen funktionellen Gruppen ein tragender Bestandteil der Porenwände sind. Durch diesen Ansatz kann die Zahl der organischen Gruppen im Netzwerk prinzipiell bis zu dem Punkt erhöht werden, an dem das poröse Material rein organisch wird.

This Review aims to give an overview of recent research in the area of porous, organic–inorganic and purely organic, functional materials. Possibilities for introducing organic groups that exhibit chemical and/or physical functions into porous materials will be described, with a focus on the incorporation of such functional groups as a supporting part of the pore walls. The number of organic groups in the network can be increased such that porous, purely organic materials are obtained.

The current established catalytic processes used in chemical industries use metals, in many cases precious metals, or metal oxides as catalysts. These are often energy-consuming and not highly selective, wasting resources and producing greenhouse gases. Metal-free heterogeneous catalysis using carbon or carbon nitride is an interesting alternative to some current industrialized chemical processes. Carbon and carbon nitride combine environmental acceptability with inexhaustible resources and allow a favorable management of energy with good thermal conductivity. Owing to lower reaction temperatures and increased selectivity, these catalysts could be candidates for green chemistry with low emission and an efficient use of the chemical feedstock. This Review highlights some recent promising activities and developments in heterogeneous catalysis using only carbon and carbon nitride as catalysts. The state-of-the-art and future challenges of metal-free heterogeneous catalysis are also discussed.