A Terminal Iridium Oxo Complex with a Triplet Ground State

A terminal iridium oxo complex with an open‐shell (S=1) ground state was isolated upon hydrogen atom transfer (HAT) from the respective iridium(II) hydroxide. Electronic structure examinations support large spin delocalization to the oxygen atom. Selected oxo transfer reactions indicate the ambiphilic reactivity of the iridium oxo moiety. Calorimetric and computational examinations of the HAT revealed a bond dissociation free energy for the IrO?H bond that is sufficient for hydrogen atom abstraction towards C?H bonds and small contributions from entropy and spin–orbit coupling to the HAT thermochemistry.     

A Convenient Route to Functionalized Branched-Chain Sugars Via a Tosyl-Epoxide Derivative

Abstract

Starting from methyl 4,6-O-benzylidene-2-deoxy-α-D-ribo-hexopyranoside-3-ulose 1 and proceeding through its corresponding tosyl-epoxide derivative 2, various branched-chain sugars (3-8) were prepared by nucleophilic and reductive ring openings. The presence of the sulfonylated oxirane group was found to be compatible with chemical transformations of the benzylidene acetal group (9-11), allowing facile access to the 6-deoxyhexoses (12-13).     

A Stable,Soluble, and Crystalline Supramolecular System with a Triplet Ground State

A supramolecular complex was constructed by encapsulation of a ³O₂ molecule inside an open‐cage C₆₀ derivative. Its single‐crystal X‐ray diffraction analysis revealed the presence of the ³O₂ at the center of the fullerene cage. The CV measurements suggested that unprecedented dehydrogenation was promoted by the encapsulated ³O₂ after two‐electron reduction. The ESR measurements displayed the triplet character as well as the anisotropy of the ³O₂. Additionally, the SQUID measurements also demonstrated the paramagnetic behavior above 3 K without an antiferromagnetic transition. Upon photoirradiation with visible light, three phosphorescent bands at the NIR region were observed, arising from the exited ¹O₂ generated by self‐sensitization with the outer cage, whose lifetimes were not affected by the environments. These studies confirmed that the complex is a crystalline triplet system with incompatible “high spin density” but “small interspin interaction” properties.     

A Stable,Soluble, and Crystalline Supramolecular System with a Triplet Ground State

A supramolecular complex was constructed by encapsulation of a ³O₂ molecule inside an open‐cage C₆₀ derivative. Its single‐crystal X‐ray diffraction analysis revealed the presence of the ³O₂ at the center of the fullerene cage. The CV measurements suggested that unprecedented dehydrogenation was promoted by the encapsulated ³O₂ after two‐electron reduction. The ESR measurements displayed the triplet character as well as the anisotropy of the ³O₂. Additionally, the SQUID measurements also demonstrated the paramagnetic behavior above 3 K without an antiferromagnetic transition. Upon photoirradiation with visible light, three phosphorescent bands at the NIR region were observed, arising from the exited ¹O₂ generated by self‐sensitization with the outer cage, whose lifetimes were not affected by the environments. These studies confirmed that the complex is a crystalline triplet system with incompatible “high spin density” but “small interspin interaction” properties.     

Bis-Olefin Based Crystalline Schlenk Hydrocarbon Diradicals with a Triplet Ground State

A modular approach for the synthesis of isolable crystalline Schlenk hydrocarbon diradicals from m-phenylene bridged electron-rich bis-triazaalkenes as synthons is reported. EPR spectroscopy confirms their diradical nature and triplet electronic structure by revealing a half-field signal. A computational analysis confirms the triplet state to be the ground state. As a proof-of-principle for the modular methodology, the 4,6-dimethyl-m-phenylene was further utilized as a coupling unit between two alkene motifs. The steric conjunction of the 4,6-dimethyl groups substantially twists the substituents at the nonbonding electron bearing centers relative to the central coupling m-phenylene motif. As a result, the spin delocalization is decreased and the exchange coupling between the two unpaired spins, hence, significantly reduced. Notably, 108 years after Schlenk's m-phenylene-bis(diphenylmethyl) synthesis as a diradical, for the first time we were able to isolate its derivative with the same spacer, i.e. m-phenylene, between two radical centers in a crystalline form.     

Superparamagnetic Reduced Graphene Oxide with Large Magnetoresistance: A Surface Modulation Strategy

The graphene system is actively pursued in spintronics for its nontrivial sp electron magnetism and its potential for the flexible surface chemical tuning of magnetoelectronic functionality. The magnetoresistance (MR) of graphene can be effectively tuned under high magnetic fields at cryogenic temperatures, but it remains a challenge to achieve sensitive magnetoelectric response under ambient conditions. We report the use of surface modulation to realize superparamagnetism in reduced graphene oxide (rGO) with sensitive magnetic field response. The superparamagnetic rGO was obtained by a mild oxidation process to partially remove the thiol groups covalently bound to the carbon framework, which brings about large low‐field negative MR at room temperature (?8.6 %, 500 Oe, 300 K). This strategy provides a new approach for optimizing the intrinsic magnetoelectric properties of two‐dimensional materials.     

A Kinetically Stabilized Nitrogen-Doped Triangulene Cation: Stable and NIR Fluorescent Diradical Cation with Triplet Ground State

A kinetically-stabilized nitrogen-doped triangulene cation derivative has been synthesized and isolated as the stable diradical with a triplet ground state that exhibits near-infrared emission. As was the case for a triangulene derivative we previously synthesized, the triplet ground state with a large singlet-triplet energy gap was experimentally confirmed by magnetic measurements. In contrast to the triangulene derivative, the nitrogen-doped triangulene cation derivative is highly stable even in solution under air and exhibits near-infrared absorption and emission because the alternancy symmetry of triangulene is broken by the nitrogen cation. Breaking the alternancy symmetry of triplet alternant hydrocarbon diradicals by a nitrogen cation would therefore be an effective strategy to create stable diradicals possessing magnetic properties similar to the parent hydrocarbons but with different electrochemical and photophysical properties.     

A Triphenylamine Derivative with Three p-(N-tert-Butyl-N-oxylamino)phenyl Radical Units and Yet a Doublet Ground State

A superexchange interaction through the lone pair of electrons on the central nitrogen atom in 1 is invoked to explain the existence of a doublet ground state; two spins on the aminoxyl radical centers couple antiferromagnetically, and one spin remains intact. This proposal is supported by EPR spectroscopic and magnetic measurements.     

Photochemistry with Cyanines in the Near Infrared: A Step to Chemistry 4.0 Technologies

Cyanines covering the absorption in the near infrared (NIR) are attractive for distinct applications. They can interact either with lasers exhibiting line-shaped focus emitting at both 808 and 980 nm or bright high intensity NIR-LEDs with 805 nm emission, respectively. This is drawing attention to Industry 4.0 applications. The major deactivation occurs through a non-radiative process resulting in the release of heat into the surrounding, although a small fraction of radiative deactivation also takes place. Most of these NIR-sensitive systems possess an internal activation barrier to react in a photonic process with initiators resulting in the generation of reactive radicals and acidic cations. Thus, the heat released by the NIR absorber helps to bring the system, consisting of an NIR sensitizer and initiator, above such internal barriers. Molecular design strategies making these systems more compatible with distinct applications in a certain oleophilic surrounding are considered as a big challenge. This includes variations of the molecular pattern and counter ions derived from super acids exhibiting low coordinating properties. Further discussion focusses on the use of such systems in Chemistry 4.0 related applications. Intelligent software tools help to improve and optimize these systems combining chemistry, engineering based on high-throughput formulation screening (HTFS) technologies, and machine learning algorithms to open up novel solutions in material sciences.     

Tuning Ground States of Bis(triarylamine) Dications: From a Closed‐Shell Singlet to a Diradicaloid with an Excited Triplet State

Three bis(triarylamine) dications were isolated by using weakly coordinating anions. Their electronic structures in the ground state were investigated by various experiments in conjunction with theoretical calculations. The ground‐state electronic structures of these species were tunable by substituent effects, with two of them as closed‐shell singlets and one of them as an open‐shell singlet in the solid state. The excited state of the latter is thermally accessible, indicated by EPR and SQUID measurements. The work provides a new and stable diradicaloid structure motif with an excited triplet sate.