Polymeric carbon nitride materials have been used in numerous light‐to‐energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K‐PHI)—a benchmark carbon nitride material in photocatalysis—by means of X‐ray powder diffraction and transmission electron microscopy. Using the crystal structure of K‐PHI, periodic DFT calculations were performed to calculate the density‐of‐states (DOS) and localize intra band states (IBS). IBS were found to be responsible for the enhanced K‐PHI absorption in the near IR region, to serve as electron traps, and to be useful in energy transfer reactions. Once excited with visible light, carbon nitrides, in addition to the direct recombination, can also undergo singlet–triplet intersystem crossing. We utilized the K‐PHI centered triplet excited states to trigger a cascade of energy transfer reactions and, in turn, to sensitize, for example, singlet oxygen (1O2) as a starting point to synthesis up to 25 different N‐rich heterocycles.

Small organic radicals are ubiquitous intermediates in photocatalysis and are used in organic synthesis to install functional groups and to tune electronic properties and pharmacokinetic parameters of the final molecule. Development of new methods to generate small organic radicals with added functionality can further extend the utility of photocatalysis for synthetic needs. Herein, we present a method to generate dichloromethyl radicals from chloroform using a heterogeneous potassium poly(heptazine imide) (K-PHI) photocatalyst under visible light irradiation for C1-extension of the enone backbone. The method is applied on 15 enones, with γ,γ-dichloroketones yields of 18-89%. Due to negative zeta-potential (−40 mV) and small particle size (100 nm) K-PHI suspension is used in quasi-homogeneous flow-photoreactor increasing the productivity by 19 times compared to the batch approach. The resulting γ,γ-dichloroketones, are used as bifunctional building blocks to access valueadded organic compounds such as substituted furans and pyrroles.

Carbon nitrides encompass a class of transition-metal-free materials possessing numerous advantages such as low cost (few Euros per gram), high chemical stability, broad tunability of redox potentials and optical bandgap, recyclability, and a high absorption coefficient (> 10 5 cm À 1), which make them highly attractive for application in photoredox catalysis. In this Review, we classify carbon nitrides based on their unique properties, structure, and redox potentials. We summarize recently emerging concepts in heterogeneous carbon nitride photocatalysis, with an emphasis on the synthesis of organic compounds: 1) Illumination-Driven Electron Accumulation in Semiconductors and Exploitation (IDEASE); 2) singlet-triplet intersystem crossing in carbon nitride excited states and related energy transfer; 3) architectures of flow photoreactors; and 4) dual metal/carbon nitride photocatalysis. The objective of this Review is to provide a detailed overview regarding innovative research in carbon nitride photocatalysis focusing on these topics.

Organic π-conjugated polymers are promising heterogeneous photocatalysts that involve photoredox or energy transfer processes. In such settings, the materials are usually applied in the form of dispersion in liquid medium, which is bound to certain technological limits of applicability. Herein, we present an innovative approach using carbon nitride thin films prepared via chemical vapor deposition at different vessel walls and using them as batch and microfluidic photoreactors. This approach allows us not only to fabricate technologically relevant and reusable devices but also to improve photophysical properties of carbon nitride, such as the singlet−triplet energy gap and lifetime of triplet excited states, when the material is assembled in thin films. These morphological changes are employed to maximize the performance of the materials in photocatalytic reactions, in which the carbon nitride thin films show at least 1 order of magnitude higher activity per area unit compared to photocatalysis using suspended particles.

Chromoselective photocatalysis offers an intriguing opportunity to enable a specific reaction pathway out of a potentially possible multiplicity for a given substrate by using a sensitizer that converts the energy of incident photon into the redox potential of the corresponding magnitude. Several sensitizers possessing different discrete redox potentials (high/low) upon excitation with photons of specific wavelength (short/long) have been reported. Herein, we report design of molecular structures of two-dimensional amorphous covalent triazine-based frameworks (CTFs) possessing intraband states close to the valence band with strong red edge effect (REE). REE enables generation of a continuum of excited sites characterized by their own redox potentials, with the magnitude proportional to the wavelength of incident photons. Separation of charge carriers in such materials depends strongly on the wavelength of incident light and is the primary parameter that defines efficacy of the materials in photocatalytic bromination of electron rich aromatic compounds. In dual Ni-photocatalysis, excitation of electrons from the intraband states to the conduction band of the CTF with 625 nm photons enables selective formation of C‒N cross-coupling products from arylhalides and pyrrolidine, while an undesirable dehalogenation process is completely suppressed.