Herein, we have developed a strategy of Rh(III)-catalyzed C–H activation of N-nitrosoanilines and iodonium ylides to construct novel tetralydrocarbzol-4-one scaffolds, which provided valuable templates for sequential C-H functionalization such as alkylation, alkenyla-tion, amidation and (hetero)arylation at C5-position of tetralydrocarbzol-4-one with different coupling partners. Gram-scale synthesis and further transformation of tetralydrocarbzol-4-one derivatives to Ondansetron and its analogues demonstrated the utility of this protocol, which enabled the concise and diverse construction of biologically active molecules.

We developed a novel Pd-catalyzed [4 + 4] cycloaddition of benzofuran-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated from α-allyl malonate derivatives, affording an array of benzofuro[3,2-b]azocines with good to excellent yields (up to 96%) and exclusive regioselectivities. This methodology featured mild reaction conditions and good functional group tolerance. The synthetic utility was demonstrated by a gram-scale reaction. Furthermore, the catalytic asymmetric [4 + 4] cycloaddition version has also been explored.

Organic luminogens with persistent room temperature phosphorescence (RTP) have drawn tremendous attentions due to their prom-ising potentials in optoelectronic devices, information storage, biological imaging, and anti-counterfeiting. In this work, six triazatrux-ene-based lumiogens with different peripheral substituents and configurations are synthesized and systematically studied. The results show that their fluorescence quantum yields in solid states range from 15.73% to 37.58%. Dispersing the luminogens as guest into the host (PPh3) could turn on the persistent RTP, where PPh3 acts as not only a rigid matrix to suppress the non-radiative transitions of the guest, but also provides energy transfer channels to the guest. The maximum phosphorescence efficiency and the longest lifetime could reach 29.35% and 0.99 s in co-crystal films of 6-TAT-CN/PPh3 and 5-TAT-H/PPh3, respectively. Moreover, these host-guest co-crystalline films exhibit great potentials in advanced dynamic data encryption and anti-counterfeiting. This work deepens the insight for low cost, halogen-free, and facile fabrication of all-organic persistent RTP materials.

Pd-catalyzed asymmetric allylic C−H functionalization has emerged as a powerful tool to access chiral, densely functionalized molecules from easily ac-cessible alkenes, enabling the increase of the step- or atom-economy by minimizing functional group manipulations for preparing allylating reagents. Due to the inadequacy of stereoselection strategies, the asymmetric allylic C-H functionalization is still in the early stage. In this essay, we will describe our journey to identification of asymmetric catalytic systems, mechanism of allylic C−H activation, control of stereo- and regioselectivity, and applica-tions in asymmetric synthesis.

By employing thiazole and 4-chlorothiazole as the A′ units, two A-D-A′-D-A type nonfused-ring electron acceptors (NFREAs) Tz-H and Tz-Cl were designed and synthesized. Replacing thiazole in Tz-H with 4-chlorothiazole can not only remarkably shorten the synthetic route through C-H direct arylation but also enhance molecular planarity with the simultaneous incorporation of S···N and S···Cl non-covalently conformational locks (NoCLs). The photovoltaic devices based on PM6:Tz-Cl exhibited a power conversion efficiency as high as 11.10%, much higher than that of PM6:Tz-H (6.41%), mainly due to more efficient exciton dissociation, better and more balanced carrier mobility, less charge recombination, and more favorable morphology. These findings demonstrate the great potential of NoCLs in achieving low-cost and high-performance NFREAs.

An asymmetric isomerization/intramolecular coupling reaction of allylic alcohols to synthesize chiral dihydrocoumarins was suc-cessfully accomplished through ruthenium catalysis. This method demonstrates a wide substrate applicability, excellent tolerance for various functional groups, and good enantioselectivities (up to 90% ee). It provides a convenient pathway to produce a diverse range of structurally distinct chiral dihydrocoumarins in good efficiency.

Herein, we present a method for the homogeneous hydrogenation of nitroarenes to produce aromatic amines using low catalyst loading (1 mo%) of air-stable copper N-heterocyclic carbene complexes as the catalyst and ammonia borane as the source of hydrogen. A wide range of nitroarenes, featuring diverse functional groups, were selectively transformed into their corresponding primary aromatic amines with high yields. This process can be readily scaled up and exhibits compatibility with various sensitive functional groups, including halogen, trifluoromethyl, aminomethyl, alkenyl, cyano, ester, amide, and hydroxyl. Notably, this catalytic methodology finds application in the synthesis of essential drug compounds. Mechanistic investigations suggest that the in-situ-generated Cu-H species may serve as active intermediates, with reduction pathways involving species such as azobenzene, 1,2-diphenylhydrazine, nitrosobenzene, and N-phenylhydroxylamine.

In recent years, there has been a shift towards using nonfullerene electron acceptors in organic solar cells (OSCs) as a replacement for fullerene derivatives. This change requires polymer donors that possess compatible physical properties, such as absorption range, HOMO energy level, miscibility, and crystallinity. Moreover, the high cost and poor batch-to-batch reproducibility of polymer donors also hinder future large-scale manufacturing. These emphasize the need to explore alternative types of polymer donors. The imide-functionalized building units possess several key attributes that make their polymers highly promising for non-fullerene OSCs. These attributes include ease of synthesis, strong electron-withdrawing ability, rigid and co-planar structure, and the ability to easily tune solubility through imide side chains. In this review, we summarized the synthetic routes of imide building units, and the struc-tural evolution of imide-functionalized polymer donors by focusing on the effects of polymer structure on their physical, optoelec-tronic, and photovoltaic properties. We hope that this mini-review will serve as a catalyst for future research on imide-functionalized polymers toward high-performance, cost-effective, and durable organic solar cells (OSCs).

Dynamic fluorescent materials used in data encryption suffer from photodegradation, poor latency, and susceptibility to unauthorized access. Herein, we propose a photochemically modulated dynamic fluorescent encryption system based on 1O2 sensitization of fluorescent composites, comprising a 1O2-sensitive fluorophore (F2) and non-emissive polymers. After UV irradiation, in-situ generation of 1O2 from the polymer effectively binds with F2 to form endoperoxides (F2EPO), resulting in a significant redshift in emission, up to 150 nm. The 1O2 concentration is closely related to the irradiation time, enabling time-gated encryption with diverse fluorescent colors. Moreover, polymer properties can be manipulated to further regulate F2EPO emission. Relying on these merits, we develop a dynamic data encryption method with various non-emissive polymers as the data storage media, UV light irradiation as the data encoder, and F2 as the data decoder. UV light irradiation of diverse polymer solutions generates 1O2 at different concentrations, effectively encoding the data, which remains invisible under both UV and natural lights. The addition of F2 to these irradiated polymer produces different redshifted fluorescence, enabling secure data decryption. Attributing to the non-emissive polymers, time-gated readout fashion, excellent latency of 1O2, and subtle interactions between 1O2 and F2, this data encryption is nearly undecipherable.

Organic difluoroboron complexes is a kind of potential platforms for a wide range of applications owing to their excellent photo-physical properties. Herein, we have explored a simple and direct synthesis methodologies for a library of N,O-Bidentate difluoroboron complexes from quinoxalin-2(1H)-ones and ketones in one shot. The photophysical properties of the generated com-plexes were evaluated and the application potential of these compound on subcellular was also explored.

The conversion of CF3-alkenes to gem-difluoroalkenes using reductive cross-coupling strategy has received much attention in recent years, however, the use of green and readily available reducing salt to mediate these reactions remains to be explored. In this work a concise construction of gem-difluoroalkenes, which requires neither a catalyst nor a metal reducing agent, was established. Rongalite, a safe and inexpensive industrial product, was employed as both a radical initiator and reductant. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates (>70 examples). The utility of this approach was demonstrated through gram-scale synthesis and efficient late-stage functionalizations of anti-inflammatory drugs.

The development of switchable solvent-free multicomponent reactions to build high-value-added products is an important demand for organic synthesis. Herein, we detailed the successful implementation of a switchable strategy for the construction of diverse 4-fluoroalkyl-1,4-dihydropyrimidines and 4-fluoroalkyl-pyrimidines via a solvent/additive-free [3 + 2 + 1] annulation, starting from readily available enamines, trifluoroacetaldehyde hydrate or 1-ethoxy-2,2-difluoroethanol and amidines hydrochloride. This reaction conforms to the concept of green synthesis, and provides a new avenue to access valuable fluorinated heterocycles.

Cathode interlayers (CILs) play an essential role in achieving efficient organic solar cells (OSCs). However, the electronic structure at the electrode/CIL/active layer interfaces and the underlying mechanisms for electron collection remain unclear, which becomes a major obstacle to develop high-performance CILs. Herein, we investigate the relationship of the electron collection abilities of four cross-linked and n-doped CILs (c-NDI:P0, c-NDI:P1, c-NDI:P2, c-NDI:P3) with their electronic structure of space charge region at hetero-junction interface. By accurately calculating the depletion region width according to the barrier height, doping density and permittivi-ty, we put forward that the optimal thickness of CIL should be consistent with the depletion region width to realize the minimum en-ergy loss. As a result, the depletion region width is largely reduced from 13 nm to 0.8 nm at the indium tin oxide (ITO)/c-NDI:P0 in-terface, resulting in a decent PCE of 17.7% for the corresponding inverted OSCs.

Indole-based atropisomers are a very important class of axially chiral compounds. However, the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored. In this study, we report the successful synthesis of atropisomeric 2-arylindoles using direct amination of indoles with p-quinonediimines in the presence of chiral phosphoric acid as a catalyst. Quinonediimine acts as an aminating reagent through formal polarity inversion of imine. The malonate group on the 2-aryl of 2-indoles was found to be essential for high enantioselectivity of the products. This could be due to the additional interaction between the ester group and the catalyst, as well as the intramolecular hydrogen bonding. Our findings provide a new strategy for the asymmetric construction of 2-arylindole atropisomers.

Herein we report an asymmetric two-component alkenyl Catellani reaction for the construction of C–N axial chirality through a pal-ladium/chiral norbornene cooperative catalysis and an axial-to-axial chirality transfer process. Various partially aromatic iodinated 2-pyridones, quinolones, coumarin and uracil substrates react with 2,6-disubstituted aryl bromides with a tethered amide group, to afford a wide variety of polycyclic C–N atropisomers (38 examples, up to 97% e.e.). The obtained C–N axial chirality is originated from the preformed transient C–C axial chirality with high fidelity. The synthetic utility of this chemistry is demonstrated by facile preparation of complex quinoline and pyridine based C–N atropisomers through a N-deprotection and aromatization sequence. In addition, a remote axial-to-central diastereoinduction process dictated by C–N axial chirality is observed with excellent diastere-ocontrol.

The [2.2]paracyclophane-derived oxazole-pyrimidine ligands with planar chirality (PYMCOX) were designed, synthesized and successfully applied in nickel-catalyzed asymmetric 1,2-reduction of α,β-unsaturated ketones, affording the chiral allylic alcohols with up to 99% yield and 99% ee. Meanwhile, this reduction reaction could be conducted on gram-scale without loss of activity and enantioselectivity, and the chiral ligand could be conveniently recovered with high yield.

The asymmetric hydrogenation of N-heteroarenes provides an efficient method for the synthesis of optically active cyclic secondary amines. In this paper, we described an asymmetric hydrogenation of phenanthridines using a chiral mono-alkene-derived borane. A variety of dihydrophenanthridines were furnished in high yields with up to 93% ee. The current catalytic system was very sensitive for the steric hindrance of phenanthridines. Bulky substituents at one phenyl group of phenanthridines were required to obtain the high enantioselectivity. But large substituents adjacent to the C=N bonds would diminish the reactivity sharply.

A metal-free, green, and sustainable functionalization of unactivated alkyl sp3 C–H bonds is reported using iodine (III) as a feasible dehydrogenation agent under visible light or KBr, and alkyl chlorides, bromides, alcohols, and ketones could be constructed by addi-tion of different coupling reagents. Cheap and safe iodobenzene diacetate was used to form a strong radical to activate the alkyl sp3 C–H bond in a highly efficient manner, which can construct different alkylation products by adding corresponding coupling reagents.