Ultralong organic phosphorescence (UOP) has attracted increasing attention due to its potential applications in optoelectronics, bioelectronics, and security protection. However, achieving UOP with high quantum efficiency (QE) over 20 % is still full of challenges due to intersystem crossing (ISC) and fast non‐radiative transitions in organic molecules. Here, we present a novel strategy to enhance the QE of UOP materials by modulating intramolecular halogen bonding via structural isomerism. The QE of CzS2Br reaches up to 52.10 %, which is the highest afterglow efficiency reported so far. The crucial reason for the extraordinary QE is intramolecular halogen bonding, which can not only effectively enhance ISC by promoting spin–orbit coupling, but also greatly confine motions of excited molecules to restrict non‐radiative pathways. This work provides a reasonable strategy to develop highly efficient UOP materials for practical applications.
Recently, reactive iron species (RFeS)
have shown great potential
for the selective degradation of emerging organic contaminants (EOCs).
However, the rapid generation of RFeS for the selective and efficient
degradation of EOCs over a wide pH range is still challenging. Herein,
we constructed FeN4 structures on a carbon nanotube (CNT)
to obtain single-atom catalysts (FeSA-N-CNT) to generate
RFeS in the presence of peroxymonosulfate (PMS). The obtained FeSA-N-CNT/PMS system exhibited outstanding and selective reactivity
for oxidizing EOCs over a wide pH range (3.0–9.0). Several
lines of evidences suggested that RFeS existing as an FeN4O intermediate was the predominant oxidant, while SO4
·– and HO· were the
secondary oxidants. Density functional theory calculation results
revealed that a CNT played a key role in optimizing the distribution
of bonding and antibonding states in the Fe 3d orbital, resulting
in the outstanding ability of FeSA-N-CNT for PMS chemical
adsorption and activation. Moreover, CNT could significantly enhance
the reactivity of the FeN4O intermediate by increasing
the overlap of electrons of the Fe 3d orbital, O 2p orbital, and bisphenol
A near the Fermi level. The results of this study can advance the
understanding of RFeS generation in a heterogeneous system over a
wide pH range and the application of RFeS in real practice.
Flexible hydrogen-bonded organic frameworks (FHOFs) are quite rare but promising for applications in separation, sensing and host-guest chemistry. They are difficult to stabilize, making their constructions a major challenge. Here, a flexible HOF (named 8PN) with permanent porosity has been successfully constructed. Nine single crystals of 8PN with different pore structures are obtained, achieving a large-scale void regulation from 4.4% to 33.2% of total cell volume. In response to external stimuli, multimode reversible structural transformations of 8PN accompanied by changes in luminescence properties have been realized. Furthermore, a series of high-quality co-crystals containing guests of varying shapes, sizes, aggregation states and even amounts are obtained, showing that 8PN can adapt to different guests by regulating the molecular conformations and assembling forms of its building blocks. The unexpected flexibility of 8PN makes it a promising material for enriching the applications of existing porous materials.
Soft luminescent materials are attractive for optoelectronic applications, however, switching dominant chromophores for property enrichment remains a challenge. Herein, we report the first case of a soft organic molecule (DOS) featuring selective expression of chromophores. In response to various external stimuli, different chromophores of DOS can take turns working through conformation changes, exhibiting full‐colour emissions peaking from 469 nm to 583 nm from ten individual single crystals. Dynamic triplet‐exciton behaviours including thermally activated delayed fluorescence (TADF), room‐temperature phosphorescence (RTP), mechanoluminescence (ML), and distinct mechano‐responsive luminescence (MRL) can all be realized. This novel designed DOS molecule provides a multifunctional platform for detection of volatile organic compounds (VOCs), multicolour dynamic displays, sensing, anticounterfeiting, and hopefully many others.
The
maximization of the numbers of exposed active sites in supported
metal catalysts is important to achieve high reaction activity. In
this work, a simple strategy for anchoring single atom Fe on SBA-15
to expose utmost Fe active sites was proposed. Iron salts were introduced
into the as-made SBA-15 containing the template and calcined for simultaneous
decomposition of the iron precursor and the template, resulting in
single atom Fe sites in the nanopores of SBA-15 catalysts (SAFe-SBA).
X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy
(UV–vis DRS), high-angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM), and extended X-ray absorption fine
structure (EXAFS) imply the presence of single atom Fe sites. Furthermore,
EXAFS analysis suggests the structure of one Fe center with four O
atoms, and density functional theory calculations (DFT) simulate this
structure. The catalytic performances of SAFe-SBA were evaluated in
Fenton-like catalytic oxidation of p-hydroxybenzoic
acid (HBA) and phenol. It was found that the single atom SAFe-SBA
catalysts displayed superior catalytic activity to aggregated iron
sites (AGFe-SBA) in both HBA and phenol degradation, demonstrating
the advantage of SAFe-SBA in catalysis.
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