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Two-coordinate coinage metal complexes have been exploited for various applications. Herein, a new donor-metal-acceptor (D-M-A) complex PZI-Au-TOT, using bulky pyrazine-fused N-heterocyclic carbene (PZI) and trioxytriphenylamine (TOT) ligands, was synthesized. PZI-Au-TOT displays decent thermally activated delayed fluorescence (TADF) with a quantum yield of 93 % in doped film. The crystals of PZI-Au-TOT show simultaneous TADF, polymorphism, and linearly polarized luminescence (LPL). The polymorph-dependent emission properties with widely varied peaks from 560 to 655 nm are attributed to different packing modes in terms of isolated monomers, discrete π-π stacked dimers or dimer PLUS. Two well-defined microcrystals of PZI-Au-TOT exhibit linearly polarized thermally activated delayed fluorescence with a degree of polarization up to 0.64. This work demonstrates that the molecular rotational flexibility of D-M-A type complexes endows an integration of multiple functions into one complex through manipulation of supramolecular aggregation. This type of complexes is expected to serve as a versatile platform for the fabrication of crystal materials for advanced photonic applications., (© 2024 Wiley-VCH GmbH.)

Multi-resonance (MR) type emitters have emerged as highly promising candidates for high-resolution organic light-emitting diodes (OLEDs). However, thermally activated delayed fluorescence (TADF) emissions with simultaneous short excited state lifetimes and ultrapure blue color (a CIE y close to 0.046 and an emission peak >440 nm) have rarely been obtained for MR emitters. Herein, we report a design of dual gold-coordinated MR molecules to achieve efficient and short-lived ultrapure blue TADF emission. The dinuclear Au(I) complex, namely iPrAuBN, shows a narrowband deep-blue emission with a peak maximum of 448 nm and a full width at half maximum (FWHM) of 29 nm in doped film. The coordination with two Au atoms significantly shortens the delayed fluorescence lifetime to 7.8 μs in comparison to 60.6 μs for the parental organic analogue. Solution-processed OLED doped with iPrAuBN demonstrates an ultrapure blue electroluminescence with a peak maximum of 442 nm, a FWHM of 19 nm, CIE coordinates of (0.154, 0.036), and a maximum external quantum efficiency of 14.8 %., (© 2024 Wiley-VCH GmbH.)

Although two-coordinate Cu(I) complexes are highly promising low-cost emitters for organic light-emitting diodes (OLEDs), the exposed metal center in the linear coordination geometry makes them suffer from poor stability. Herein, we describe a strategy to develop stable carbene-Cu-amide complexes through installing intramolecular noncovalent Cu⋅⋅⋅H interactions. The employment of 13H-dibenzo[a,i]carbazole (DBC) as the amide ligand leads to short Cu⋅⋅⋅H distances in addition to the Cu-N coordination bond. The resultant Cu(I) complexes exhibit yellow thermally activated delayed fluorescence with photoluminescence quantum yields of up to 86 % and radiative decay rate constants on the order of 10 6  s -1 . Comparing with the analogues without Cu⋅⋅⋅H interactions, the pincer complexes have significantly improved stability. The vacuum-deposited OLEDs show high-performance electroluminescence with maximum external quantum efficiencies of up to 29.5 % and extremely small roll-offs of only 3.5 % at 10,000 cd m -2 . Remarkably, the operational lifetimes (LT 90 ) are up to 68 h with an initial luminance of 3000 cd m -2 . This work proves a feasible design of robust low-coordinate metal complexes by leveraging secondary coordination interactions, which helps to overcome the long-standing stability problem., (© 2024 Wiley-VCH GmbH.)

Two-coordinate Au(I) complexes with a donor-metal-acceptor (D-M-A) structure have shown rich luminescent properties. However, charge-neutral dinuclear donor-metal-acceptor type Au(I) complexes featuring aurophilic interactions have been seldom explored. Herein, we describe the structures and photoluminescence properties of two dinuclear Au(I) complexes, namely DiAu-Ph and DiAu-Me. Single crystal X-ray structural analysis of DiAu-Ph reveals a short intramolecular Au-Au distance of 3.224 Å. In dilute solution and doped films, excitation wavelength dependent multiple phosphorescence phenomena were observed for these dinuclear complexes. Theoretical calculations reveal that the aurophilic interaction causes increased contribution of the Au d orbital to the highest occupied molecular orbitals. Thus, the gap between singlet and triplet excited states (ΔE ST ) is enlarged, which disables the thermally activated delayed fluorescence (TADF). Moreover, the large energy separation (0.45-0.52 eV) and the different orbital configurations between the various excited states result in an inefficient internal conversion, accounting for their multiple phosphorescence properties., (© 2024 Wiley-VCH GmbH.)

A new class of carbene-anilido boron complexes have been designed and synthesized. The complexes show intense fluorescence with large Stokes shift because of their charge-transfer excited states, different from typical BODIPY dyes. By using a chiral 1,1'-bi(2-naphthol) ligand, dyes exhibiting circularly polarized luminescence can also be facilely developed.

B- and N-embedded multiple resonance (MR) type thermally activated delayed fluorescence (TADF) emitters usually suffer from slow reverse intersystem crossing (RISC) process and aggregation-caused emission quenching. Here, we report the design of a sandwich structure by placing the B-N MR core between two electron-donating moieties, inducing through-space charge transfer (TSCT) states. The proper adjusting of the energy levels brings about a 10-fold higher RISC rate in comparison with the parent B-N molecule. In the meantime, a high photoluminescence quantum yield of 91 % and a good color purity were maintained. Organic light-emitting diodes based on the new MR emitter achieved a maximum external quantum efficiency of 31.7 % and small roll-offs at high brightness. High device efficiencies were also obtained for a wide range of doping concentrations of up to 20 wt % thanks to the steric shielding of the B-N core. A good operational stability with LT 95 of 85.2 h has also been revealed. The dual steric and electronic effects resulting from the introduction of a TSCT state offer an effective molecular design to address the critical challenges of MR-TADF emitters., (© 2023 Wiley-VCH GmbH.)

"Carbene-metal(I)-amide" (CMA) complexes have garnered significant attention due to their remarkable properties and potential TADF applications in organic electronics. However, the atomistic working mechanism is still elusive. Herein, we chose two CMA complexes, i.e. , cyclic (alkyl)(amino) carbene-copper[gold](I)-carbazole (CAAC-Cu[Au]-Cz), and employed both DFT and TD-DFT methods, in combination with radiative and nonradiative rate calculations, to investigate geometric and electronic structures of these two complexes in the ground and excited states, including orbital compositions, electronic transitions, absorption and emission spectra, and the luminescence mechanism. It is found that the coplanar or perpendicular conformations are coexistent in the ground state (S 0 ), the lowest excited singlet state (S 1 ), and the triplet state (T 1 ). Both the coplanar and perpendicular S 1 and T 1 states have similar ligand-to-ligand charge transfer (LLCT) character between CAAC and Cz, and some charge-transfer character between metal atoms and ligands, which is beneficial to minimize the singlet-triplet energy gaps (Δ E ST ) and increase the spin-orbit coupling (SOC). An interesting three-state (S 0 , S 1 , T 1 ) model involving two regions (coplanar and perpendicular) is proposed to rationalize the experimental TADF phenomena in the CMA complexes. In addition to the coplanar ones, the perpendicular S 1 and T 1 states also play a role in promoting the repopulation of the coplanar S 1 exciton, which is a primary source for the delayed fluorescence.

Through-space charge transfer (TSCT) has been proven effective for designing thermally activated delayed fluorescence (TADF) emitters due to the separation of the frontier molecular orbitals. Although tuning of the interaction between the donor and acceptor by controlling the conformation is known to be crucial for the photophysical properties of TSCT excited states, it remains a challenge to realize efficient red and deep-red emissions. Herein, we designed two TSCT molecules, namely TPXZ-QX and TPXZ-2QX, by using oxygen-bridged triphenylamine (TPXZ) as the electron donor with enhanced planarity and electron-donating capability. With a face-to-face orientation of the donor and acceptor segments and close π-π contacts, the new emitters have strong intramolecular noncovalent donor-acceptor interactions. The emissions of TPXZ-QX and TPXZ-2QX in doped thin films lie in the red ( λ max = 632 nm) to deep-red ( λ max = 665 nm) region. The photoluminescence quantum yields are 41% and 32% for TPXZ-QX and TPXZ-2QX, respectively. Organic light-emitting diodes (OLEDs) based on TPXZ-QX and TPXZ-2QX show external quantum efficiencies (EQEs) of up to 13.8% and 11.4%, respectively. This work indicates that the modulation of TSCT excited states based on strong intramolecular cofacial π-stacking interactions is a viable choice for the development of high-efficiency long-wavelength TADF emitters., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Transition metal complexes exhibiting thermally activated delayed fluorescence (TADF) remain underdeveloped for organic light-emitting diodes (OLEDs). Here, we describe a design of TADF Pd(II) complexes featuring metal-perturbed intraligand charge-transfer excited states. Two orange- and red-emitting complexes with efficiencies of 82 and 89% and lifetimes of 2.19 and 0.97 μs have been developed. Combined transient spectroscopic and theoretical studies on one complex reveal a metal-perturbed fast intersystem crossing process. OLEDs using the Pd(II) complexes show maximum external quantum efficiencies of 27.5 to 31.4% and small roll-offs down to 1% at 1000 cd m -2 . Moreover, the Pd(II) complexes show exceptional operational stability with LT 95 values over 220 hours at 1000 cd m -2 , benefiting from the use of strong σ-donating ligands and the presence of multiple intramolecular noncovalent interactions beside their short emission lifetimes. This study demonstrates a promising approach for developing efficient and robust luminescent complexes without using the third-row transition metals.

Two-coordinate donor-metal-acceptor type coinage metal complexes displaying efficient thermally activated delayed fluorescence (TADF) have been unveiled to be highly appealing candidates as emitters for organic light-emitting diodes (OLEDs). Herein a series of green to yellow TADF gold(I) complexes with alkynyl ligands has been developed for the first time. The complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 0.76 in doped films (5 wt % in PMMA) at room temperature. The modifications of alkynyl ligands with electron-donating amino groups together with the use of electron-deficient carbene ligands induce ligand-to-ligand charge transfer excited states that give rise to TADF emission. Spectroscopic and density functional theory (DFT) calculations reveal the roles of electron-donating capability of the alkynyl ligand in tuning the excited-state properties. Solution-processed organic light-emitting diodes (OLEDs) using the present complexes as emitters achieve maximum external quantum efficiency (EQE) of up to 20 %., (© 2022 Wiley-VCH GmbH.)

A dinuclear Pt(II) compound was reported to exhibit thermally activated delayed fluorescence (TADF); however, the luminescence mechanism remains elusive. To reveal relevant excited-state properties and luminescence mechanism of this Pt(II) compound, both density function theory (DFT) and time-dependent DFT (TD-DFT) calculations were carried out in this work. In terms of the results, the S 1 and T 2 states show mixed intraligand charge transfer (ILCT)/metal-to-ligand CT (MLCT) characters while the T 1 state exhibits mixed ILCT/ligand-to-metal CT (LMCT) characters. Mechanistically, a four-state (S 0 , S 1 , T 1 , and T 2 ) model is proposed to rationalize the TADF behavior. The reverse intersystem crossing (rISC) process from the initial T 1 to final S 1 states involves two up-conversion channels (direct T 1 →S 1 and T 2 -mediated T 1 →T 2 →S 1 pathways) and both play crucial roles in TADF. At 300 K, these two channels are much faster than the T 1 phosphorescence emission enabling TADF. However, at 80 K, these rISC rates are reduced by several orders of magnitude and become very small, which blocks the TADF emission; instead, only the phosphorescence is observed. These findings rationalize the experimental observation and could provide useful guidance to rational design of organometallic materials with superior TADF performances., (© 2022 Wiley-VCH GmbH.)

Herein we investigated the luminescence mechanism of one "carbene-metal-amide" copper compound with thermally activated delayed fluorescence (TADF) using density functional theory (DFT)/multireference configuration interaction, DFT, and time-dependent DFT methods with the polarizable continuum model. The experimentally observed low-energy absorption and emission peaks are assigned to the S 1 state, which exhibits clear interligand and partial ligand-to-metal charge-transfer character. Moreover, it was found that a three-state (S 0 , S 1 , and T 1 ) model is sufficient to describe the TADF mechanism, and the T 2 state should play a negligible role. The calculated S 1 -T 1 energy gap of 0.10 eV and proper spin-orbit couplings facilitate the reverse intersystem crossing (rISC) from T 1 to S 1 . At 298 K, the rISC rate of T 1 → S 1 (∼10 6 s -1 ) is more than 3 orders of magnitude larger than the T 1 phosphorescence rate (∼10 3 s -1 ), thereby enabling TADF. However, it disappears at 77 K because of a very slow rISC rate (∼10 1 s -1 ). The calculated TADF rate, lifetime, and quantum yield agree very well with the experimental data. Methodologically, the present work shows that only considering excited-state information at the Franck-Condon point is insufficient for certain emitting systems and including excited-state structure relaxation is important.

Carbene-Au-amide (CMA) type complexes, in which the amide and carbene ligands act as an electron donor (D) and acceptor (A), respectively, can exhibit strong delayed fluorescence (DF) from a ligand to ligand charge transfer (LLCT) excited state. Although the coplanar donor-acceptor (D-A) conformation has been suggested to be a crucial factor favoring radiative decay of the charge-transfer excited state, the geometric structural factor underpinning the excited-state mechanism of CMA complexes remains an open question. We herein develop a new class of carbene-Au-carbazolate complexes by introducing large aromatic substituents onto the carbazolate ligand, the presence of which are conceived to restrict the rotation of the Au-N bond and thus confine a twisted D-A conformation in both ground and excited states. A highly twisted D-A orientation is found for the complexes in their crystal structures. Photophysical studies reveal that the twisted conformation induces a decrease in the gap (Δ E ST ) between the lowest singlet excited state (S 1 ) and the triplet manifold (T 1 ) and thus a faster reverse intersystem crossing (RISC) from T 1 to S 1 at the expense of oscillator strength for an S 1 radiative transition. In comparison with the coplanar analogue, the twisted complexes exhibit comparable or improved DF with quantum yields of up to 94% and short emission lifetimes down to sub-microseconds. The tuning of excited-state dynamics has been well interpreted by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, which unveil much faster RISC rates for twisted complexes. Solution-processed organic light-emitting diodes (OLEDs) based on the new CMA complexes show promising performances with almost negligible efficiency rolloff at a brightness of 1000 cd m -2 . This work implies that neither a coplanar ground-state D-A conformation nor a dynamic rotation of the M-N bond is the key to the realization of efficient DF for CMA complexes.

Metal-based thermally activated delayed fluorescence (TADF) is conceived to inherit the advantages of both phosphorescent metal complexes and purely organic TADF compounds for high-performance electroluminescence. Herein a panel of new TADF Au(I) emitters has been designed and synthesized by using carbazole and pyrazine-fused nitrogen-heterocyclic carbene (NHC) as the donor and acceptor ligands, respectively. Single-crystal X-ray structures show linear molecular shape and coplanar arrangement of the donor and acceptor with small dihedral angles of <6.5°. The coplanar orientation and appropriate separation of the HOMO and LUMO in this type of molecules favour the formation of charge-transfer excited state with appreciable oscillator strength. Together with a minor but essential heavy atom effect of Au ion, the complexes in doped films exhibit highly efficient (Φ∼0.9) and short-lived (<1 μs) green emissions via TADF. Computational studies on this class of emitters have been performed to decipher the key reverse intersystem crossing (RISC) pathway. In addition to a small energy splitting between the lowest singlet and triplet excited states (ΔE ST ), the spin-orbit coupling (SOC) effect is found to be larger at a specific torsion angle between the donor and acceptor planes which favours the RISC process the most. This work provides an alternative molecular design to TADF Au(I) carbene emitters for OLED application., (© 2021 Wiley-VCH GmbH.)

The Pd complex PdN3N exhibits an unusual dual emission of room-temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF), but the mechanism is elusive. Herein, we employed both density functional theory (DFT) and time-dependent DFT (TD-DFT) methods to explore excited-state properties of this Pd complex, which shows that the S 0 , S 1 , T 1 , and T 2 states are involved in the luminescence. Both the S 1 → T 1 and S 1 → T 2 intersystem crossing (ISC) processes are more efficient than the S 1 fluorescence and insensitive to temperature. However, the direct T 1 → S 1 and T 2 -mediated T 1 → T 2 → S 1 reverse ISC (rISC) processes change remarkably with temperature. At 300 K, these two processes are more efficient than the T 1 phosphorescence and therefore enable TADF. Importantly, the T 1 → S 1 rISC and T 1 phosphorescence rates are comparable at 300 K, which leads to dual emissions of TADF and RTP, whereas these two channels become blocked at 100 K so that only the T 1 phosphorescence is recorded experimentally.

We have employed the QM(CASPT2//CASSCF)/MM method to explore the excited-state isomerization and decay mechanism of a single-bond-rotation locked photoactive yellow protein (PYP) chromophore in wild-type and mutant proteins. The S 1 state is a spectroscopically bright state in the Franck-Condon region. In this state, there exist two excited-state isomerization pathways separately related to the clockwise and anticlockwise rotations of the C=C bond. The clockwise path is favorable because of a small barrier of 2 kcal/mol and uses a novel bicycle-pedal unidirectional photoisomerization mechanism in which the involved two dihedral angles rotate asynchronously because of the reinforced hydrogen-bonding interaction between the chromophore and Cys69. Near the twisted S 1 minimum, the chromophore hops to the S 0 state via the S 1 /S 0 conical intersection. Finally, the R52A mutation has small effects on the excited-state properties and photoisomerization of the locked PYP chromophore. The present work provides new insights for understanding the photochemistry of PYP chromophores in protein surroundings.

We synthesized the scientific research carried out in Changbai Mountain from 1956 to 2018 by mapping knowledge domains and bibliometrics based on the literature from international database (WOS) and domestic databases (CNKI and CSCD). The results showed that natural science research in Changbai Mountain underwent three stages during 1956-2018, including embryo stage, growing stage, and rapid development stage. The natural research in Changbai Mountain could be divided into five fields, i.e., forest and ecological science, volcano and geology science, environmental change science, resource sciences and utilization, animal and microbial science, with a total of 20 main research directions. Since 2000, forest and ecological science, volcano and geological science, environmental change science dominated the natural science research in Changbai Mountain. The researches in recent 20 years mainly concentrated on the following seven disciplines: community ecology, forest management, soil ecology, ecosystem ecology, eco-climatology, forest responses to environmental change, and volcanic geology. International researches showed a trend of strong integration of different disciplines. We forecast that the natural science research in the Changbai Mountain would deepen its research in the next decade. Moreover, other fields such as old-growth forest and large-scale ecosystem carbon processes, forest-altitude-climate change, soil fauna and microorganisms, forest management and human activities, biodiversity, volcanic origin and eruption history, volcanic eruption dynamics and volcanic monitoring will emerge as the new research focus. Scale polarization, elements diversification, discipline crossing, and research deepening would be the future trend of natural science research in Changbai Mountain.