Tunable C-H functionalization and dearomatization enabled by an organic photocatalyst.

C-H functionalization and dearomatization constitute fundamental transformations of aromatic compounds, which find wide applications in various research areas. However, achieving both transformations from the same substrates with a single catalyst by operating a distinct mechanism remains challenging. Here, we report a photocatalytic strategy to modulate the reaction pathways that can be directed toward either C-H functionalization or dearomatization under redox-neutral or net-reductive conditions, respectively. Two sets of indoles and indolines bearing tertiary alcohols are divergently furnished with good yields and high selectivity. The key to success is the introduction of isoazatruxene ITN-2 as a novel photocatalyst (PC), which outperforms the commonly used PCs. The ready synthesis and high modulability of isoazatruxene type PCs indicate their great application potential.

Optoelectronic materials as emerging photocatalysts: opportunities in sustainable organic synthesis.

To overcome the energy and environmental crisis, the development of efficient, sustainable photocatalysts to convert inexhaustible solar energy into chemical energy is of great significance. Due to their unique optoelectronic properties, organic electronic materials have been translated into the photocatalytic field. These emerging photocatalysts are attractive because of their metal-free nature, chemical stability, and structural diversity. However, as many small molecules fail to absorb visible light solely, incorporating them into crosslinked frameworks is found to be an effective strategy to extend the conjugation and enhance visible-light absorption. In addition, the photophysical properties of these heterogeneous materials can be adjusted through structural modification and linkage engineering. Finally, these insoluble photocatalysts exhibit good recyclability and reusability. As a representative illustration, this feature article describes recent examples of the use of two types of organic electronic materials including phenothiazine and truxene in heterogeneous photocatalytic organic transformations. The synthesis and key photophysical properties of both organic electronic material-based photocatalysts are discussed combined with specific synthetic applications. We anticipate this feature article will stimulate the implementation of more diverse organic electronic materials in the field of photocatalysis, which may lead to unprecedented synthetic applications.

Synthesis of a Triazaisotruxene-Based Porous Organic Polymer and Its Application in Iodine Capture.

A new triazaisotruxene-based porous organic polymer (POP) was designed and successfully synthesized by a FeCl3-promoted crosslinking reaction. As a result of its porosity and good thermal stability, the designed POP can be utilized as a promising adsorbent for iodine, not only in the gaseous phase, but also in organic and aqueous solutions. Compared to its triazatruxene (TN) analogue, the ITN-based POP shows equal iodine uptake in the gaseous phase and in hexane solution, and better uptake in aqueous solution.

Novel triorganotin complexes based on phosphonic acid ligands: Syntheses, structures and in vitro cytostatic activity.

Six novel organotin phosphonate complexes, [(Me3Sn)4(HL1)4]n1, [(Me3Sn)2(HL2)2]n2, [(Me3Sn)2L3(H2O)]n3, [(Ph3Sn)(HL1)]64, [(Ph3Sn)2L2]n5 and [(Ph3Sn)2L3]66, derived from phosphonic acid ligands [NaHL1 = 1-C10H7OPO2(OH)Na, H2L2 = 1-C10H7PO(OH)2, H2L3 = 2-C10H7PO(OH)2], have been synthesized and characterized by elemental analysis, FT-IR, NMR (1H, 13C, 31P and 119Sn) spectroscopy and X-ray crystallography. The structural analysis reveals that complexes 1 and 5 display 1D infinite zig-zag chain structures, and complex 2 shows 1D right-handed helical chain structure, while complex 3 displays 1D left-handed helical chain structure. Complexes 4 and 6 are 24-membered macrocyclic rings interconnected by P, O and Sn atoms. Additionally, the molecules of complexes 1 and 3 are further linked through intermolecular π···π and O-H···O interaction into supramolecular structures, respectively. Furthermore, we preliminarily estimated in vitro cytostatic activity of complexes 1-6 against the human cervix tumor cells (HeLa), human hepatocellular carcinoma cells (HepG-2) and human normal breast cells (HBL-100). Importantly, the anti-proliferative properties and possible pathway of complex 6 are investigated, and the results demonstrate that complex 6 could induce apoptotic cell death via an overload of intracellular reactive oxygen species (ROS) levels and the dysfunctional depolarization of mitochondrial membranes.