Dimethylnonacethrene is the first derivative of the cethrene family that is energetically more stable than the product of its electrocyclic ring closure. Compared to the shorter homologue dimethylc...

The introduction of diarylamino groups at the 2- and 6-positions of azulene was found to invert the order of the orbital energy levels and allowed the HOMO−LUMO transition, resulting in a substantial...

In this communication we describe a helically chiral push–pull molecule named 9,10-dimethoxy-[7]helicene diimide, displaying fluorescence (FL) and circularly polarised luminescence (CPL) over nearly...

Reaction of BeCl2 with the dilithium diamide, [{SiNDipp}Li2] ({SiNDipp} = {CH2SiMe2NDipp}2), provides the dimeric chloroberyllate, [{SiNDippBeCl}Li]2, en route to the 2-coordinate beryllium amide,...

X-ray crystallography is an invaluable tool in design and development of organometallic catalysis, but application typically requires species to display sufficiently high solution concentrations and...

We report the synthesis of 2-oxo-bicyclo[2.1.1]hexanes (2-oxo-BCHs) from bicyclobutanes (BCBs) and readily available enolate precursors. Glycine-derived enolates directly give protected 2-oxo-3-ami...

We describe the synthesis and characterization of hexabenzo[5.6.7]quinarene, which is composed of an anthraquinodimethane (AQD) central core that is end-capped with fluorenyl and dibenzosuberenyl...

Fluorinated cycloparaphenylenes (FCPPs) have attracted attention as electron-accepting CPPs as well as strained fluoroarenes. Herein, we report the synthesis and properties of novel FCPPs; F16[8]CPP...

A robust multigram-scale synthesis of 1,3-disubstituted cubanes (previously only available on milligram-scale) is reported. The approach exploits a readily available enone intermediate previously...

The chemistry of low valent p-block metal complexes continues to elicit interest in the research community, demonstrating reactivity that replicates and in some cases exceeds that of their more...

We describe the synthesis and characterization of hexabenzo[5.6.7]quinarene, which is composed of an anthraquinodimethane (AQD) central core that is end-capped with fluorenyl and dibenzosuberenyl...

Phenothiazine cyclic hexamers linked at the 3,7-positions were synthesized. Effects of the cyclic structure as well as substituent effects of the nitrogen atom were disclosed. Furthermore, the cyclic...

A new armchair carbon nanobelt is successfully synthesized by tuning the regioselectivity of the Scholl reaction of 1,1′:2′,1′′:4′′,1′′′:2′′′,1′′′′-quinquephenyl. This nanobelt exhibits a preferent...

Dithienylethene-strapped calix[4]pyrrole is isomerized by 300/630 nm light between ring-open and -closed isomers, which affects the size of the anion binding site. Where for chloride this results in...

This minireview aims to cover the developments of the last few years in the design of reagents able to accomplish the umpolung of the azomethine carbon in diazo compounds namely, α-diazo-λ3-iodanes...

Functional fluorophores represent an emerging research field, distinguished by their diverse applications, especially in sensing and cellular imaging. After the discovery of quinine sulfate and...

Our efforts in carbocation chemistry have led us to target examples of such species stabilized intramolecularly by tetrel bonding. Described here is an example of such a compound in which a triaryl...

Hydrogen-bonded frameworks were prepared from a tetra-amidinium component and three-dimensional cubane and bicyclopentane dicarboxylate linkers. Despite the incorporation of aliphatic components, the...

Certain metal sandwich complexes undergo dimerization through metal–metal bond formation. Here, we found that a reductive dimerization of mixed-metal Pd2Pt or PdPt2 sandwich complexes proceeds...

Heptagon-embedded polycyclic aromatic dicarboximides were developed as new push–pull fluorescent dyes through palladium-catalysed [4+3] annulation followed by nucleophilic substitution. The introdu...

Resonant acoustic mixing (RAM) enables mechanoredox catalysis with BaTiO3 as the piezoelectric catalyst on model diazonium coupling reactions. RAM proceeds without formal grinding or impact media, is...

Ultrafast C–H bond activation and functionalization in confinement using visible light will enable engineering chemical reactions with extraordinary speed and selectivity. To provide a transition...

Phenothiazine cyclic hexamers linked at the 3,7-positions were synthesized. Effects of the cyclic structure as well as substituent effects of the nitrogen atom were disclosed. Furthermore, the cyclic...

[{SiNDipp}MgNa]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3) reacts directly with H2 to provide a heterobimetallic hydride. Although the transformation is complicated by the simultaneous...

Herein we introduce 3-vinyl-1,2,4-triazines derivatives as dual-reactive linkers that exhibit selectivity towards cysteine and specific strained alkynes, enabling conjugate addition and inverse...

Phosphino(silyl)carbenes are known for their ineptitude to form transition metal complexes. We describe the synthesis of phosphino(silyl)carbenes bearing N-heterocyclic imine groups and show that...

Tacticity is critical to polymer properties. The influence of solvent on tacticity in the catalytic synthesis of cyclic polynorbornene (c-PNB) is reported. In toluene cis,syndiotactic c-PNB forms; in...

The synthesis and characterisation of [Co2(η4-P2C2tBu2)2(μ:η4:η4-P2C2tBu2)] (1) is described, featuring two cobalt atoms and three diphosphacyclobutadiene ligands. This compound is the first triple...

Dynamic covalent bonds have been advantageously used to direct the synthesis of crystalline porous covalent organic frameworks (COFs). Unlike the standard synthetic protocols that involve harsh...

The development of novel catalysts for C–H activation reactions with increased reactivity and improved selectivities has been attracting significant interest over the last two decades. More recently,...

Although alkynes are one of the smallest functional groups, they are among the most versatile building blocks for organic chemistry, with applications ranging from biochemistry to material sciences....

Herein we introduce 3-vinyl-1,2,4-triazines derivatives as dual-reactive linkers that exhibit selectivity towards cysteine and specific strained alkynes, enabling conjugate addition and inverse...

The aluminium salt [(NHC)Al(tol)(C6F5)2][B(C6F5)4], (NHC = C3H2(N(iPr2C6H3))2) is shown to behave as a Lewis superacid as it abstracts fluoride from [SbF6]−. It also acts as a Lewis acid catalyst for...

Photochromic conducting molecules have emerged because of their unique capacity to modulate electrical conductivity upon exposure to light, toggling between high and low conductive states. This...

Hexafluoroisopropanol (HFIP) is a solvent with unique properties that has recently gained attention for promoting a wide range of challenging chemical reactions. It was initially believed that HFIP...

Biaryl sulfonamides are excellent candidates for the azologization approach that yields photoswitchable drugs more active in their metastable cis state, compared to the stable trans state. Here we...

The traditional and widespread rationale behind the stability trend of alkyl-substituted carbocations is incomplete. Through state-of-the-art quantum chemical analyses, we quantitatively established...

The non-bonding carbone lone pair in geometrically-constrained antimony and bismuth carbodiphosphorane complexes readily complexed AuCl to afford rare examples of geminal bimetallic carbone coordin...

Multimetallic catalysis is a powerful strategy to access complex molecular scaffolds efficiently from easily available starting materials. Numerous reports in the literature have demonstrated the...

A doubly-interlocked [2]catenane – or Solomon link – undergoes a complex conformational change upon addition of sulfate in methanol. This transformation generates a single pocket where two SO42−...

We describe the rational development of a design for pleochroic molecular solids, by using C−I⋯π halogen bonds to pre-organise different chromophores in a cocrystal. Using the structure of a known...

We report an iridium system constructed around a long-tethered PGeP ligand that facilitates access to the less common germylene form, so far unreported for an ‘NHC-type’ Ge ligand. Its bonding is...

Three-dimensional covalent connectors are valuable synthons for accessing crystalline or amorphous networks. Currently, fused polycyclic alkanes are employed as connectors in this context. We debut...

Herein, we describe the design and synthesis of an unusual azobenzene-bearing macrocycle 1, whose trans isomer was found able to 100% transform into its cis configuration under photoirradiation, for...

A robust multigram-scale synthesis of 1,3-disubstituted cubanes (previously only available on milligram-scale) is reported. The approach exploits a readily available enone intermediate previously...

In this communication we describe a helically chiral push–pull molecule named 9,10-dimethoxy-[7]helicene diimide, displaying fluorescence (FL) and circularly polarised luminescence (CPL) over nearly...

The design of bright short-wave infrared fluorophores remains a grand challenge. Here we investigate the impact of deuteration on the properties in a series of heptamethine dyes, the absorption of...

Ammonium-dibenzo[24]crown-8 [2]catenane functionalisation of a 3,5-bis-iodotriazole-pyridine motif produces a potent halogen bonding (XB) receptor capable of binding anions in aqueous-acetone solvent...

Chemical double mutant cycles were used to measure the interaction of a N-methyl pyridinium cation with a π-box in a calix[4]pyrrole receptor. Although the cation–π interaction is attractive (−11 kJ...

A three-dimensional skeleton, π-fused [4.3.3]propellane, was constructed and derivatized by selective π-extension at the two naphthalene units. The obtained propellanes existed as stereoisomers...

We report aqueous, site-selective modification of proteins using a reactive peptide interface comprising a nine-residue sequence. This interface is the fastest (second-order rate constant of 152 M−1...

We present a readily available calix[5]arene derived cavitand receptor that is stabilized in the closed cone conformer through intermolecular hydrogen bonding with methanol molecules. The receptor...

Herein, we report the insertion of a difluoromethylene into 1,1,2,2-tetrafluoro-2-arylethyl copper complexes to synthesize extended perfluoroalkyl-bridged compounds that have various functional...

The conversion of light alkanes into bulk chemicals is becoming an important challenge as it effectively avoids the use of prefunctionalized alkylating reagents. The implementation of such processes...

Hydrogen-bonded organic frameworks (HOFs) constructed from naphthalene-diimide bearing tectons undergo photochromic changes whilst forming radical bearing species within the framework structure.

Triphenylborane catalyzes the polymerization of anhydrides and epoxides along with the block co-polymerization of anhydride/epoxides with epoxides/CO2. Switching to the more Lewis acidic borane,...

The synthesis and properties of photoswitchable electron-rich phosphines containing N-heterocyclic imines equipped with a photochromic dithienylethene unit are reported. Heteronuclear NMR spectrosc...