Chemical Science

Highly organized π-aggregate architectures can strongly affect electronic couplings, leading to important photophysical behaviors. With the escalating interest in two-dimensional (2D) materials attributed to their exceptional electronic and optical characteristics, there is growing anticipation that 2D radial-π-stacks built upon radial π-conjugation nanorings, incorporating intra- and inter-ring electronic couplings within the confines of a 2D plane, will exhibit superior topological attributes and distinct properties...

The boom of aqueous Zn-based energy storage devices, such as zinc-iodine (Zn-I2 ) batteries, is quite suitable for safe and sustainable energy storage technologies. However, in rechargeable aqueous Zn-I2 batteries, the shuttle phenomenon of polyiodide ions usually leads to irreversible capacity loss resulting from both the iodine cathode and the zinc anode, and thus impinges on the cycle lifespan of the battery. Herein, a nontoxic, biocompatible, and economical polymer of polyvinyl alcohol (PVA) is exploited as an electrolyte additive...

In the era of the Internet of Things and wearable electronics, 3D-printed micro-batteries with miniaturization, aesthetic diversity and high aspect ratio, have emerged as a recent innovation that solves the problems of limited design diversity, poor flexibility and low mass loading of materials associated with traditional power sources restricted by the slurry-casting method. Thus, a comprehensive understanding of the rational design of 3D-printed materials, inks, methods, configurations and systems is critical to optimize the electrochemical performance of customizable 3D-printed micro-batteries...

Organic deep-red (DR) and near-infrared (NIR) emitters with high photoluminescence quantum yield (PLQY) are rare due to the strong non-radiative ( k nr ) decay. Here, we report two DR/NIR emitters with high PLQY, TPANZPyPI and TPANZ3PI. Interestingly, the TPANZPyPI film exhibits 46.5% PLQY at 699 nm. Theoretical calculations indicate that TPANZPyPI can achieve this high PLQY in the near-infrared emission region due to its small S1 to S0 internal conversion (IC) rate. Meanwhile, research has found that, compared to TPANZ3PI, TPANZPyPI with a more rigid structure can effectively suppress the T2 to T1 IC process, which is conducive to higher exciton utilization efficiency (EUE)...

The comparison of homologous metalloenzymes, in which the same inorganic active site is surrounded by a variable protein matrix, has demonstrated that residues that are remote from the active site may have a great influence on catalytic properties. In this review, we summarise recent findings on the diverse molecular mechanisms by which the protein matrix may define the oxygen tolerance, catalytic directionality and catalytic reversibility of hydrogenases, enzymes that catalyse the oxidation and evolution of H2 ...

Tetrapyridyl-functionalized phosphinines were prepared and structurally characterized. The donor-functionalized aromatic phosphorus heterocycles react highly selectively and even reversibly with water. Calculations reveal P,N-cooperativity for this process, with the flanking pyridyl groups serving to kinetically enhance the formal oxidative addition process of H2 O to the low-coordinate phosphorus atom via H-bonding. Subsequent tautomerization forms 1,2-dihydrophosphinine derivatives, which can be quantitatively converted back to the phosphinine by applying vacuum, even at room temperature...

The synthesis of BN-containing molecules, which have an interesting isosteric relationship to their parent all-C cores, has drawn a great deal of attention as an avenue to alter and tune molecular function. Nevertheless, many cores with embedded BN are still hard to synthesize, and thus, further effort is required in this direction. Herein, we present an integrated approach to BN-containing polycycles rooted in an exceptionally clean B-N condensation of amines with a tri-allylborane. Having released propene as the only byproduct, the resulting BN precursors are seamlessly telescoped into BN-containing polycyclic cores via a set of additional methodologies, either developed here ad-hoc or applied for the first time for the synthesis of BN-cycles...

Highly substituted trans -hydrindanes were synthesized by the three-component coupling reactions of 1,3-diethyl 2-(2-oxopropylidene)propanedioate and two different α,β-unsaturated aldehydes catalyzed by diphenylprolinol silyl ether. The reaction proceeds via two successive independent catalytic domino reactions in a one-pot reaction by a single chiral catalyst. Domino reactions involve Michael/Michael and Michael/aldol reactions to afford trans -hydrindanes with excellent diastereoselectivity and nearly optically pure form...

The ability of molecular switches to reversibly interconvert between different forms promises potential applications at the scale of single molecules up to bulk materials. One type of molecular switch comprises cobalt-dioxolene compounds that exhibit thermally-induced valence tautomerism (VT) interconversions between low spin Co(iii)-catecholate (LS-CoIII -cat) and high spin Co(ii)-semiquinonate (HS-CoII -sq) forms. Two families of these compounds have been investigated for decades but have generally been considered separately: neutral [Co(diox)(sq)(N2 L)] and cationic [Co(diox)(N4 L)]+ complexes (diox = generic dioxolene, N2 L/N4 L = bidentate/tetradentate N-donor ancillary ligand)...

Exploratory synthesis has been the main generator of new inorganic materials for decades. However, our Edisonian and bias-prone processes of synthetic exploration alone are no longer sufficient in an age that demands rapid advances in materials development. In this work, we demonstrate an end-to-end attempt towards systematic, computer-aided discovery and laboratory synthesis of inorganic crystalline compounds as a modern alternative to purely exploratory synthesis. Our approach initializes materials discovery campaigns by autonomously mapping the synthetic feasibility of a chemical system using density functional theory with AI feedback...

Di- tert -butyldiphosphatetrahedrane ( t BuCP)2 (1) is a mixed carbon- and phosphorus-based tetrahedral molecule, isolobal to white phosphorus (P4 ). However, despite the fundamental significance and well-explored reactivity of the latter molecule, the precise structure of the free ( t BuCP)2 molecule (1) and a detailed analysis of its electronic properties have remained elusive. Here, single-crystal X-ray structure determination of 1 at low temperature confirms the tetrahedral structure. Furthermore, quantum chemical calculations confirm that 1 is isolobal to P4 and shows a strong largely isotropic diamagnetic response in the magnetic field and thus pronounced spherical aromaticity...

Exploring novel electrochemiluminescence (ECL) molecules with high efficiency and good stability in aqueous solutions is crucial for achieving highly sensitive detection of analytes. However, developing chiral luminophores with efficient ECL performance is still a challenge. Herein, we first uncover that artemisinin (ART), a well-known chiral antimalarial drug, features a strong ECL emission at 726 nm with the assistance of a co-reactant potassium persulfate (K2 S2 O8 ), and an ECL efficiency of 195.3%, compared to that of standard Ru(bpy)3 Cl2 /K2 S2 O8 ...

Previously, we have shown that native ambient mass spectrometry imaging allows the spatial mapping of folded proteins and their complexes in thin tissue sections. Subsequent top-down native ambient mass spectrometry of adjacent tissue section enables protein identification. The challenges associated with protein identification by this approach are (i) the low abundance of proteins in tissue and associated long data acquisition timescales and (ii) irregular spatial distributions which hamper targeted sampling of the relevant tissue location...

In quantum dot-sensitized solar cells (QDSCs), optimized quantum dot (QD) loading mode and high QD loading amount are prerequisites for great device performance. Capping ligand-induced self-assembly (CLIS) mode represents the mainstream QD loading strategy in the fabrication of high-efficiency QDSCs. However, there remain limitations in CLIS that constrain further enhancement of QD loading levels. This review illustrates the development of various QD loading methods in QDSCs, with an emphasis on the outstanding merits and bottlenecks of CLIS...

Palladium-catalyzed enantioselective domino Heck/intramolecular C-H functionalization reaction, as a valuable strategy for creating molecular diversity, has remained a prominent challenge. Here, we describe a Pd/XuPhos catalyst for asymmetric domino Heck/intermolecular C-H alkylation of unactivated alkenes with diverse polyfluoro- and heteroarenes in a highly chemo- and enantioselective manner. This process enables efficient synthesis of various dihydrobenzofurans, indolines and indanes, which are of interest in pharmaceutical research and other areas...

A combined computational and experimental study reveals that ortho -, meta - and para -aminobiphenyl isomers undergo distinctly different photochemical reactions involving proton transfer. Deuterium exchange experiments show that the ortho -isomer undergoes a facile photoprotonation at a carbon atom via excited-state intramolecular proton transfer (ESIPT). The meta -isomer undergoes water-assisted excited-state proton transfer (ESPT) and a photoredox reaction via proton-coupled electron transfer (PCET). The para -isomer undergoes a water-assisted ESPT reaction...

The direct functionalization of unactivated organic moieties via C-C bond formation has long fascinated synthetic chemists. Although base-metal systems are steadily emerging in this area, achieving multitasking activity in a single catalyst to execute several such functionalizations under mild conditions is challenging. To address this, we herein report an effective protocol for the selective C-alk(en)ylation of indene/fluorene with alcohol as a green alkylating agent employing a naturally abundant and eco-friendly zinc-derived compound, for the first time...

Azasulfur(vi) compounds such as sulfoximines and sulfonimidamides are attractive due to the unique properties of the S[double bond, length as m-dash]N bond. While the synthesis of these carbon-attached sulfonimidoyl derivatives is well-established, the situation is different for their heteroatom-bound counterparts. In this work, we propose azasulfur(iv) esters as platform chemicals that can be derivatized to obtain all types of SVI [double bond, length as m-dash]N functional groups, among these are the poorly accessible, all-heteroatom imidosulfate esters...

Metal-organic frameworks (MOFs) incorporating open metal sites (OMS) have been identified as promising sorbents for many societally relevant-adsorption applications including CO2 capture, natural gas purification and H2 storage. This has been ascribed to strong specific interactions between OMS and the guest molecules that enable the MOF to achieve an effective capture even under low gas pressure conditions. In particular, the presence of OMS in MOFs was demonstrated to substantially boost the H2 binding energy for achieving high adsorbed hydrogen densities and large usable hydrogen capacities...

Molecular metal-nitrogen-carbon (M-N-C) catalysts with well-defined structures and metal-coordination environments exhibit distinct structural properties and excellent electrocatalytic performance, notably in the oxygen reduction reaction (ORR) for fuel cells. Metal-doped azaphthalocyanine (AzPc) catalysts, a variant of molecular M-N-Cs, can be structured with unique long stretching functional groups, which make them have a geometry far from a two-dimensional geometry when loaded onto a carbon substrate, similar to a "dancer" on a stage, and this significantly affects their ORR efficiency at different pH levels...