The atroposelective C-H cyanation of 1-aryl isoquinolines using rhodium(III) catalysis was realized. In the presence of a chiral binaphthyl O-linked Cp rhodium (BOCpRh) complex, highly atroposelective C-H cyanation of 1-aryl isoquinolines with N-cyano-N-phenyl-p-toluenesulfonamide proceeded smoothly to afford a wide range of axially chiral 1-aryl isoquinoline nitriles in up to 94% yield and 91% ee. This method provides a facile access to axially chiral nitriles under mild conditions. The transformations of the products and preliminary mechanistic studies have been carried out.

Narrowband organic room-temperature phosphorescence (RTP) remains rare due to significant high-frequency vibronic coupling in T1 -> S0 electronic transition, where T1 and S0 represent the lowest triplet excited state and ground state, respectively. Here, we report coronene-derived (CoDe) luminophores exhibiting ultra-narrowband RTP (full width at half maximum FWHM = 11.2 nm) with a 1.5 s lifetime and 38% afterglow efficiency in a phenyl benzoate (PhB) matrix. The narrow emission arises from enhanced coupling with low-frequency vibrational modes in localized excitation (LE) states, as supported by vibronic simulations. Under high-power excitation, the CoDe-PhB further exhibits organic long-persistent luminescence (OLPL) lasting over 40 min (FWHM = 14.7 nm), governed by a two-photon ionization-induced charge-separation mechanism. The materials are processable via melt-casting and excitable by ambient or white light, offering practical utility for high-color-purity afterglow display and lighting applications. This work establishes low-frequency vibronic engineering as a new route to narrowband RTP and OLPL emitters beyond conventional multi-resonance-based designs.

Copolymerization of more activated methacrylates and less activated vinyl esters is challenging because of their large difference in reactivity ratio. This severely limits the development of high-performance materials. Herein, we design a side-armed bisoxazoline (SaBOX)/CoBr2 catalyst with sheltered coordination environment to achieve strong binding ability to propagating radicals in photoinduced cobalt-mediated radical polymerization (CMRP) of vinyl ester and methacrylate. This enables the efficient synthesis and structure regulation of methacrylate-vinyl ester copolymers. The catalytic system efficiently and directly produces di- and tri-block copolymers via in-situ chain extension. Moreover, homogeneous random copolymers of vinyl ester and methacrylate are also facilely synthesized. The mechanistic studies are consistent with the polymerization results, which validate the CMRP mechanism and our catalyst design concept.

The real-time monitoring of key metabolites, notably glucose and dopamine, has emerged as a critical imperative for advancing human healthcare. Biosensors, especially for electrochemical detection, present a cost-effective and practical approach to achieve rapid and efficient molecular detection. This study presented a strategic advancement in electrochemical sensing technology through the rational design of a hybrid nanocomposite as substrate. By integrating multifunctional graphene oxide (GO) nanosheets with carbon nanotubes (CNT), we engineered a platform for the immobilization and stabilization of gold nanoparticles (AuNPs), yielding a highly dispersed and electroactive Au@SH-GO-PEG/CNT nanocomposite. Concretely, in Au@SH-GO-PEG/CNT dispersion, the compatible polymer (PEG) was conjugated on GO sheets to ensure colloidal stability and uniform dispersion, thiol groups were introduced into GO sheets to anchor AuNPs, and CNT was integrated into GO for enhancement of electrochemical activity. In subsequent electrochemical detection of glucose and dopamine, it was informed that GCE/Au@SH-GO-PEG/CNT could serve as a promising substrate for a sensitive and stable electrochemical sensor, on account of systemic CV curves and corresponding amperometric responses. Thus, it is reasonable to anticipate that this rationally designed GO-CNT hybrid nanocomposite can act as an effective platform for stabilizing AuNPs while preserving their inherent properties. The strategic integration of CNT within GO could synergistically amplify the electrochemical activity of the AuNPs/GO system. (c) 2025 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.

Selectivity control is a very challenging topic in catalytic oxidations of alcohols using oxygen as an oxidant. Of particular interest is the catalytic aerobic lactonization of diols; due to the selectivity issue referring to the two hydroxy groups, the reaction afforded a mixture of isomeric products. Herein, we report an efficient catalytic recipe of easily available earth-abundant metal catalysts Fe(NO3)39H2O and FeCl3 together with TEMPO for the highly selective aerobic oxidative lactonization of 1,6-diols, affording a variety of epsilon-caprolactones. The reaction was conducted under mild conditions with an O2 balloon or under ambient air enjoying high chemo- and regioselectivity for the oxidative lactonization of non-symmetric diols by the subtle recognition of the steric environment of the two hydroxy groups. Furthermore, reduction and selective aerobic oxidative lactonization constitute a formal carbonyl walking over the epsilon-caprolactones. Mechanistic experiments reveal a process with a hemiacetal as the intermediate. This protocol unlocks an efficient pathway to derive monomers for polycaprolactones.

Chiral N-heterocycles such as piperidines and tetrahydroisoquinolines are privileged structural motifs in drug discovery and pharmaceutical industry. The development of efficient and practical asymmetric synthetic methods towards pharmaceutically important chiral N-heterocycles constitutes an important subject in synthetic chemistry. Asymmetric synthesis of 2,3-cis-disubstituted piperidines bearing two consecutive chiral centers is particularly challenging in terms of both diastereoselective and enantioselective control. In this work, a regiospecific and enantioselective cyclizative aminoboration is designed to tackle this problem by employing Cu/(S, S)-Ph-BPE as the chiral catalyst, leading to a series of 2,3-cis-disubstituted piperidines as well as C1-substituted tetrahydroisoquinolines in moderate to good yields and excellent enantioselectivities. The asymmetric six-membered ring-closing aminoboration features a broad substrate scope, mild reaction conditions, and excellent functional group compatibility. DFT calculation reveals the importance of noncovalent interactions between substrate and Cu catalyst in controlling the enantioselectivity. The synthetic utility and practicality of this cyclization protocol have been exemplified by the synthesis of the key chiral intermediates of avacopan and L-733,060.

A nickel-catalyzed allylation of imines, including cyclic imines such as dibenzoxazepines, quinazolinones, and quinoxalin-2(1H)-ones and linear imines, using allylic alcohols as pro-nucleophiles has been developed. This transformation affords homoallylic amines in good to excellent yields with high levels of regio- and diastereoselectivity. Mechanistic studies suggest that the bis(pi-allyl)nickel(II) intermediate serves as a crucial intermediate in the catalytic cycle, exhibiting nucleophilic reactivity through its eta 1,eta 3 coordination mode.

Two-dimensional conjugated covalent organic frameworks (COFs) have emerged as a new class of promising photocatalysts for solar-hydrogen energy conversion. The regulation of their interlayer stacking mode is an important strategy to modulate their properties and photocatalytic performance. Historically, the staggered AB mode has seldom demonstrated greater photoactivity than the corresponding eclipsed AA mode. Herein, a contrary example is presented, wherein the AB-stacked PyDBTSO-AB COF outperforms its AA-stacked isomer, PyDBTSO-AA COF. This pair of isostructured COFs was synthesized from the same tetraaniline-functionalized pyrene (Py) monomer and dibenzaldehyde-functionalized dibenzothiophene sulfone (DBTSO) monomer under conventional solvothermal conditions in an o-dichlorobenzene/butanol/acetic acid-mixed medium and under ionothermal conditions in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid, respectively. Structural characterizations revealed that PyDBTSO-AA possesses a larger specific surface area and void pore volume, whereas PyDBTSO-AB exhibits greater hydrophilicity and a shorter interlayer pi-pi stacking distance. Furthermore, electrochemical impedance spectroscopy and photocurrent responsive experiments revealed that PyDBTSO-AB has a smaller charge transport impedance and a larger photocurrent responsiveness than PyDBTSO-AA. Finally, in photocatalytic hydrogen production experiments conducted with Pt co-catalyst under full-arc Xe light irradiation, PyDBTSO-AB achieved a hydrogen evolution rate of 109.6 mmol g-1 h-1, more than twice that displayed by PyDBTSO-AA. Consequently, this research emphasizes the equal importance of the AB-stacking mode in comparison to the AA-stacking mode within the realm of photocatalytic COF design and provides new insights into the manner in which their interlayer-stacking modes influence the ultimate photocatalytic activities.