One of the bottlenecks associated with supramolecular polymerization of functional pi-systems is the spontaneous assembly of monomers leading to one- or two-dimensional (1D or 2D) polymers without control over chain length and optical properties. In the case of supramolecular copolymerization of monomers that are structurally too diverse, preferential self-sorting occurs unless they are closely interacting donor-acceptor pairs. Herein, we establish that the spontaneous 1D polymerization of a phenyleneethynylene (PE) derivative and the 2D polymerization of a Bodipy derivative (BODIPY) can be controlled by copolymerizing them in different ratios, leading to unusual spindle-shaped structures with controlled aspect ratio, as evident by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM) studies. For example, when the content of BODIPY is 50% in the BODIPY-PE mixture, the 1D polymerization of PE is significantly restricted to form elongated spindle-like structures having an aspect ratio of 4-6. The addition of 75% of BODIPY to PE resulted in circular spindles having an aspect ratio of 1-2.5, thereby completely restricting the 1D polymerization of PE monomers. Moreover, the resultant supramolecular copolymers exhibited morphology and aspect ratio dependent emission features as observed by the time-resolved emission studies.

Surface modification of indium tin oxide (ITO) electrodes with organic molecules is known to tune their work function which results in higher charge carrier selectivity in corresponding organic electronic devices and hence influences the performance of organic solar cells. In recent years, N-heterocyclic carbenes (NHCs) have also been proven to be capable to modify the work function of metals and semimetals compared to the unfunctionalized surface via the formation of strong covalent bonds. In this report, we have designed and performed the modification of the ITO surface with NHC by using the zwitterionic bench stable IPr-CO2 as the NHC precursor, applied via spin coating. Upon modification, the work function of ITO electrodes was reduced significantly which resulted in electron selective contacts in corresponding organic photovoltaic devices. In addition, various characterization techniques and analytical methods are used to elucidate the nature of the bound species and the corresponding binding mechanism of the material to the ITO surface.

To realize organic integrated optoelectronic circuits, there is a need for anisotropic optical waveguides at the micro/nanoscale. Anisotropic alignment of one-dimensional (1D)-ordered supramolecular structures composed of light-emissive π-conjugated molecules in a crystal may meet the requirements of such waveguides. Here, we designed a bipyridyl-appended acrylonitrile-based π-conjugated molecule 1, which produced a 1D supramolecular polymer constructed through non-covalent bonding between a lone pair in 1 and a σ-hole in 1,4-diiodo-2,3,5,6-tetrafluorobenzene 2. The 1D copolymer of 1 and 2 is aligned horizontally with the two-dimensional (2D) crystal surface because of the angle-controlled supramolecular synthons. As a result of control over the non-covalent bonding direction, anisotropic photoluminescence and photon transport (optical waveguiding) characteristics are realized by orienting the transition dipole moment horizontally with respect to the 2D surface. Compared with the loss coefficient αL =52dBcm-1 for the long-axis direction of the 2D platelet cocrystal, a very large difference of αS =2111dBcm-1 is present in the crystal short-axis direction. The anisotropic waveguiding ability, αL/αS, is estimated to be 41, which is more than an order of magnitude greater than previously reported 2D platelet crystal waveguides. This supramolecular synthon provides an approach to designing anisotropic photon transporters and highly regulated optical logic circuits.

Oxidation of a base-stabilised phosphinidene (k2-***** (12, NNP= phosphinoamidinate) with N2O afforded a labile phopshinidene oxide (k2-*****=O (16) which was characterized by NMR spectroscopy. Further oxidation of 16 by N2O or reaction of 12 with two equivalents of pyridine oxide afforded the isolable dioxide (k2-NNP)PO2 which was characterized by NMR and SC XRD. Trapping of 16 with tolyl Isocyanate resulted in P=O/N=C metathesis, eventually affording a urea-ligated phosphine (k1-*****(NTol)2C=O (17) The mechanism of this reaction was elucidated by DFT calculations. Reactions of phosphinidene 12 with azides generated transient imines (*****=NR, which in the case of R=Tol underwent cycloaddition with tolyl Isocyanate to afford the urea product 17, and in the case of R=SiMe3 reacts with N3SiMe3 via the addition of N-Si across the P=N bond affording, after the extrusion of dinitrogen, a P,N-heterocyclic compound. Both products of the reactions with azides have been fully characterized, both in solution and the solid-state. Finally, reaction of phosphinidene 12 with one equivalent of sulfur resulted in the isolation of the base-stabilized phosphinidene sulfide (k2-*****=S that has also been fully characterized.

A series of Mn(I) complexes Mn(L1)(CO)3Br, Mn(L2)(CO)3Br, Mn(L1)(CO)3(OAc) and Mn(L3)(CO)3Br [L1 = 2-(5-tert-butyl-1H-pyrazol-3-yl)-1,8-naphthyridine, L2 = 2-(5-tert-butyl-1H-pyrazol-3-yl)pyridine, L3 = 2-(5-tert-butyl-1-methyl-1H-pyrazol-3-yl)-1,8-naphthyridine] were synthesized and fully characterized. The acid-base equilibrium between the pyrazole and the pyrazolato forms of Mn(L1)(CO)3Br was studied by 1H NMR and UV-vis spectra. These complexes are screened as catalysts for acceptorless dehydrogenative coupling (ADC) of primary alcohols and aromatic diamines for the synthesis of benzimidazole and quinoline derivatives with the release of H2 and H2O as byproducts. The protic complex Mn(L1)(CO)3Br shows the highest catalytic activity for the synthesis of 2-substituted benzimidazole derivatives with broad substrate scope, whereas a related complex [Mn(L3)(CO)3Br], which is devoid of the proton responsive β-NH unit, shows significantly reduced catalytic efficiency validating the crucial role of the β-NH functionality for the alcohol dehydrogenation reactions. Control experiments, kinetic and deuterated studies, and density functional theory (DFT) calculations reveal a synchronous hydride-proton transfer by the metal-ligand construct in the alcohol dehydrogenation step.

A silica zeolite (RWZ-1) with a very high framework density (FD) was synthesized from highly crystalline natural layered silicate magadiite, bridging the gap between the two research areas of zeolites and dense silica polymorphs. Magadiite was topotactically converted into a 3D framework through two-step heat treatment. The resulting structure had a 1D micropore system of channel-like cavities with an FD of 22.1 Si atoms/1000 Å3. This value is higher than those of all other silica zeolites reported so far, approaching those of silica polymorphs (tridymite (22.6) and α-quartz (26.5)). RWZ-1 is a slight negative thermal expansion material with thermal properties approaching those of dense silica polymorphs. It contributes to the creation of a new field on microporous high-density silica/silicates. Synergistic interactions are expected between the micropores with molecular sieving properties and the dense layer-like building units with different topologies which provide thermal and mechanical stability.

We herein reported the design and synthesis of a ferrocene-based tetradentate ligand that is featured with modular synthesis and rigid skeleton. Its iron(II) complex facilitates asymmetric hydrogenation of ketones without the participation of extra strong-field ligand such as CO and isocyanide. Hydride donor LAH converted non-reactive Fe(II) species to reactive Fe(II) hydride species. With this catalyst, various chiral alcohols including the intermediate for montelukast could be prepared with satisfactory yields and enantioinduction.

Post-synthetic modification (PSM) imparts additional functionality to metal-organic frameworks (MOFs) that is often difficult to access using solvothermal synthesis. As such, expanding the repertory of PSM reactions available to the practitioner is of increased importance for the generation of materials tailored for desired applications. Herein, we describe a method for the protecting group-free installation of diverse functional groups within the pores of a MIL-53(Al) analogue via disulfide bond formation. The majority of the reactions proceed with thiol-to-disulfide conversions ranging from high to nearly quantitative. The disulfide bonds are stable in various solvents and can be cleaved in the presence of a reducing agent.

The creation of complementary products via templating is a hallmark feature of nucleic acid replication. Outside of nucleic acid-like molecules, the templated synthesis of a hetero-complementary copy is still rare. Herein we describe one cycle of templated synthesis that creates homomeric macrocyclic peptides guided by linear instructing strands. This strategy utilizes hydrazone formation to pre-organize peptide oligomeric monomers along the template on a solid support resin, and microwave-assisted peptide synthesis to couple monomers and cyclize the strands. With a flexible templating strand, we can alter the size of the complementary macrocycle products by increasing the length and number of the binding peptide oligomers, showing the potential to precisely tune the size of macrocyclic products. For the smaller macrocyclic peptides, the products can be released via hydrolysis and characterized by ESI-MS.

Robust scaffolds were typically applied in thermally activated delayed fluorescence (TADF) molecules to suppress the non-radiative decay, trigger the fast spin-flipping, and enhance the light out-coupling efficiency. Herein, we disclosed for the first time the positive effect of flexible conformation of ancillary groups on the photophysical properties of TADF emitter. The red TADF emitter Ph-TPA with flexible conformation demonstrated small excited-state structural distortion and low reorganization energy compared to the counterpart Mc-TPA with a rigid macrocycle. Consequently, Ph-TPA showed an excellent photoluminescent quantum yield (PLQY) of 92% and a state-of-the-art external quantum efficiency (EQE) of 30.6% at 630 nm. This work could deepen our understanding of structure-property relationships of organic luminophores and help us to rationalize the design of efficient TADF materials.

Alzheimer's disease (AD) continues to be a major global health challenge, and the recent approval of Aduhelm and Leqembi has opened new avenues for its treatment. Small-molecule inhibitors targeting Aβ aggregation hold promise as an alternative to monoclonal antibodies. In this study, we evaluated the ability of berbamine hydrochloride (BBMH), a member of the bisbenzylisoquinoline alkaloids, to reduce Aβ aggregation and cytotoxicity. Thioflavin T kinetics, circular dichroism spectroscopy, and atomic force microscopy results indicated that BBMH effectively inhibited Aβ aggregation. Surface plasmon resonance and molecular docking results further revealed that BBMH could bind to Aβ fibrils, thereby hindering the aggregation process. This physical picture has been confirmed in a quantitative way by chemical kinetics analysis, which showed BBMH tends to bind with the fibril ends and thus prevents the transition from protofibrils to mature fibrils as well as the elongation process. Additionally, our MTT results showed that BBMH was able to reduce the cytotoxicity of Aβ40 on N2a cells. Our results demonstrate, for the first time, the potential of BBMH to inhibit Aβ aggregation and cytotoxicity, offering a promising direction for further research and drug development efforts in the fight against Alzheimer's disease.

The synthesis of undescribed b-aminodifluoroethylsulfinates and their uses in the hydroaminodifluoroalkylation of alkenes is reported. This reaction is performed in the presence of a photocatalyst (4CzIPN, Ru complexes) and enables the direct incorporation of a b-difluoroamine moiety onto vinylic aryls, unactivated alkenes, and electron–rich, or –deficient alkenes. The mechanism was studied and the formation of a gem-difluoromethyl radical is observed after the selective oxidation of the sulfinate function.

We report a selectivity-switchable nickel hydride-catalyzed methodology that enables the stereocontrolled semi-reduction of internal alkynes to E- or Z-alkenes under very mild conditions. The proposed transfer semi-hydrogenation process involves the use of a dual nickel/photoredox catalytic system and triethylamine, not only as a sacrificial reductant, but also as a source of hydrogen atoms. Mechanistic studies revealed a pathway involving photo-induced generation of nickel hydride, syn-hydronickelation of alkyne, and alkenylnickel isomerization as key steps. Remarkably, mechanistic experiments indicate that the control of the stereoselectivity is not ensuing from a post-reduction alkene photoisomerization under our conditions. Instead, we demonstrate that the stereoselectivity of the reaction is dependent on the rate of a final protonolysis step which can be tuned by adjusting the pKa of an alcohol additive.

Recent trends in catalysis are devoted to mimicking some peculiar features of enzymes like site selectivity, through functional group recognition, and substrate selectivity, through recognition of the entire surface of the substrate. The latter is a specific feature of enzymes that is seldomly present in homogeneous catalysis. Supramolecular catalysis, thanks to the self-assembly of simple subunits, enables the creation of cavities and surfaces whose confinement effects drive the preferential binding of a substrate among others with consequent substrate selectivity. The topic is an emerging field that exploits recognition phenomena to discriminate the reagents based on their size and shape. This review deals this cutting-edge field of research covering examples of supramolecular self-assembled molecular containers and catalysts operating in organic as well as aqueous media, with special emphasis for catalytic systems dealing with direct competitive experiments involving two or more substrates.

The prominent role of gold-N-heterocyclic carbene (NHC) complexes in numerous research areas such as homogeneous (photo)catalysis, medicinal chemistry and materials science has prompted organometallic chemists to design gold-based synthons that permit access to target complexes through simple synthetic steps under mild conditions. In this review, the main gold-NHC synthons employed in organometallic synthesis are discussed. Mechanistic aspects involved in their synthesis and reactivity as well as applications of gold-NHC synthons as efficient pre-catalysts, antitumor agents and/or photo-emissive materials are presented.

We report a heterocyclic merging approach to construct novel indazolo-piperazines and indazolo-morpholines. Starting from chiral diamines and amino alcohols, novel regiochemically (1,3 and 1,4) and stereochemically diverse (relative and absolute) cohorts of indazolo-piperazines and indazolo-morpholines were obtained within 6-7 steps. The key transformations involved are a Smiles rearrangement to generate the indazole core structure and a late stage Michael addition to build the piperazine and morpholine heterocycles. We further explored additional vector diversity by incorporating substitutions on the indazole aromatic ring, generating a total of 20 unique enantiomerically pure heterocyclic scaffolds.

Nanostructures intrinsically possessing two different structural or functional features, often called Janus nanoparticles, are emerging as a potential material for sensing, catalysis, and biomedical applications. Herein, we report the synthesis of plasmonic gold Janus nanostars (NSs) possessing a smooth concave pentagonal morphology with sharp tips and edges on one side and, contrastingly, a crumbled morphology on the other. The methodology reported herein for its synthesis using a single-step growth reaction is unique to any other Janus nanoparticle preparation involving either template-assisted growth or a masking technique. Interestingly, a coexistence of lower and higher index facets has been found in these Janus NSs. The general paradigm for synthesizing Au Janus NSs was investigated by understanding the mechanism of its kinetic control with the combinatorial effect of all the reagents responsible for its structure. Optical property of the Janus NSs has been realized by corelating their extinction spectrum with the simulated data. The size-dependent surface-enhanced Raman scattering (SERS) activity of these Janus NSs has been studied with 1,4-BDT as the model analyte. Finite-difference time-domain (FDTD) simulations for different sized particles revealed the distribution of electromagnetic hot-spots over the particles resulting in the enhancement of the SERS signal in a size dependent manner.

A novel two-step method for formylation of fluoropyridines with silylformamidine 1 under catalyst-free conditions was developed. A series of possible 18 fluoropyridines featuring one to four fluorine atoms were subjected to the reaction with 1 existing in equilibrium with its carbenic form 1′.12 Fluoropyridines were shown to react via C-H insertion. The reaction proceeded either at β- or γ-positions affording the corresponding aminals. The more fluorine atoms in pyridines, the easier the reaction proceeded. We also hypothesized that the pyridines in which the fluorine was substituted by other halogens would react in a similar manner. To test the hypothesis, a set of 3,5-disubstituted pyridines with various combination of halogen atoms was prepared. 3,5-Difluoropyridine was taken as a compound for comparison. All the pyridines in the series also reacted likewise. In most cases, hydrolysis of the aminals afforded the corresponding aldehydes. As DFT calculations indicate, the reaction mechanism includes deprotonation of pyridine by 1′ as a strong base and the following rearrangement of the formed tight ionic pair to the final product. An alternative reaction pathway involving addition of 1′ to the pyridine carbon with the following hydrogen transfer via a three-membered transition state structure required much higher activation energy.

Organofunctionalized tetranuclear clusters [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (1, M = Co; 2, M = Zn) containing an unprecedented oxometallacyclic {M2V2Cl2N4O8} (M = Co, Zn) framework are prepared by solvothermal reactions. The new oxo-alkoxide compounds are fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab-initio computational methods, and complete single crystal X-ray diffraction structure analysis. The isostructural clusters are formed of edge-sharing octahedral {VO5N} and trigonal bipyramidal {MO3NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of 1 and 2 in an unusual two-mode fashion, unobserved previously. In the crystalline state, the clusters of 1 and 2 are joined by hydrogen-bonds to form a three-dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [Jiso(VIV-VIV) = -5.4(1); -3.9(2) cm-1], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [Jiso (VIV-CoII) = -12.6 and -7.5 cm-1] contained in 1.

Liquid exfoliation can be considered as a viable approach for scalable production of 2D materials due to its various benefits, although the polydispersity in the obtained nanosheet size hinders their straightforward incorporation. Size-separation can help alleviate these concerns, however a correlation between nanosheet size and property needs to be established to bring about size-specific applicability. Herein, size-selected aqueous nanosheet dispersions have been obtained via centrifugation-based protocols, and their chemical activity in the spontaneous reduction of chloroplatinic acid is investigated. Growth of ultrasmall Pt nanoparticles was achieved on nanosheet surfaces without a need for reducing agents, and stark differences in the nanoparticle coverage were observed as a function of nanosheet size. Defects in the nanosheets were probed via Raman spectroscopy, and correlated to the observed size-activity. Additionally, the effect of reaction temperature during synthesis was investigated. The electrochemical activity of the ultrasmall Pt nanoparticle decorated MoS2 nanosheets was evaluated for hydrogen evolution reaction, and enhancement in performance was observed with nanosheet size, and nanoparticle decoration density. These findings shine light on the significance of nanosheet size in controlling spontaneous reduction reactions, and provide a deeper insight to intrinsic properties of liquid exfoliated nanosheets.