Electro-assisted Molecular Assembly Giving Atomic-Scale Catalytic Active-Site Detection

The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom.     

Acridone-Based Host Materials for Green Phosphorescent and Thermally Activated Delayed Fluorescent OLEDs with Low-Efficiency Roll-Offs

By linking the carbazole unit to the nitrogen atom of acridone through phenyl or pyridyl, two compounds, named 10-(4-(9H-carbazol-9-yl)phenyl)acridin-9(10H)-one (AC-Ph-Cz) and 10-(5-(9H-carbazol-9-yl)pyridin-2-yl)acridin-9(10H)-one (AC-Py-Cz) were designed and synthesized. These two materials, characterized with highly twisted and rigid structure, good thermal stability, and balanced carrier-transporting properties, were employed as host materials for green phosphorescent and thermally activated delayed fluorescent organic light-emitting diodes (OLEDs). The carbazole group, despite its small contribution to the highest occupied molecular orbitals (HOMOs) of these two materials, plays an essential role as an intramolecular host in energy delivering and improving the hole transporting ability of these two hosts. The incorporation of the electron-deficient pyridyl group as a linking group slightly improves the electron transporting capability of AC-Py-Cz. The green phosphorescent OLED (PhOLED) based on AC-Py-Cz exhibited excellent device performance with a turn-on voltage of 2.5 V, a maximum power efficiency and an external quantum efficiency (η_ext) of 89.8 lm W⁻¹ and 25.2 %, respectively, benefitting from the better charge-balancing ability of AC-Py-Cz host due to the presence of the pyridyl bridge. More importantly, all the devices based on these two hosts showed low efficiency roll-off at high brightness due to the suppressed non-radiative transition in the emitting layer. In particular, the AC-Py-Cz-hosted green PhOLED exhibited an efficiency roll-off of 1.6 % from the maximum next at a high brightness of 1000 cd m⁻² and a roll-off of 15.9 % at an extremely high brightness of 10000 cd m⁻². This study manifests that acridone-based host materials have great potential in fabricating OLEDs with low efficiency roll-off.     

A smooth homotopy method for incomplete markets

Mathematical Programming - In the general equilibrium with incomplete asset markets (GEI) model, the excess demand functions are typically not continuous at the prices for which the assets have...     

On s-hamiltonian line graphs of claw-free graphs

For an integer $s\ge 0$, a graph $G$ is $s$-hamiltonian if for any vertex subset $S?V\left(G\right)$ with $\left|S\right|\le s$, $G?S$ is hamiltonian, and $G$ is $s$-hamiltonian connected if for any vertex subset $S?V\left(G\right)$ with $\left|S\right|\le s$, $G?S$ is hamiltonian connected. Thomassen in 1984 conjectured that every 4-connected line graph is hamiltonian (see Thomassen, 1986), and Ku?zel and Xiong in 2004 conjectured that every 4-connected line graph is hamiltonian connected (see Ryjá?ek and Vrána, 2011). In Broersma and Veldman (1987), Broersma and Veldman raised the characterization problem of $s$-hamiltonian line graphs. In Lai and Shao (2013), it is conjectured that for $s\ge 2$, a line graph $L\left(G\right)$ is $s$-hamiltonian if and only if $L\left(G\right)$ is $(s+2)$-connected. In this paper we prove the following.(i) For an integer $s\ge 2$, the line graph $L\left(G\right)$ of a claw-free graph $G$ is $s$-hamiltonian if and only if $L\left(G\right)$ is $(s+2)$-connected.(ii) The line graph $L\left(G\right)$ of a claw-free graph $G$ is 1-hamiltonian connected if and only if $L\left(G\right)$ is 4-connected.     

Nickel/Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling of Racemic α-Chloro Esters with Aryl Iodides

A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions.     

Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate

Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc₃N@C₈₀ to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc₃N@C₈₀ and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.