Mechanochromic luminescence (MCL) materials have a high requirement in high-tech applications such as pressure sensors and data storage. Nevertheless, the diversity of these emitters was still rather restricted owing to...
The fluorescence-phosphorescence dual solvoluminescence (SL) of water-soluble metal nanoclusters (NCs) at room temperature was successfully achieved by a simple solvent-stimulated strategy. The strong interaction between carboxylate ligands and the metal core at the nanoscale interface not only induces rigid conformations of carbonyl groups but also affords a perfect carbonyl cluster that acts as an exact chromophore of metal NCs for aggregation-induced emission (AIE) mechanics. The clustering of carbonyl groups bearing on the polymer backbone chain is promoted by newly discovered n → π* noncovalent interactions. The efficient delocalization of electrons in overlapped C═O double bonds between neighboring carbonyl groups triggered by strong n → π* interactions in the polymer cluster accounts for its unique SL properties, especially the abnormal phosphorescence. This was further confirmed by controlled experiments for the presence of intersystem crossing (ISC) transitions. The results provide novel insights for understanding the complex SL process and open up a new way to study the inherent mechanism of SL by broadening the application of metal NCs.
Dinuclear Pt(III)
complexes were commonly reported to have short-lived
lowest-lying triplet states, resulting in extremely weak or no photoluminescence.
To overcome this obstacle, a new series of dinuclear Pt(III) complexes,
named Pt2a-Pt2c, were strategically designed and synthesized
using donor (D)–acceptor (A)-type oxadiazole-thiol chelates
as bridging ligands. These dinuclear Pt(III) complexes possess a d7–d7 electronic configuration and exhibit
intense phosphorescence under ambient conditions. Among them, Pt2a exhibits orange phosphorescence maximized at 618 nm in
degassed dichloromethane solution (Φp ≈ 8.2%,
τp ≈ 0.10 μs) and near-infrared (NIR)
emission at 749 nm (Φp ≈ 10.1% τp ≈ 0.66 μs) in the crystalline powder and at
704 nm (Φp ≈ 33.1%, τp ≈
0.34 μs) in the spin-coated neat film. An emission blue-shifted
by more than 3343 cm–1 is observed under mechanically
ground crystalline Pt2a, affirming intermolecular interactions
in the solid states. Time-dependent density functional theory (TD-DFT)
discloses the lowest-lying electronic transition of Pt2a-Pt2c complexes to be a bridging ligand–metal–metal charge
transfer (LMMCT) transition. The long-lived triplet states of these
dinuclear platinum(III) complexes may find potential use in lighting.
Employing Pt2a as an emitter, high-performance organic
light-emitting diodes (OLEDs) were fabricated with NIR emission at
716 nm (η = 5.1%), red emission at 614 nm (η = 8.7%),
and white-light emission (η = 11.6%) in nondoped, doped (in
mCP), and hybrid (in CzACSF) devices, respectively.
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