A Conjugate Addition Approach to Diazo-Containing Scaffolds with β Quaternary Centers

Structurally complex diazo-containing scaffolds are formed by conjugate addition to vinyl diazonium salts. The electrophile, a little studied α-diazonium-α,β-unsaturated carbonyl compound, is formed at low temperature under mild conditions by treating β-hydroxy-α-diazo carbonyls with Sc(OTf)₃. Conjugate addition occurs selectively at the 3-position of indole to give α-diazo-β-indole carbonyls, and enoxy silanes react to give 2-diazo-1,4-dicarbonyl products. These reactions result in the formation of tertiary and quaternary centers, and give products that would be otherwise difficult to form. Importantly, the diazo functional group is retained within the molecule for future manipulation. Treating an α-diazo ester indole addition product with Rh₂(OAc)₄ caused a rearrangement to occur to give a 2-(1H-indol-3-yl)-2-enoate. In the case of diazo ketone compounds, this shift occurred spontaneously on prolonged exposure to the Lewis acidic reaction conditions.     

A Single-Atom Manipulation Approach for Synthesis of Atomically Mixed Nanoalloys as Efficient Catalysts

Synthesis of well-defined atomically mixed alloy nanoparticles on desired substrates is an ultimate goal for their practical application. Herein we report a general approach for preparing atomically mixed AuPt, AuPd, PtPd, AuPtPd NAs(nanoalloys) through single-atom level manipulation. By utilizing the ubiquitous tendency of aggregation of single atoms into nanoparticles at elevated temperatures, we have synthesized nanoalloys on a solid solvent with CeO₂ as a carrier and transition-metal single atoms as an intermediate state. The supported nanoalloys/CeO₂ with ultra-low noble metal content (containing 0.2 wt % Au and 0.2 wt % Pt) exhibit enhanced catalytic performance towards complete CO oxidation at room temperature and remarkable thermostability. This work provides a general strategy for facile and rapid synthesis of well-defined atomically mixed nanoalloys that can be applied for a range of emerging techniques.     

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

Electron momentum spectroscopy, scanning tunneling microscopy, and photoelectron spectroscopy provide unique information about electronic structure, but their interpretation has been controversial. This essay discusses a framework for interpretation. Although this interpretation is not new, we believe it is important to present this framework in light of recent publications. The key point is that these experiments provide information about how the electron distribution changes upon ionization, not how electrons behave in the pre‐ionized state. Therefore, these experiments do not lead to a “selection of the correct orbitals” in chemistry and do not overturn the well‐known conclusion that both delocalized molecular orbitals and localized molecular orbitals are useful for interpreting chemical structure and dynamics. The two types of orbitals can produce identical total molecular electron densities and therefore molecular properties. Different types of orbitals are useful for different purposes.     

Meta Junction Promoting Efficient Thermally Activated Delayed Fluorescence in Donor-Acceptor Conjugated Polymers

The meta junction is proposed to realize efficient thermally activated delayed fluorescence (TADF) in donor–acceptor (D-A) conjugated polymers. Based on triphenylamine as D and dicyanobenzene as A, as a proof of concept, a series of D-A conjugated polymers has been developed by changing their connection sites. When the junction between D and A is tuned from para to meta, the singlet–triplet energy splitting (ΔE_ST) is found to be significantly decreased from 0.44 to 0.10 eV because of the increasing hole–electron separation. Unlike the para-linked analogue with no TADF, consequently, the meta-linked polymer shows a strong delayed fluorescence. Its corresponding solution-processed organic light-emitting diodes (OLEDs) achieve a promising external quantum efficiency (EQE) of 15.4 % (51.9 cd A⁻¹, 50.9 lm W⁻¹) and CIE coordinates of (0.34, 0.57). The results highlight the bright future of D-A conjugated polymers used for TADF OLEDs.     

Accelerating Electrochemical Reactions in a Voltage-Controlled Interfacial Microreactor

Microdroplet chemistry is attracting increasing attention for accelerated reactions at the solution–air interface. We report herein a voltage-controlled interfacial microreactor that enables acceleration of electrochemical reactions which are not observed in bulk or conventional electrochemical cells. The microreactor is formed at the interface of the Taylor cone in an electrospray emitter with a large orifice, thus allowing continuous contact of the electrode and the reactants at/near the interface. As a proof-of-concept, electrooxidative C−H/N−H coupling and electrooxidation of benzyl alcohol were shown to be accelerated by more than an order of magnitude as compared to the corresponding bulk reactions. The new electrochemical microreactor has unique features that allow i) voltage-controlled acceleration of electrochemical reactions by voltage-dependent formation of the interfacial microreactor; ii) “reversible” electrochemical derivatization; and iii) in situ mechanistic study and capture of key radical intermediates when coupled with mass spectrometry.     

High-Capacity and Stable Li-O2 Batteries Enabled by a Trifunctional Soluble Redox Mediator

Li-O₂ batteries with ultrahigh theoretical energy densities usually suffer from low practical discharge capacities and inferior cycling stability owing to the cathode passivation caused by insulating discharge products and by-products. Here, a trifunctional ether-based redox mediator, 2,5-di-tert-butyl-1,4-dimethoxybenzene (DBDMB), is introduced into the electrolyte to capture reactive O₂⁻ and alleviate the rigorous oxidative environment of Li-O₂ batteries. Thanks to the strong solvation effect of DBDMB towards Li⁺ and O₂⁻, it not only reduces the formation of by-products (a high Li₂O₂ yield of 96.6 %), but also promotes the solution growth of large-sized Li₂O₂ particles, avoiding the passivation of cathode as well as enabling a large discharge capacity. Moreover, DBDMB makes the oxidization of Li₂O₂ and the decomposition of main by-products (Li₂CO₃ and LiOH) proceed in a highly effective manner, prolonging the stability of Li-O₂ batteries (243 cycles at 1000 mAh g⁻¹ and 1000 mA g⁻¹).     

Supramolecular Catalysis of the oxa-Pictet–Spengler Reaction with an Endohedrally Functionalized Self-Assembled Cage Complex

An endohedrally functionalized self-assembled Fe₄L₆ cage complex can catalyze oxa-Pictet—Spengler cyclizations of tryptophols and various aldehyde derivatives, showing strong rate accelerations and size-selectivity. Selective molecular recognition of substrates controls the reactivity, and the cage is capable of binding and activating multiple different species along the multistep reaction pathway. The combination of a functionalized active site, size-selective reactivity, and multistep activation, all from a single host molecule, illustrates the biomimetic nature of the catalysis.     

Atomistic Insight Into the Host–Guest Interaction of a Photoresponsive Metal–Organic Framework

Photoresponsive functional materials have gained increasing attention due to their externally tunable properties. Molecular switches embedded in these materials enable the control of phenomena at the atomic level by light. Metal–organic frameworks (MOFs) provide a versatile platform to immobilize these photoresponsive units within defined molecular environments to optimize the intended functionality. For the application of these photoresponsive MOFs (pho-MOFs), it is crucial to understand the influence of the switching state on the host–guest interaction. Therefore, we present a detailed insight into the impact of molecular switching on the intermolecular interactions. By performing atomistic simulations, we revealed that due to different interactions of the guest molecules with the two isomeric states of an azobenzene-functionalized MOF, both the adsorption sites and the orientation of the molecules within the pores are modulated. By shedding light on the host–guest interaction, our study highlights the unique potential of pho-MOFs to tailor molecular interaction by light.     

Atropisomers of meso Tetra(N-Mesyl Pyrrol-2-yl) Porphyrins: Synthesis,Isolation and Characterization of All-Pyrrolic Porphyrins

Atropisomerism has been observed in a variety of biaryl compounds and meso-aryl substituted porphyrins. However, in porphyrins, this phenomenon had been shown only with o-substituted 6-membered aromatic groups at the meso-position. We show herein that a 5-membered heteroaromatic (N-mesyl-pyrrol-2-yl) group at the meso-position leads to atropisomerism. In addition, we report a ‘one-pot’ synthetic route for the synthesis of ‘all-pyrrolic’ porphyrin (APP) with several N-protection groups (Boc, Cbz, Ms and Ts). Among these groups, we found that only the Ms group gave four individually separable atropisomers of meso-tetra(N-Ms-pyrrol-2-yl) porphyrin. Furthermore, the reductive removal of Cbz- was achieved to obtain meso-tetra(pyrrol-2-yl) porphyrin. Thus, our synthetic procedure provides an easy access to a group of APPs and stable atropisomers, which is expected to expand the application of novel APP-based materials.     

Ring Enlargement of Three-Membered Heterocycles by Treatment with In Situ Formed Tricyanomethane

Although the chemistry of elusive tricyanomethane (cyanoform) has been studied during a period of more than 150 years, this compound has very rarely been utilized in the synthesis or modification of heterocycles. Three-membered heterocycles, such as epoxides, thiirane, aziridines, or 2H-azirines, are now treated with tricyanomethane, which is generated in situ by heating azidomethylidene-malonodinitrile in tetrahydrofuran at 45 °C or by adding sulfuric acid to potassium tricyanomethanide. This leads to ring expansion with formation of 2-(dicyanomethylidene)oxazolidine derivatives or creation of the corresponding thiazolidine, imidazolidine, or imidazoline compounds and opens up a new access to these push–pull-substituted olefinic products. The regio- and stereochemistry of the ring-enlargement processes are discussed, and the proposed reaction mechanisms were confirmed by using ¹⁵N-labeled substrates. It turns out that different mechanisms are operating; however, tricyanomethanide is always acting as a nitrogen-centered nucleophile, which is quite unusual if compared to other reactions of this species.