Cucurbit[8]uril-stabilized charge transfer: An efficient supramolecular approach toward a heterogeneous organic photocatalyst for aerobic oxidation reactions.

Host-stabilized charge transfer (HSCT) has been widely utilized in macrocycle-derived supramolecular assemblies and architectures. However, there has been less research attention focused on the direct fabrication of pure organic photocatalysts using HSCT. Herein, four viologen derivatives (m-PV2+, m-BPV2+, d-PV2+, and d-BPV2+) with different electron donor-acceptor (D-A) structures were synthesized.

Facile Fabrication of Novel S-scheme AgPO/g-CN/Zeolite Photocatalyst for Boosting Photocatalytic Tetracycline Degradation and Hydrogen Production.

This study presents a novel ternary AgPO/g-CN/zeolite composite for photocatalytic H production and TC degradation through S-scheme electron transport. The S-scheme AgPO/g-CN heterojunction was successfully constructed on zeolite surface through calcination and precipitation processes. The results indicated that AgPO/g-CN/zeolite-50 % presented dramatically enhanced photocatalytic TC degradation performance, and the TC degradation efficiency was up to 92.

Diverse Multinuclear Alkali Metallated (Li, Na, K, Rb, Cs) Family of the 1,3,5-tris-2-aminopyridyl-2,4,6-triethylbenzene Framework.

Literature on Group One organoelement chemistry is dominated by lithium, though sodium and potassium also feature prominently, whereas rubidium and caesium are rarely mentioned. With recent breakthroughs hinting that organoelement compounds of these two heavier metals can perform better than their lighter congeners in particular applications, important advantages could be missed unless complete sets of alkali metals are included in studies. Here, we report the synthesis and characterisation of a complete set of multi-alkali-metallated molecular compounds of the 1,3,5-tris[(4,6-dimethylpyridin-2-yl)aminomethyl]-2,4,6-triethylbenzene framework.

Role of Secondary Structure and Time-Dependent Binding on Disruption of Phthalocyanine Aggregates by Guanine-Rich Nucleic Acids.

Phthalocyanines are versatile photodynamic therapy agents whose biological activity depends on their aggregation state, which is expected to be influenced by binding to biomolecules. Here, guanine-rich nucleic acid binding of a water-soluble cationic, regiopure C zinc phthalocyanine bearing four triethylene glycol methyl ether and four N-methyl-4-pyridinium substituents (1) is reported. In contrast to double-stranded DNA, guanine systems GpG, (GG), poly(G) and quadruplex DNA are shown to effectively disrupt phthalocyanine aggregates in buffered solution.

Chiral Pd(II) Nanofiber Promoting Electron Transfer of g-CN for Efficient Photocatalytic Hydrogen Production.

The rapid transfer and separation of photogenerated electrons is very important for the improvement of photocatalytic efficiency. Here, chiral induced spin selectivity effect (CISS effect) was developed to accelerate electron transfer for efficient photocatalytic hydrogen production. A chiral and achiral racemic supramolecular Pd(II) complex nanofiber was fabricated via supramolecular self-assembly of chiral L-Py or its racemes with Pd(II) and used to modify carbon nitride (g-CN).

An Electrosynthesis of 1,3,4-Oxadiazoles from N-Acyl Hydrazones.

The 1,3,4-oxadiazole is a widely encountered motif in the areas of pharmaceuticals, materials, and agrochemicals. This work has established a mediated electrochemical synthesis of 2,5-disubstituted 1,3,4-oxadiazoles from N-acyl hydrazones. Using DABCO as the optimal redox mediator has enabled a mild oxidative cyclisation, without recourse to stoichiometric oxidants.

C-H Activation and Hydrogen Isotope Exchange of Aryl Carbamates Using Iridium(I) Complexes Bearing Chelating NHC-Phosphine Ligands.

Hydrogen isotope exchange (HIE) via C-H activation constitutes an efficient method for the synthesis of isotopically-enriched compounds, which are crucial components of the drug discovery process and are extensively employed in mechanistic studies. A series of iridium(I) complexes, bearing a chelating phosphine-N-heterocyclic carbene ligand, was designed and synthesized for application in the catalytic HIE of challenging N- and O-aryl carbamates. A broad range of substrates were labeled efficiently, and applicability to biologically-relevant systems was demonstrated by labeling an ʟ-tyrosine-derived carbamate with excellent levels of deuterium incorporation.

Correspondence on "Beyond the Dimer and Trimer: Tetraspiro[2.1.2.1.2.1.2.1]hexadecane-1,3,5,7-tetraone - the Cyclic Tetramer of Carbonylcyclopropane".

The International Union of Pure and Applied Chemistry (IUPAC) name given in the title is incorrect. The correct IUPAC name for this molecule is tetraspiro[2.1.

Modular Synthesis of Azines Bearing a Guanidine Core from N-Heterocyclic Carbene (NHC)-Derived Selenoureas and Diazo Reagents.

N-Heterocyclic carbene (NHC)-derived selenoureas comprise a fundamentally important class of NHC derivatives, with key applications in coordination chemistry and the determination of NHC electronic properties. Considering the broad reactivity of chalcogen-containing compounds, it is surprising to note that the use of NHC-derived selenoureas as organic synthons remains essentially unexplored. The present contribution introduces a novel, straightforward transformation leading to azines bearing a guanidine moiety, through the reaction of a wide range of NHC-derived selenoureas with commercially available diazo compounds, in the presence of triphenylphosphine.

O/S Exchange Reaction in Synthesizing Sulfur-Containing Polymers.

Using carbon disulfide (CS) and carbonyl sulfide (COS) as sulfur-containing and one-carbon feedstocks to make value-added products is paramount for both pure and applied chemistry and environmental science. One of the practical strategies is to copolymerize these bulk chemicals with epoxides to produce sulfur-containing polymers. This approach contributes to improving the sustainability of polymer manufacturing, provides highly desired functional polymer materials, and has attracted much attention.

Electrophilic Behavior of the "Nucleophilic" Pyramidane: Reactivity of Ge-Pyramidane towards Organolithium Reagents.

The particular reactivity of the recently discovered class of the main group element polyhedral clusters, pyramidanes, remains largely unexplored. In this communication, we report the reaction of the germapyramidane with tert-butyllithium leading to the rather unusual organogermanium compound [Li(thf)]⋅2, as the product of the formal insertion of a Ge-apex into the C-Li bond. This reactivity mode exemplifies unusual electrophilic behaviour of a pyramidane, which is a priori considered as a nucleophilic reagent.

Ruthenium(II) Polypyridyl Complexes with Benzoxazole Derivatives and Non-Innocent Ligands as Effective Antioxidants in Human Neuroblasts.

Ruthenium(II) polypyridyl complexes continue to raise increasing interest for the encouraging results in several biomedical areas. Considering their vast chemical-physical repertoire, in particular the possibility to switch from the sensitization of reactive oxygen species (ROS) to ROS-scavenging abilities by tuning the nature of their ligands, it is therefore surprising that their potential as antioxidants has not been largely investigated so far. Herein, we explored the antioxidant behaviour of the novel ruthenium compound [Ru(dbpy)(2,3-DAN)Cl]PF (Ru1), featuring a benzoxazole derivative (dpby=2,6-bis(4-methyl-2-benzoxazolyl)pyridine) and the non-innocent 2,3-diamminonaftalene (2,3-DAN) ligand, along with the reference tpy-containing analogue [Ru(tpy)(2,3-DAN)Cl]PF (Ru2) (tpy=2,2':6',2''-terpyridine).

Strategies to Design Chemocatalytic Racemization of Tertiary Alcohols: State of the Art & Utilization for Dynamic Kinetic Resolution.

The synthesis of enantiomerically pure tertiary alcohols is an important issue in organic synthesis of a range of pharmaceuticals including molecules such as the anti-HIV drug Efavirenz. A conceptually elegant approach to such enantiomers is the dynamic kinetic resolution of racemic tertiary alcohols, which, however, requires efficient racemization strategies. The racemization of tertiary alcohols is particularly challenging due to various side reactions that can occur because of their high tendency for elimination reactions.

Organometallic Bridge Diversification of Bicyclo[1.1.1]pentanes.

Bicyclo[1.1.1]pentane (BCP) derivatives have attracted significant recent interest in drug discovery as alkyne, tert-butyl and arene bioisosteres, where their incorporation is frequently associated with increased compound solubility and metabolic stability.

Modification of a Common β-diketiminate NacNac Framework via Sequential Lithiation and Small Molecule Insertion.

A widely utilised class of ligands in synthesis and catalysis, β-diketiminate (BDI) or NacNac compounds were initially considered innocent in the sense that they remained intact in all their applications. That changed when the γ-C-H unit of their NCCCN backbone was found to engage in reactions with electrophiles. Here, we show that this special reactivity can be used advantageously to prepare tripodal modifications of the common NacNac ligand derived from 2,6-diisopropylphenyl-β-methyldiketimine [NacNacH (Me, Dipp)].

Copper-Mediated N-Trifluoromethylation of O-Benzoylhydroxylamines.

The use of trifluoromethyl containing compounds is well established within medicinal chemistry, with a range of approved drugs containing C-CF and O-CF moieties. However, the utilisation of the N-CF functional group remains relatively unexplored. This may be attributed to the challenging synthesis of this unit, with many current methods employing harsh conditions or less accessible reagents.

Water-Based Synthesis of β-Sheet-Like Supramolecular Metallohydrogel Organized by Using a Native Ultrashort Peptide Sequence.

Designing supramolecular hydrogels using short peptides is challenging. To control self-assembly, a certain amount of organic solvent is typically added to the system, or the short peptide is modified with a functional group that is hydrophobic, hydrophilic, or highly coordinative. We discovered that l-His-l-Ile-l-Thr (HIT), a very short unmodified "native" tripeptide, selectively responds to Cu ions in pure water to form a transparent supramolecular metallohydrogel.

Controllable Structural Transformation of Non-Porous Propyl-Malonate Hexakis[60]fullerene by Chloroform Uptake/Release.

The design of dynamic structures with high recognition host-guest materials capable to host selectively small volatile molecules is an emergent field of research with both fundamental and applied implications. The challenge of exploring novel materials with advanced functionalities has led to the development of dynamic crystalline structures promoted by soft interactions. Here, a new pure organic dynamic framework based on hexakis[60]fullerene that are held together by weak van der Waals interactions is described.

Formation and Growth of Atomic Scale Seeds of Au Nanoparticle in the Nanospace of an Organic Cage Molecule.

Seed-mediated growth has been widely used to synthesize noble metal nanoparticles with controlled size and shape. Although it is becoming possible to directly observe the nucleation process of metal atoms at the single atom level by using transmission electron microscopy (TEM), it is challenging to control the formation and growth of seeds with only a few metal atoms in homogeneous solution systems. This work reports site-selective formation and growth of atomic scale seeds of the Au nanoparticle in a nanospace of an organic cage molecule.

Multiply exo-Methylated Corannulenes.

Invited for the cover of this issue are Shinobu Aoyagi (Nagoya City University), Takahiro Sasamori (University of Tsukuba), and Hideki Yorimitsu (Kyoto University). The image depicts multiply exo-methylated corannulenes (flowers) synthesized from corannulene (central large flower) by the reduction with sodium (soil) to form anionic corannulenes and the subsequent methylation with reduction-resistant dimethyl sulfate (butterflies). Read the full text of the article at 10.

Highly Enantioselective Synthesis of Pharmaceuticals at Chiral-Encoded Metal Surfaces.

Enantioselective catalysis is of crucial importance in modern chemistry and pharmaceutical science. Although various concepts have been used for the development of enantioselective catalysts to obtain highly pure chiral compounds, most of them are based on homogeneous catalytic systems. Recently, we successfully developed nanostructured metal layers imprinted with chiral information, which were applied as electrocatalysts for the enantioselective synthesis of chiral model compounds.

Dual Chalcogen-Bonding Interactions for the Conformational Control of Urea.

Dual chalcogen-bonding interactions is proposed as a novel means for the conformational control of urea derivatives. The formation of a chalcogen-bonding interaction at both sides of the urea carbonyl group was unambiguously confirmed by X-ray diffraction as well as computational studies including non-covalent interaction (NCI) plot index analysis, quantum theory of atoms in molecules (QTAIM) analysis, and natural bond orbital (NBO) analysis via DFT calculations. By virtue of this dual interaction, urea derivatives that bear chalcogen atoms (X=S and Se) adopt a planar structure via the carbonyl oxygen (O) with an X⋅⋅⋅O⋅⋅⋅X arrangement on the same side of the molecule.

The Structure of Maneb, An Important Manganese-Containing Bis(dithiocarbamate) Fungicide.

Maneb is a manganese(II)-containing fungicide with a multi-site effect and no resistance, therefore it is widely applied in many parts of the world. There is, however, mounting evidence for neurotoxic effects with Parkinson-like symptoms (manganism) related to usage of Maneb. Due to its insolubility in most solvents and its paramagnetism, structural elucidation is not trivial, and thus its exact molecular structure remains unknown.

Structural Conversion of Supramolecular Assembly in Solution by Thermally Induced Intramolecular Electron Transfer of [Co Fe ] Complex.

Invited for the cover of this issue is the group of Masayuki Nihei at the University of Tsukuba. The image depicts the electron transfer-triggered structural conversion of the supramolecular assembly of a [Co Fe ] complex between reverse vesicles and entangled one-dimensional chains. Read the full text of the article at 10.