ABSTRACT
Low-cost molecular emitters that merge circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (TADF) properties are attractive for many high-tech applications. However, the design of such emitters remains a difficult task. To address this challenge, here, we propose a simple and efficient strategy, demonstrated by the design of pseudochiral-at-metal complexes [Cu(L*)DPEPhos]PF6 bearing a (+)/(-)-menthol-derived 1,10-phenanthroline ligand (L*). These complexes exhibit a yellow CP-TADF with a record-high quantum yield (close to 100%) and high dissymmetry factor (|glum| ~ 1×10-2). Remarkably, the above compounds also show a negative thermal-quenching (NTQ) of luminescence in the 300-77 K range. Exploiting the designed Cu(I) emitters, we fabricated efficient CP-TADF OLEDs displaying mirror-imaged CPL bands with high |gEL| factors of 1.5×10-2 and the maximum EQE of 6.15%. Equally important, using the (+)-[Cu(L*)DPEPhos]PF6 complex, we have discovered that an external magnetic field noticeably suppresses CP-TADF of Cu(I) emitters. These findings are an important contribution to the CPL phenomenon and provide access to highly efficient, low-cost and robust CP-TADF emitters.
ABSTRACT
Over recent years, Mn(II)-organic materials showing circularly polarized luminescence (CPL) have attracted great interest because of their eco-friendliness, cheapness, and room temperature phosphorescence. Using the helicity design strategy, herein, chiral Mn(II)-organic helical polymers are constructed featuring long-lived circularly polarized phosphorescence with exceptionally high glum and ΦPL magnitudes of 0.021% and 89%, respectively, while remaining ultrarobust toward humidity, temperature, and X-rays. Equally important, it is disclosed for the first time that the magnetic field has a remarkably high negative effect on CPL for Mn(II) materials, suppressing the CPL signal by 4.2-times at B â $\vec{B}$ = 1.6 T. Using the designed materials, UV-pumped CPL light-emitting diodes are fabricated, demonstrating enhanced optical selectivity under right- and left-handed polarization conditions. On top of all this, the reported materials display bright triboluminescence and excellent X-ray scintillation activity with a perfectly linear X-ray dose rate response up to 174 µGyair s-1 . Overall, these observations significantly contribute to the CPL phenomenon for multi-spin compounds and promote the design of highly efficient and stable Mn(II)-based CPL emitters.
ABSTRACT
We report here an unprecedentedly fast and reversible transformation between 1D and 2D MOFs/CPs induced through organic solvent vapours. The transformations occur at room temperature in just 15-20 min, accompanied by a significant change in the observed phosphorescence. These findings provide a new insight into the design of luminescent networks with stimuli-switchable dimensionality.
ABSTRACT
We introduce here a new subclass of copper(I) hybrid emitters simultaneously containing [CuxIy]z- anions and Cu+ cations, separated in space by a Janus head ligand. When UV-irradiated at 298 K, these unique "Two-In-One" hybrids exhibit a short-lived green TADF with near-unity quantum yield and a strong solvatochromic effect. Moreover, they manifest a strong radioluminescence upon X-ray irradiation. These findings open up new possibilities for the design of highly performing TADF materials.
ABSTRACT
Exploiting 2-(alkylsulfonyl)pyridines as 1,3-N,S-ligands, herein we have constructed 1D CuI-based coordination polymers (CPs) bearing unprecedented (CuI)n chains and possessing remarkable photophysical properties. At room temperature, these CPs show efficient TADF, phosphorescence or dual emission in the deep-blue to red range with outstandingly short decay times of 0.4-2.0 µs and good quantum performance. Owing to great structural diversity, the CPs demonstrate a variety of emissive mechanisms, spanning from TADF of 1(M + X)LCT type to 3CC and 3(M + X)LCT phosphorescence. Moreover, the designed compounds emit strong X-ray radioluminescence with the quantum efficiency of up to an impressive 55% relative to all-inorganic BGO scintillators. The presented findings push the boundaries in designing TADF and triplet emitters with very short decay times.
ABSTRACT
Herein, we report the characterization of two types of luminescent carbon dots (CDs) synthesized by the hydrothermal treatment of citric acid and trans-aconitic acid by using ammonia solution as a nitrogen dopant. The lateral size range of nanoparticles for CDs lies in the range of 3-15 nm. The intense blue photoluminescence (PL) was emitted by the CDs at around 409-435 nm under the excitation of 320 nm. The PL quantum yield of the synthesized CDs ranged from 26.4 to 51%. Our results of the structural and optical properties of CDs imply that molecular fluorophores are an important part of the structure; in particular, the main contribution to the PL is carried by the fluorophores based on citrazinic acid derivatives, which formed during the synthesis of CDs.
ABSTRACT
Elimination of the chloride ion from the [(PPh3)AuCl] complex using silver triflate (AgOTf) in the presence of 2,2'-bipyridine R2bpy (the Au : R2bpy molar ratio is 2 : 1) in dichloromethane at room temperature leads to dinuclear gold(I) complexes [(PPh3Au)2(µ-R2bpy)](OTf)2 (R2bpy = bpy (1), dbbpy (2), CH3Obpy (3), 3-CO2CH3bpy (4), 4-CO2CH3bpy (5)) in high yields. The crystal structures for all compounds were determined using X-ray diffraction analysis. In all structures, gold ions are in a typical linear environment, and the bipyridine molecule is twisted, which allows intramolecular aurophilic interactions. Relatively short Au(I)â¯Au(I) contacts (3.1262 (2)-3.400 (1) Å) are found in structures 3-5. DFT calculations show the presence of bond critical points (3, -1) for aurophilic interactions in these structures. In structures 1 and 2, the Au(I)â¯Au(I) distances are noticeably larger and equal to 4.479 (1) and 4.589 (1) Å respectively; there are no bond critical points (3, -1) for aurophilic interactions. All complexes show photoluminescence in solid state at room temperature when excited at 300 nm in a wide spectral range: from blue or blue-green emission (400-460 nm) for 1-4 to orange emission (580 mn) for 5. The lifetimes of the excited state are in the microsecond range which is characteristic of phosphorescence. TD-DFT calculations reveal that electronic transitions of different nature are responsible for the photoluminescence of these compounds.
ABSTRACT
A family of brightly luminescent dinuclear complexes of [Cu(µ2-X)(N^N)]2 type (X = I or SCN) has been synthesized in 76-90% yields by the reaction of bis(2-pyridyl)phosphine oxides (N^N) with the corresponding Cu(i) salts. The X-ray diffraction study reveals that the Cu2I2 core of the [Cu(µ2-I)(N^N)]2 complexes has either a butterfly- or rhomboid-shaped structure, while the eighth-membered [Cu()Cu] ring in the [Cu2(SCN)2(N^N)]2 complexes is nearly planar. In the solid state, these compounds exhibit a strong green-to-yellow emission (λ = 536-592 nm) with high PLQYs (up to 63%) and short lifetimes (1.9-10.0 µs). The combined photophysical and DFT study indicates that the ambient-temperature emission of the complexes obtained can be assigned to the thermally activated-delayed fluorescence (TADF) from the 1(M + X)LCT excited state, while at 77 K, phosphorescence from the 3(M + X)LCT state is likely observed.
ABSTRACT
An unprecedented silver-centered P-tetracapped [Ag@Ag4(µ3-P)4] tetrahedron inscribed within a N12 icosahedral cage has been discovered in the novel family of luminescent clusters. The latter are easily self-assembled by reacting AgI salts with tris(2-pyridyl)phosphine (Py3P).