Designing naphthopyran mechanophores with tunable mechanochromic behavior

Mechanochromic molecular force probes conveniently report on stress and strain in polymeric materials through straightforward visual cues. We capitalize on the versatility of the naphthopyran framework to design a series of mechanochromic mechanophores that exhibit highly tunable color and fading kinetics after mechanochemical activation. Structurally diverse naphthopyran crosslinkers are synthesized and covalently incorporated into silicone elastomers, where the mechanochemical ring–opening reactions are achieved under tension to generate the merocyanine dyes. Strategic structural modifications to the naphthopyran mechanophore scaffold produce dramatic differences in the color and thermal electrocyclization behavior of the corresponding merocyanine dyes. The color of the merocyanines varies from orange-yellow to purple upon the introduction of an electron donating pyrrolidine substituent, while the rate of thermal electrocyclization is controlled through electronic and steric factors, enabling access to derivatives that display both fast-fading and persistent coloration after mechanical activation and subsequent stress relaxation. In addition to identifying key structure–property relationships for tuning the behavior of the naphthopyran mechanophore, the modularity of the naphthopyran platform is demonstrated by leveraging blends of structurally distinct mechanophores to create materials with desirable multicolor mechanochromic and complex stimuli-responsive behavior, expanding the scope and accessibility of force-responsive materials for applications such as multimodal sensing.

Structure–activity relationships for strategic substitution of the naphthopyran mechanophore scaffold enable polymeric materials with tunable mechanochromic behavior.     

A modular approach to mechanically gated photoswitching with color-tunable molecular force probes

Molecular force probes conveniently report on mechanical stress and/or strain in polymers through straightforward visual cues. Unlike conventional mechanochromic mechanophores, the mechanically gated photoswitching strategy decouples mechanochemical activation from the ultimate chromogenic response, enabling the mechanical history of a material to be recorded and read on-demand using light. Here we report a completely redesigned, highly modular mechanophore platform for mechanically gated photoswitching that offers a robust, accessible synthesis and late stage diversification through Pd-catalyzed cross-coupling reactions to precisely tune the photophysical properties of the masked diarylethene (DAE) photoswitch. Using solution-phase ultrasonication, the reactivity of a small library of functionally diverse mechanophores is demonstrated to be exceptionally selective, producing a chromogenic response under UV irradiation only after mechanochemical activation, revealing colored DAE isomers with absorption spectra that span the visible region of the electromagnetic spectrum. Notably, mechanically gated photoswitching is successfully translated to solid polymeric materials for the first time, demonstrating the potential of the masked diarylethene mechanophore for a variety of applications in force-responsive polymeric materials.

A highly modular and synthetically accessible mechanophore platform enables mechanically gated photoswitching in solution and in solid polymeric materials.     

Mechanochemical generation of acid-degradable poly(enol ether)s

In an effort to develop polymers that can undergo extensive backbone degradation in response to mechanical stress, we report a polymer system that is hydrolytically stable but unmasks easily hydrolysable enol ether backbone linkages when force is applied. These polymers were synthesized by ring-opening metathesis polymerization (ROMP) of a novel mechanophore monomer consisting of cyclic ether fused bicyclohexene. Hydrogenation of the resulting polymers led to significantly enhanced thermal stability (T_d > 400 °C) and excellent resistance toward acidic or basic conditions. Solution ultrasonication of the polymers resulted in up to 65% activation of the mechanophore units and conversion to backbone enol ether linkages, which then allowed facile degradation of the polymers to generate small molecule or oligomeric species under mildly acidic conditions. We also achieved solid-state mechano-activation and polymer degradation via grinding the solid polymer. Force-induced hydrolytic polymer degradability can enable materials that are stable under force-free conditions but readily degrade under stress. Facile degradation of mechanically activated polymechanophores also facilitates the analysis of mechanochemical products.

A mechanically responsive polymer system that is hydrolytically stable without stress, but unmasks enol ether backbone linkages under force to allow facile hydrolytic degradation.     

Multiplexed and amplified chemiluminescence resonance energy transfer (CRET) detection of genes and microRNAs using dye-loaded hemin/G-quadruplex-modified UiO-66 metal–organic framework nanoparticles

Dye-loaded UiO-66 metal–organic framework nanoparticles (NMOFs) modified with catalytic hemin/G-quadruplex DNAzyme labels act as functional hybrid modules for the chemiluminescence resonance energy transfer (CRET) analysis of miRNAs (miRNA-155 or miRNA-21) or genes (p53 or BRCA1). The dye-loaded NMOFs (dye = fluorescein (Fl) or rhodamine 6G (Rh 6G)) are modified with hairpin probes that are engineered to include in their loop domains recognition sequences for the miRNAs or genes, and in their stem regions caged G-quadruplex domains. In the presence of the analytes miRNAs or genes, the hairpin structures are opened, leading, in the presence of hemin, to the self-assembly of hemin/G-quadruplex DNAzyme labels linked to the dye-loaded NMOFs. In the presence of luminol and H₂O₂, the hemin/G-quadruplex DNAzyme labels catalyze the generation of chemiluminescence that provides radiative energy to stimulate the process of CRET to the dye loaded in the NMOFs, resulting in the luminescence of the loaded dye without external excitation. The resulting CRET signals relate to the concentrations of the miRNAs or the genes and allow the sensitive analysis of miRNAs and genes. In addition, the DNA hairpin-functionalized dye-loaded NMOF sensing modules were further applied to develop amplified miRNA or gene CRET-based sensing platforms. The dye-loaded NMOFs were modified with hairpin probes that include in their loop domain the recognition sequences for miRNA-155 or miRNA-21 or the recognition sequences for the p53 or BRCA1 genes. Subjecting the hairpin-modified NMOFs to the respective miRNAs or genes, in the presence of two hairpins H_i and H_j that include in their stem regions caged G-quadruplex subunit domains, results in the analyte-triggered opening of the probe hairpin linked to the NMOFs, and the opened hairpin tethers induce the cross-opening of the hairpins H_i and H_j by the hybridization chain reaction, HCR, resulting in the assembly of G-quadruplex wires tethered to the NMOFs. The binding of hemin to the HCR-generated chains yields hemin/G-quadruplex DNAzyme wires that enhance, in the presence of luminol/H₂O₂, the CRET processes in the hybrid nanostructures. These amplification platforms lead to the amplified sensing of miRNAs and genes. By mixing the Fl- and Rh 6G-loaded hairpin-functionalized UiO NMOFs, the multiplexed CRET detection of miRNA-155, miRNA-21 and the p53 and BRCA1 genes is demonstrated.

Hemin/G-quadruplex DNAzyme-modified metal–organic framework nanoparticles act as functional hybrids for the catalyzed oxidation of luminol by H₂O₂, causing chemiluminescence and activation of chemiluminescence resonance energy transfer to the dye loads.     

Rh(i)- and Rh(ii)-catalyzed C–H alkylation of benzylamines with alkenes and its application in flow chemistry

The Rh-catalyzed C–H alkylation of benzylamines with alkenes using a picolinamide derivative as a directing group is reported. Both Rh(i) and Rh(ii) complexes can be used as active catalysts for this transformation. In addition, a flow set up was designed to successfully mimic this process under flow conditions. Several examples are presented under flow conditions and it was confirmed that a flow process is advantageous over a batch process. Deuterium labelling experiments were performed to elucidate the mechanism of the reaction, and the results indicated a possible carbene mechanism for this C–H alkylation process.

Rh(i)- and Rh(ii)-catalyzed C–H alkylation of benzylamines with alkenes using a picolinamide derivative as a directing group is reported under both batch and flow.     

Palladium-catalyzed hydroalkylation of methylenecyclopropanes with simple hydrazones

A palladium-catalyzed hydroalkylation reaction of methylenecyclopropanes via highly selective C–C σ-bond scission was achieved under mild conditions, in which simple hydrazones served as carbanion equivalents. This method featured good functional group compatibility, affording high yields of C-alkylated terminal alkenes.

A palladium-catalyzed hydroalkylation of methylenecyclopropanes via selective C–C σ-bond scission was achieved, in which simple hydrazones served as carbanion equivalents. This method affords high yields of C-alkylated terminal alkenes with good functional group compatibility.     

Rh(i)-catalyzed stereoselective desymmetrization of prochiral cyclohexadienones via highly exo-selective Huisgen-type [3 + 2] cycloaddition

A Rh(i)-catalyzed highly stereoselective desymmetrization of 2-alkynylbenzaldehyde-tethered cyclohexadienones triggered by intramolecular Huisgen-type [3 + 2] cycloaddition has been developed. This method enables convergent construction of complex epoxy-bridged polycyclic ring systems with five contiguous stereocenters with excellent exo-selectivity and broad substrate scope. The highly atom-economical process involves 6-endo-dig cyclization of carbonyl oxygen onto an activated alkyne resulting in a highly reactive metal–benzopyrylium intermediate, which readily undergoes intramolecular [3 + 2] annulation/hydration. Asymmetric induction is also achieved for the first time in Rh(i)-catalyzed 1,3-dipolar cycloaddition using an easily accessible chiral diene as the ligand.

A Rh(i)-catalyzed highly stereoselective desymmetrization of 2-alkynylbenzaldehyde-tethered cyclohexadienones triggered by intramolecular Huisgen-type [3 + 2] cycloaddition has been developed.     

Photocatalytic Umpolung of N- and O-substituted alkenes for the synthesis of 1,2-amino alcohols and diols

We report an organophotocatalytic 1,2-oxyalkynylation of ene-carbamates and enol ethers using Ethynyl BenziodoXolones (EBXs). 1-Alkynyl-1,2-amino alcohols and diols were obtained in up to 89% yield. Photocatalytic formation of radical cations led to Umpolung of the innate reactivity of the alkenes, enabling addition of a nucleophilic benzoate followed by radical alkynylation.

Photocatalytic Umpolung with organic dyes overcoming the innate nucleophilicity of enecarbamates and enol ethers for oxyalkynylation with EBX reagents to access 1-alkynyl-1,2-amino alcohols and diols.     

Asymmetric synthesis of 1,2-fluorohydrin: iridium catalyzed hydrogenation of fluorinated allylic alcohol

We have developed a simple protocol for the preparation of 1,2-fluorohydrin by asymmetric hydrogenation of fluorinated allylic alcohols using an efficient azabicyclo thiazole-phosphine iridium complex. The iridium-catalyzed asymmetric synthesis of chiral 1,2-fluorohydrin molecules was carried out at ambient temperature with operational simplicity, and scalability. This method was compatible with various aromatic, aliphatic, and heterocyclic fluorinated compounds as well as a variety of polyfluorinated compounds, providing the corresponding products in excellent yields and enantioselectivities.

We have developed a simple protocol for the preparation of 1,2-fluorohydrin by asymmetric hydrogenation of fluorinated allylic alcohols using an efficient azabicyclo thiazole-phosphine iridium complex.     

Mechanophores with a Reversible Radical System and Freezing‐Induced Mechanochemistry in Polymer Solutions and Gels

Visualization and quantitative evaluation of covalent bond scission in polymeric materials are highly important for understanding failure, fatigue, and deterioration mechanisms and improving the lifetime, durability, toughness, and reliability of the materials. The diarylbibenzofuranone‐based mechanophore radical system enabled, through electron paramagnetic resonance spectroscopy, in situ quantitative evaluation of scission of the mechanophores and estimation of mechanical energy induced along polymer chains by external forces. The coagulation of polymer solutions by freezing probably generated force but did not cleave the mechanophores. On the other hand, cross‐linking led to efficient propagation of the force of more than 80 kJ mol^?1 to some mechanophores, resulting their cleavage and generation of colored stable radicals. This mechanoprobe concept has the potential to elucidate other debated issues in the polymer field as well.     

A pyrone remodeling strategy to access diverse heterocycles: application to the synthesis of fascaplysin natural products

The synthesis of diverse N-fused heterocycles, including the pyrido[1,2-a]indole scaffold, using an efficient pyrone remodeling strategy is described. The pyrido[1,2-a]indole core was demonstrated to be a versatile scaffold that can be site-selectively functionalized. The utility of this novel annulation strategy was showcased in a concise formal synthesis of three fascaplysin congeners.

The synthesis of diverse N-fused heterocycles, including the pyrido[1,2-a]indole scaffold, using an efficient pyrone remodeling strategy is described.     

Recent developments in nickel-catalyzed intermolecular dicarbofunctionalization of alkenes

Nickel-catalyzed three-component alkene difunctionalization has rapidly emerged as a powerful tool for forging two C–C bonds in a single reaction. Building upon the powerful modes of bond construction in traditional two-component cross-coupling, various research groups have demonstrated the versatility of nickel in enabling catalytic 1,2-dicarbofunctionalization using a wide range of carbon-based electrophiles and nucleophiles and in a fully intermolecular fashion. Though this area has emerged only recently, the last few years have witnessed a proliferation of publications on this topic, underscoring the potential of this strategy to develop into a general platform that offers high regio- and stereoselectivity. This minireview highlights the recent progress in the area of intermolecular 1,2-dicarbofunctionalization of alkenes via nickel catalysis and discusses lingering challenges within this reactivity paradigm.

Nickel-catalyzed three-component alkene difunctionalization has rapidly emerged as a powerful tool for forging multiple C–C bonds in a single step.     

High-performance polymer field-effect transistors: from the perspective of multi-level microstructures

The multi-level microstructure of conjugated polymers is the most critical parameter determining the charge transport property in field-effect transistors (FETs). However, controlling the hierarchical microstructures and the structural evolution remains a significant challenge. In this perspective, we discuss the key aspects of multi-level microstructures of conjugated polymers towards high-performance FETs. We highlight the recent progress in the molecular structures, solution-state aggregation, and polymer crystal structures, representing the multi-level microstructures of conjugated polymers. By tuning polymer hierarchical microstructures, we attempt to provide several guidelines for developing high-performance polymer FETs and polymer electronics.

The multi-level microstructures of conjugated polymers, including solution-state aggregation and crystal structures, are reviewed due to their influence on charge transport in polymer field-effect transistors.     

Chemiluminescence of 1,2-dioxetane. Reaction mechanism uncovered

The thermal decomposition of 1,2-dioxetane and the associated production of chemiluminescent products, model for a wide range of chemiluminescent reactions, has been studied at the multistate multiconfigurational second-order perturbation level of theory. This study is in qualitative and quantitative agreement with experimental observations with respect to the activation energy and the observed increase of triplet and singlet excited products as substituents are added to the parent molecule. The, previously incomplete, reaction mechanism of the chemiluminescence of 1,2-dioxetane is now rationalized and described as mainly due to a particular form of entropic trapping.     

C60 fullerene, as ultraefficient quencher of singlet-excited adamantanone generated in photo-and chemiexcitation

Quenching of the fluorescence of Ad=O and its singlet-exited state (¹Ad=O*) generated in chemiluminescent reaction of adamantylideneadamantane-1,2-dioxetane (AdOOAd) termolysis by C₆₀ fullerene was detected and investigated. The “quenching efficiency-C₆₀ concentration” plots obtained from the decrease in the fluorescence and chemiluminescence intensities obey the Stern-Volmer law. The bimolecular rate constants (k _bim) were determined and the overlap integrals of the Ad=O fluorescence spectra with the C₆₀ absorption spectra (∫ _Ov) were calculated. Based on the nonconstant k _bim/∫_Ov ratios for different singlet-exited energy donors obtained for the ¹PAH*-C₆₀ systems (PAH are polycyclic aromatic hydrocarbons) and ¹Ad=O*-C₆₀, a conclusion is drawn that quenching of ¹Ad=O* by C₆₀ fullerene is a result of inductive-resonant singlet-singlet (major contribution) and exchange-resonant singlet-triplet (minor contribution) energy transfer. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1044–1046, May, 2007.     

Isomeric anthracene diimide polymers

N-type semiconducting polymers are attractive for organic electronics, but desirable electron-deficient units for synthesizing such polymers are still lacking. As a cousin of rylene diimides such as naphthalene diimide (NDI) and perylene diimide (PDI), anthracene diimide (ADI) is a promising candidate; its polymers, however, have not been achieved yet because of synthetic challenges for its polymerizable monomers. Herein, we present ingenious synthesis of two dibromide ADI monomers with dibromination at differently symmetrical positions of the ADI core, which are further employed to construct ADI polymers. More interestingly, the two obtained ADI polymers possess the same main-chain and alkyl-chain structures but different backbone conformations owing to varied linking positions between repeating units. This feature enables their different optoelectronic properties and film-state packing behavior. The ADI polymers offer first examples of conjugated polymer conformational isomers and are highly promising as a new class of n-type semiconductors for various organic electronics applications.

Two anthracene diimide (ADI) polymers with the backbone conformational isomerism, new members of aromatic diimide polymers family, have been synthesized as a class of highly promising n-type semiconductors for organic electronics.     

Oxidative regulation of the mechanical strength of a C–S bond

The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness. Methods by which the intrinsic molecular strength of the constituents of a given polymeric material might be switched are therefore potentially useful both for applications in which triggered property changes are desirable, and as tests of molecular theories for bulk behaviors. Here we report that the sequential oxidation of sulfide containing polyesters (PE-S) to the corresponding sulfoxide (PE-SO) and then sulfone (PE-SO2) first weakens (sulfoxide), and then enhances (sulfone), the effective mechanical integrity of the polymer backbone; PE-S ∼ PE-SO2 > PE-SO. The relative mechanical strength as a function of oxidation state is revealed through the use of gem-dichlorocyclopropane nonscissile mechanophores as an internal standard, and the observed order agrees well with the reported bond dissociation energies of C–S bonds in each species and with the results of CoGEF modeling.

The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness.     

Hydrophosphination of boron–boron multiple bonds

Five compounds containing boron–boron multiple bonds are shown to undergo hydrophosphination reactions with diphenylphosphine in the absence of a catalyst. With diborenes, the products obtained are highly dependent on the substitution pattern at the boron atoms, with both 1,1- and 1,2-hydrophosphinations observed. With a symmetrical diboryne, 1,2-hydrophosphination yields a hydro(phosphino)diborene. The different mechanistic pathways for the hydrophosphination of diborenes are rationalised with the aid of density functional theory calculations.

Compounds containing boron–boron double and triple bonds are shown to undergo uncatalysed hydrophosphination reactions with diphenylphosphine.     

Rapidly self-deoxygenating controlled radical polymerization in water via in situ disproportionation of Cu(i)

Rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated. The disproportionation of Cu(i)/Me₆Tren in water towards Cu(ii) and highly reactive Cu(0) leads to O₂-free reaction environments within the first seconds of the reaction, even when the reaction takes place in the open-air. By leveraging this significantly fast O₂-reducing activity of the disproportionation reaction, a range of well-defined water-soluble polymers with narrow dispersity are attained in a few minutes or less. This methodology provides the ability to prepare block copolymers via sequential monomer addition with little evidence for chain termination over the lifetime of the polymerization and allows for the synthesis of star-shaped polymers with the use of multi-functional initiators. The mechanism of self-deoxygenation is elucidated with the use of various characterization tools, and the species that participate in the rapid oxygen consumption is identified and discussed in detail.

The rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated.     

Rhodium-catalyzed cascade reactions of triazoles with organoselenium compounds – a combined experimental and mechanistic study

Herein, we report on our studies on the reaction of organoselenium compounds with triazoles under thermal conditions using simple Rh(ii) catalysts. These reactions do not provide the product of classic rearrangement reactions. Instead two different cascade reactions were uncovered. While allyl selenides react in a cascade of sigmatropic rearrangement and selenium-mediated radical cyclization reaction to give dihydropyrroles, cinnamyl selenides undergo a double rearrangement reaction cascade involving a final aza-Cope reaction to give the product of 1,3-difunctionalization. Theoretical and experimental studies were conducted to provide an understanding of the reaction mechanism of these cascade reactions. The former provide an important insight into fundamental question on the nature of the ylide intermediate in rearrangement reactions and reveal that organoselenium compounds take up multiple roles in rearrangement reactions and mediate a free ylide reaction mechanism.

Herein, we report on our studies on the reaction of organoselenium compounds with triazoles under thermal conditions using simple Rh(ii) catalysts.