Spin-Enhanced O-H Cleavage in Electrochemical Water Oxidation.

Herein we report the vital role of spin polarization in proton-transfer-mediated water oxidation over a magnetized catalyst. During the electrochemical oxygen evolution reaction (OER) over ferrimagnetic Fe3O4, the external magnetic field induced a remarkable increase in the OER current, however, this increment achieved in weakly alkaline pH (pH 9) was almost 20 times that under strongly alkaline conditions (pH 14). The results of the surface modification experiment and H/D kinetic isotope effect investigation confirm that, at weakly alkaline pH, during the nucleophilic attack of FeIV=O by molecular water, the magnetized Fe3O4 catalyst polarizes the spin states of the nucleophilic attacking intermediates. The spin-enhanced singlet O-H cleavage and triplet O-O bonding occur synergistically, which promotes the O2 generation more significantly than the strongly alkaline case involving only spin-enhanced O-O bonding.

Nonconfinement growth of edge-curved molecular crystals for self-focused microlasers.

Synthesis of single-crystalline micro/nanostructures with curved shapes is essential for developing extraordinary types of optoelectronic devices. Here, we use the strategy of liquid-phase nonconfinement growth to controllably synthesize edge-curved molecular microcrystals on a large scale. By varying the molecular substituents on linear organic conjugated molecules, it is found that the steric hindrance effect could minimize the intrinsic anisotropy of molecular stacking, allowing for the exposure of high-index crystal planes. The growth rate of high-index crystal planes can be further regulated by increasing the molecular supersaturation, which is conducive to the cogrowth of these crystal planes to form continuously curved-shape microcrystals. Assisted by nonrotationally symmetric geometry and optically smooth curvature, edge-curved microcrystals can support low-threshold lasing, and self-focusing directional emission. These results contribute to gaining an insightful understanding of the design and growth of functional molecular crystals and promoting the applications of organic active materials in integrated photonic devices and circuits.

Spin-Enhanced Reverse Intersystem Crossing and Electroluminescence in Copper Acetate-Doped Thermally Activated Delayed Fluorescence Material.

Thermally activated delayed fluorescence (TADF) materials are attractive for next-generation organic light-emitting diodes (OLEDs) because of their utilization of nonradiative triplets via reverse intersystem crossing (RISC), which requires not only a small singlet-triplet energy splitting but also the conservation of spin angular momentum. Here we use copper acetate as a spin sensitizer to facilitate RISC and thus enhance electroluminescence in TADF-exciplex OLEDs. Copper acetate is involved in the radiative decay process due to its coordination interaction with exciplex molecules having intermolecular charge-transfer characteristics, which causes significant changes in the photoluminescence intensity and lifetime. Meanwhile, magneto-photoluminescence reveals that the addition of copper acetate promotes spin conversion in the RISC process. It allows the enhancement of the electroluminescence (∼80%) from spin-sensitized OLEDs, accompanied by the suppression of magneto-electroluminescence upon the doping of copper acetate. These results illustrate that using a spin sensitizer may overcome the limitation of harvesting nonradiative triplets in organic luminescent materials and devices.

Discrete Supracrystalline Heterostructures from Integrative Assembly of Nanocrystals and Porous Organic Cages.

Although self-assembly across multiple length scales has been well recognized and intensively investigated in natural biological system, the design of artificial heterostructures enabled by integrative self-assembly is still in its infancy. Here we report a strategy toward the growth of discrete supracrystalline heterostructures from inorganic nanocrystals and porous organic cages (CC3-R), which in principle relies on the host-guest interactions between alkyl chains coated on nanocrystals and the cavity of cage molecules. Density functional theory calculation indicates that an attractive energy of ∼-2 kBT is present between an alkyl chain and the cavity of a CC3-R molecule, which is responsible for the assembly of nanocrystal superlattices on the CC3-R octahedral crystals. Of particular interest is that, determined by the shape of the nanocrystals, two distinct assembly modes can be controlled at the mesoscale level, which eventually produce either a core/shell or heterodimer supracrystalline structure. Our results highlight opportunities for the development of such a noncovalent integrative self-assembly not limited to a particular length scale and that could be generally applicable for flexible integration of supramolecular systems.