Local Excited State Research Articles

Hybrid Local and Charge Transfer Emitters Utilizing Hyperconjugation Effect Towards Solution‐Processed Ultra‐Deep‐Blue OLEDs with External Quantum Efficiency Approaching 12 %

AbstractHybrid local and charge transfer (HLCT) excited state materials, which possess weak donor‐acceptor (D–A) pure organic structures, deserve one of the most promising efficient and stable blue emitters. Through high‐lying reverse intersystem crossing (hRISC) process, 75 % triplet excitons generated by electrical excitation could be harvested and utilized in organic light‐emitting diodes (OLEDs). However, there are still significant challenges to achieve high‐efficiency ultra‐deep‐blue HLCT emitters with low Commission Internationale de l'Eclairage (CIE) 1931 chromaticity coordinate y values. Here, a series of novel blue HLCT emitters based on spiro[1,8‐diazafluorene‐9,2′‐imidazole] structure were designed and synthesized by fine‐tuning the spiro[fluorene‐9,2′‐imidazole] core structure in our previous work through heteroatom substitution and hyperconjugation effect. The target emitters were endowed with excellent photophysical and electrochemical merits, thermal stability and solution processibility. The solution‐processed OLED based on 4′,5′‐bis(4‐(9H‐carbazol‐9‐yl)phenyl)spiro[1,8‐diazafluorene‐9,2′‐imidazole] (NFIP‐CZ) achieved efficient ultra‐deep‐blue emission (CIEx,y=0.1581, 0.0422) with the maximum external quantum efficiency (EQEmax), maximum current efficiency (CEmax) and maximum power efficiency (PEmax) of 11.94 %, 4.07 cd ⋅ A−1 and 2.56 lm ⋅ W−1. The record EQE is a breakthrough in both solution‐processed and vacuum vapor deposition ultra‐deep‐blue HLCT OLEDs currently.

Study of the Energy Crossing Between Excited States Affected by the Electronegativity of Substituents for Three 4-Azido-1,8-naphthalimide Derivatives.

Rapid detection of H2S is crucial for human physiological health and natural ecosystems. In this study, the fluorescent sensing mechanisms of three 4-azido-1,8-naphthalimide-based fluorescent probes to monitor H2S were theoretically investigated by density functional theory and time-dependent density functional theory. The potential energy curve of the charge transfer (CT) state has a crossover with that of the locally excited (LE) state proved by the constructed linear interpolating internal coordinate pathway. Thus, the transform takes place from the LE state to the CT state causing the fluorescence quenching of the probes from a nonradiative transition process of the CT state. The distance between the Franck-Condon point and the minimal energy conical intersection becomes larger with the increase of the electronegativity of substituents on the 1,8-naphthalimide fluorophore. In addition, the degree of charge separation is closely related to the energy difference between the CT and the LE states which are also essentially affected by the electronegativity of the substituents. Since the electronegativity of the substituents has proved important for the probes, our work lays a certain theoretical foundation for the design and synthesis of more sensitive 4-azido-1,8-naphthalimide-based fluorescent probes.

Chalcogen bonds enable efficient photoreduction of sulfur-containing heterocycles.

Chalcogen bonding interactions have attracted significant attention in a broad chemistry community, with a particular focus on their ability to stabilise the key transition states in various organic synthetic routes. In this work, we demonstrate that they can also be harnessed in selective photoredox reactions, which cannot be otherwise achieved with alternative approaches to photoreduction. We demonstrate this concept through the photoreduction of the sulfur-containing DNA nucleoside precursor thioanhydrouridine to 2'-deoxy-thiouridine, revealing the previously unrecognized role of bisulfide in this process. Based on quantum chemical simulations, we identify a stable chalcogen-bonding complex of the hydrosulfide anion and thionhydrouridine (HS-…S contacts), which enables directional photoinduced electron transfer, resulting in the formation of non-canonical DNA nucleoside. We also disprove the possibility that photoreduction of thioanhydronucleosides could be initiated by hydrated electrons generated from irradiated bisulfide anions which do not interact with the chromophore. Finally, we show that selective photoreduction mediated by chalcogen bonds can only occur for chromophores, which exhibit sufficiently long excited-state lifetimes in the locally-excited states to undergo transition to the productive charge transfer state. These findings can be further used in the design of similar photoredox reactions which can employ the potential of chalcogen bonding interactions.

Exploring the interaction between derivatives of urea with resorcinol-based acridinedione dyes by employing fluorescence methods and molecular docking approach

Akyl urea derivatives, either symmetrical or unsymmetrical in nature possessing a free N-H or N-alkyl moieties in the molecular framework of urea governs the excited state properties of acridinedione dye (ADR1) which is a resorcinol-based derivative. Fluorescence enhancement (FE) of ADR1 dye is observed on the addition of unsymmetrical urea derivatives, whereas a decrease in the fluorescence intensity resulted upon the addition of symmetrical urea derivatives. The nature of the urea derivatives controls the suppression of photoinduced electron transfer (PET) via space, which is the cause of the FE. FQ results from the donor and acceptor moieties of ADR1 dye promoting the PET process. Urea (U), symmetrical and unsymmetrical urea derivatives (except Tetramethyl urea (TMU)) results no significant shift of the localized excited (LE) state emission of ADR1 dye. Studies of the ADR1 dye’s fluorescence lifetime in the presence of urea compounds show a significant increase in lifetime. This phenomenon is explained by a significant difference in the hydrogen-bonding (HB) pattern, which causes variationin the microenvironment created by thesolute molecules in the aqueous phase. Both the hydrophobic effects of the alkyl group substituents in the urea molecular framework and the HB interactions between the solute and solvent influence the excited state features of ADR1 dye. Further, the role of urea derivatives and ADR1 dye (both are considered as competitive guest molecules) energetics and molecular interactions were studied in the presence of host molecule, Human Serum Albumin (HSA). The binding energy (BE) and several bimolecular interactions driven by urea derivatives in the presence of ADR1-HSA complex in comparison with that of urea derivatives-HSA complex were investigated by molecular docking (Mol.Doc) methodology. Incorporating theoretical research along withsteady state and time-resolved fluorescence investigations proved to be an effective method to evaluate the interactions of competing solutes comprising bothhydrophobic and HB functional groups.

Solvent polarity-driven modulation of excited states: A DFT and spectroscopic analysis

The relationship between the photophysical properties of N,N,N’,N’-tetra-p-tolyl-benzidine (TTB) and [1,4-bis[2-[4-[N,N-di(p-tolyl)amino]phenyl]vinyl]benzene (DSB) molecules and solvent polarity was explored through steady-state spectroscopy, femtosecond transient absorption spectroscopy, and quantum chemical calculations. Computational results and steady-state spectra reveal that the lowest singlet excited states of TTB and DSB are primarily characterized by localized excited (LE) states in nonpolar cyclohexane (CHX), whereas intramolecular charge transfer (ICT) components predominate in highly polar acetonitrile (ACN). Compared to TTB, the excited-state potential of DSB demonstrates a heightened sensitivity to solvent polarity, exhibiting larger dipole moments due to enhanced electron transfer enabled by the incorporation of styrene groups. Ultrafast femtosecond transient absorption spectroscopy distinctly shows the transition from LE states in nonpolar CHX to ICT states in highly polar ACN. The deactivation mechanisms were further elucidated to understand how solvent polarity modulates excited states and high quantum yields, providing valuable insights for the design and application of photophysical materials.

Hybrid Local and Charge Transfer Emitters Utilizing Hyperconjugation Effect Towards Solution-Processed Ultra-Deep-Blue OLEDs with External Quantum Efficiency Approaching 12.

Hybrid local and charge transfer (HLCT) excited state materials, which possess weak donor-acceptor (D-A) pure organic structures, deserve one of the most promising efficient and stable blue emitters. Through high-lying reverse intersystem crossing (hRISC) process, 75% triplet excitons generated by electrical excitation could be harvested and utilized in organic light-emitting diodes (OLEDs). However, there are still significant challenges to achieve high-efficiency ultra-deep-blue HLCT emitters with low Commission Internationale de l'Eclairage (CIE) 1931 chromaticity coordinate y values. Here, a series of novel blue HLCT emitters based on spiro[1,8-diazafluorene-9,2'-imidazole] structure were designed and synthesized by fine-tuning the spiro[fluorene-9,2'-imidazole] core structure in our previous work through heteroatom substitution and hyperconjugation effect. The target emitters were endowed with excellent photophysical and electrochemical merits, thermal stability and solution processibility. The solution-processed OLED device based on 4',5'-bis(4-(9H-carbazol-9-yl)phenyl)spiro[1,8-diazafluorene-9,2'-imidazole] (NFIP-CZ) achieved efficient ultra-deep-blue emission (CIEx,y = 0.1581, 0.0422) with the maximum external quantum efficiency (EQEmax), maximum current efficiency (CEmax) and maximum power efficiency (PEmax) of 11.94%, 4.07 cd·A-1 and 2.56 lm·W-1. The record EQE is a breakthrough in both solution-processed and vacuum vapor deposition ultra-deep-blue HLCT-OLEDs currently.

Excited-State Dynamics of a Bright Fluorescent Dye with Precise Control of Emission Color Using Acid-Base Equilibrium, Intramolecular Charge Transfer, and Host-Guest Chemistry.

A fluorescent dye, a dithiophene-conjugated benzothiazole derivative (DTBz), was prepared to have high fluorescence emission quantum yields (ΦF) across various organic solvents. Its emission color modulation, from bright blue to deep red, was achieved through intramolecular charge transfer (ICT), acid-base equilibrium, and host-guest chemistry. Although it exhibits a weak solvatochromic effect, DTBz exhibited a bright fluorescence emission around 480 nm upon excitation at 390 nm in most solvents. In polar solvents, such as MeOH (methanol), EtOH (ethanol), DMF (N,N-dimethylforamide), and DMSO (dimethyl sulfoxide), an additional ICT emission band emerged around 640 nm, notably intense in DMSO, resulting in a bright greenish-white emission (ΦF = 0.67). The addition of 1,8-diazabicyclo[5,4.0]undec-7-ene (DBU) altered emission characteristics, reducing emission from the local excited (LE) state and enhancing ICT state emission. The degree of emission spectral change saturation with DBU addition varied with the solvent nature. Polar solvents with high dielectric constants, like DMSO and DMF, saw a complete disappearance of LE state emission with 5 equiv of DBU, resulting in a deep red emission (ΦFs of 0.53 and 0.48, respectively). Femtosecond transient absorption spectroscopy and time-resolved photoluminescence measurements elucidated the excited-state dynamics, revealing a long-lived excited state (τ-H = 10.3 ns) at a lower energy emission (640 nm), identified as DTBz-*, supported by transient absorption spectra analysis. Further analysis, including time-resolved fluorescence decay measurements and time-dependent density-functional theory (TD-DFT) calculations, underscored the role of deprotonation of DTBz's hydroxyl group in promoting the ICT process. The CIE coordination plot demonstrated wide linear emission color changes upon successive DBU additions in all solvents, while emission color precision was achieved through host-guest chemistry. Emission changes induced by DBU were reverted to the original state upon beta-cyclodextrin (β-CD) addition, with the 1H NMR study revealing the competition between acid-base equilibrium and host-guest complex formation as the cause of emission color change.

Deep-blue electroluminescence with orthogonal donor-acceptor structure: The role of charge-transfer excited state component in hybrid local and charge-transfer (HLCT) excited state

In this work, three orthogonally bonded phenanthroimidazole based donor-acceptor (D-A) structured blue-emissive materials N-SBPMCN, N-ABPMCN and N-TBPMCN with different donor moieties are designed synthesized. Theoretical combined experimental researches proved that the involving of weak donor (spiro-fluorene and anthracene) and strong donor triphenylamine can form different locally-emissive (LE) dominated hybrid local and charge-transfer (HLCT) excited state, which can contribute to their high photoluminescent quantum yield (PLQY), satisfied electroluminescence performance and blue purity. Specifically, N-TBPMCN with strong donor triphenylamine that possesses more CT excited state components demonstrates the best electroluminescence performance and blue purity among the three materials, revealing that the molecular design of orthogonal D-A structure is of great potential in blue-emissive functional materials. Additionally, we also discovered that intermolecular CT state can also contribute to high exciton utilization.

Mechanochromic luminescent material with high quantum yield for multi-mode anti-counterfeiting applications

The multi-mode anti-counterfeiting materials, constructed by mechanochromic luminescent materials with high quantum yield, can effectively prevent illegal counterfeiting, but their design and construction still present significant challenges. Herein, a twisting D-A-D conjugated molecule, FBtF, is obtained with a special hybridized local and charge transfer excited state, and shows approximately 100 % photoluminescence quantum yield in the coating film. The self-assembled FBtF microplates exhibit bathochromic-shifted emission from green to orange, accompanied by the photoluminescence quantum yield increase from 47.8 % to 89.0 % upon grinding, which is the highest in reported MCL materials, to the best of our knowledge. In contrast, a D-π-D type molecule (FBenF) and a D-D’-D molecule (FAnF) maintain the blue-emission after grinding. Through mechanistic investigation, the force-induced molecular conformational planarization and the breakage of the intermolecular charge transfer collaboratively lead to the emission-color change and photoluminescence quantum yield increase. The FBtF microplates are designed as ink for anti-counterfeiting applications based on multi-mode output signals, including the UV light-excited image and the grinding-induced emission color change together with the photoluminescence quantum yield increase. The written tags exhibit high stability in various harsh environments, and demonstrate superior anti-counterfeiting performance in practical applications, such as medicine anti-counterfeiting.

(Invited) Manipulation of Locally-Excited, Charge-Transfer, and Charge-Separated States at Organic-Inorganic Heterointerfaces

Precise engineering of excited-state interactions between an organic conjugated molecule and a two-dimensional semiconducting inorganic nanosheet, specifically the manipulation of locally-excited (LE), charge-transfer (CT), and charge-separated (CS) states, still remains a challenge for state-of-the-art photochemistry. In this study we successfully observed a long-lived, highly emissive CT state at structurally well-defined hetero-nanostructure interfaces of photoactive pyrene and two-dimensional (2D) MoS2 nanosheet via N-benzyl succinimide bridge (Py-Bn-MoS2). Spectroscopic measurements revealed that the LE state of pyrene in Py-Bn-MoS2 efficiently generates an unusual emissive CT state without further yielding the CS state. Theoretical studies supported the interaction of MoS2 vacant orbitals with the pyrene excited state to form a CT state. This is the first example of realizing a mixing luminescence property of organic–inorganic 2D hetero-nanostructures by an accurate design of bridge structure, and therefore represents an important step in their applications for energy conversion and optoelectronic devices and sensors.[1] J. Baek, T. Umeyama, W. Choi, Y. Tsutsui, H. Yamada, S. Seki, H. Imahori, Chem. Eur. J., 24, 1561 (2018).[2] T. Umeyama, T. Ohara, Y. Tsutsui, S. Nakano, S. Seki, H. Imahori, Chem. Eur. J., 26, 6726 (2020).[3] T. Umeyama, H. Xu, T. Ohara, Y. Tsutsui, S. Seki, and H. Imahori, J. Phys. Chem. C, 125, 13954 (2021).[4] T. Umeyama, D. Mizutani, Y. Ikeda, W. R. Osterloh, F. Yamamoto, K. Kato, A. Yamakata, M. Higashi, T. Urakami, H. Sato, H. Imahori, Chem. Sci., 14, 11914 (2023).

Deep Blue Emitter with a Combination of Hybridized Local and Charge Transfer Excited State and Aggregation-Induced Emission Features for Efficient Non-Doped OLED.

Herein, a deep blue emitter (PI-TPB-CN) with a synergistic effect of hybridized local and charge transfer excited state (HLCT) and aggregation-induced emission (AIE) properties is successfully designed and synthesized to improve the performance of deep blue organic light-emitting diodes (OLEDs). It is constructed using a 1,2,4,5-tetraphenylbenzene (TPB) as an π-conjugated AIE core being asymmetrically functionalized with a phenanthro[9,10-d]imidazole (PI) as a weak donor (D) and a benzonitrile (CN) as an acceptor (A), thereby formulating D-π-A type fluorophore. Its HLCT and AIE properties verified by theoretical calculations, solvatochromic effects, and transient photoluminescence decay experiments, bring about a strong blue emission (452 nm) with a high photoluminescence quantum yield of 74 % in the thin film. PI-TPB-CN is successfully employed as a blue emitter in OLEDs. Non-doped OLED with the structure of ITO/HAT-CN (6 nm)/NPB (30 nm)/TCTA (10 nm)/PI-TPB-CN (30 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm) demonstrates excellent electroluminescence (EL) performance with blue emission (451 nm) and maximum external quantum efficiency (EQEmax) of 7.38 %. The device with a thinner layer of PI-TPB-CN (20 nm) and TPBi (30 nm) exhibits a deeper blue emission (444 nm) with CIE coordinates of (0.156, 0.096), a low turn-on voltage of 3.0 V, and EQEmax of 6.45 %.

Fluorescent properties of chitosan-stabilized bisdemethoxycurcumin-silver nanoparticles: Synthesis and characterization

The extraction and modification of naturally-occurring compounds are widely performed due to their valuable medicinal and physical properties. Herin, we reported the extraction of bis-demethoxycurcumin from Ragbrai turmeric root. The isolated derivative was characterized by X-ray diffraction, IR, and NMR spectroscopy. Also, the green synthesis of bis-demethoxycurcumin chitosan silver BDMC-Ag-Ch nanoparticles is illustrated. These nanoparticles are identified by atomic force microscopy AFM and exhibit average particle size ∼ 53.41 nm The crystalline structure was confirmed by XRD analysis, which showed distinct peaks corresponding to silver oxide nanoparticles and Zeta power measurements revealed stable dispersion of the nanoparticles, indicating a good chitosan coating on the surface of bis-demethoxycurcumin Ag nanoparticles. The absorption bands at 240 and 405 nm are due to oxygen atom (n → π*) and aromatic (π → π*) transitions in curcumin and Chitosan molecules. The photoluminescence (PL) study of synthesized BDMC-Ag-Ch nanoparticles demonstrated an existence of two emission excited states in light-emitting, namely local excited (LE) and intramolecular charge transfer (ICT) emission states, due to the aromatic conjugation system within BDMC units and intra charge transfer between the silver ion and organic part.

Regulating Planarized Intramolecular Charge Transfer for Efficient Single-Phase White-Light Emission in Undoped Metal-Organic Framework Nanocrystals.

The technology of combining multiple emission centers to exploit white-light-emitting (WLE) materials by taking advantage of porous metal-organic frameworks (MOFs) is mature, but preparing undoped WLE MOFs remains a challenge. Herein, a pressure-treated strategy is reported to achieve efficient white photoluminescence (PL) in undoped [Zn(Tdc)(py)]n nanocrystals (NCs) at ambient conditions, where the Commission International del'Eclairage coordinates and color temperature reach (0.31, 0.37) and 6560 K, respectively. The initial [Zn(Tdc)(py)]n NCs exhibit weak-blue PL consisting of localized excited (LE) and planarized intramolecular charge transfer (PLICT) states. After pressure treatment, the emission contributions of LE and PLICT states are balanced by increasing the planarization of subunits, thereby producing white PL. Meanwhile, the reduction of nonradiative decay triggered by the planarized structure results in 5-fold PL enhancement. Phosphor-converted light-emitting diodes based on pressure-treated samples show favorable white-light characteristics. The finding provides a new platform for the development of undoped WLE MOFs.

The Role of Locally Excited State and Charge Transfer State in Organic Room Temperature Phosphorescence and Corresponding Applications

AbstractDonor–acceptor (D–A) structure with charge transfer (CT) effect is widely utilized in the construction of organic luminescent materials. The adjustment of their CT effect and related luminescent property usually relies on the changes of molecular structure with different D or A moieties, which will lead to some uncertainties in structure‐property relationship. With the aim to explore the clear inherent luminescent mechanism for D–A molecule with CT effect, it is ideal that the regulation of intramolecular charge transfer in one same D–A molecule can be realized. Accordingly, three D–A type organic phosphorescence luminogens are designed and synthesized. Once being doped into different polymer matrixes, disparate charge transfer effects and related room temperature phosphorescence (RTP) properties can be achieved for a single molecule. Subsequent experiments confirm that different distributions of molecules with locally excited (LE) state and CT state are mainly responsible for their distinct RTP behaviors, exhibiting the well‐clarified structure‐property relationship of D–A type phosphorescence luminogens. Furthermore, the transition from CT to LE state can even be realized through chemical reaction, leading to the activated RTP effect for practical applications.

Excitation configuration analysis for divide-and-conquer excited-state calculation method using dynamical polarizability.

The authors previously developed a divide-and-conquer (DC)-based non-local excited-state calculation method for large systems using dynamical polarizability [Nakai and Yoshikawa, J. Chem. Phys. 146, 124123 (2017)]. This method evaluates the excitation energies and oscillator strengths using information on the dynamical polarizability poles. This article proposes a novel analysis of the previously developed method to obtain further configuration information on excited states, including excitation and de-excitation coefficients of each excitation configuration. Numerical applications to simple molecules, such as ethylene, hydrogen molecule, ammonia, and pyridazine, confirmed that the proposed analysis could accurately reproduce the excitation and de-excitation coefficients. The combination with the DC scheme enables both the local and non-local excited states of large systems with an excited nature to be treated.

Symmetry Molecular Design Strategy for Highly Efficient Blue Electroluminescence with Hot Exciton Mechanisms

AbstractEmitters with a hot exciton mechanism are regarded as one of the most promising candidates for organic light‐emitting diodes (OLEDs). In this study, a deep‐blue emitter with the hot exciton mechanism is reported, namely 2An‐PCz, by integrating a pair of carbazole groups with a 9,9′‐bi‐anthracene nucleus. Owing to the symmetric molecular architecture and intrinsic local excited state character, multiple high‐lying reverse intersystem cross (hRISC) channels and large overlaps of frontier molecular orbits (FMOs) can be formed, facilitating rapid hRISC processes as well as enhancement of radiative transition rates simultaneously. Combined with the strong luminescence properties brought by the unique X‐packing mode, a high photoluminescence quantum yield of 60.5% is achieved in the non‐doped state. Strikingly, non‐doped deep‐blue OLEDs exhibited a maximum external quantum efficiency (EQE) of 10.50% with minimal efficient roll‐off, which is one of the highest values for deep‐blue organic light‐emitting devices based on hot exciton emitters thus far. The magneto‐electroluminescence (MEL) experiment and transient electroluminescence measurements corroborated that both the high EQE and suppressed efficiency roll‐off are attributable to the rapid “hot exciton” channels.

Stepwise Charge/Energy Transfer in MR-TADF Molecule-Doped Exciplex for Ultralong Persistent Luminescence Activated with Visible Light.

Organic long-persistent luminescence (OLPL), which relies on energy storage for delayed light emission by the charge separation state, has attracted intense attention in various optical applications. However, charge separation (CS) is efficient only under ultraviolet excitation in most OLPL systems because it requires a driving force from the large energy difference between the local excited (LE) and charge transfer (CT) states. In this study, a multiresonance thermally activated delayed fluorescence (MR-TADF) molecule is incorporated into an exciplex system to achieve efficient OLPL in a composite material activated by visible light via a stepwise charge/energy transfer process. The enhanced absorption of the composite material facilitated a tenfold increase in the duration of the OLPL, which can last for several hours under visible light excitation. The excited state of the MR-TADF molecule tends to charge transfer to the acceptor, followed by energy transfer to the exciplex, which benefits from the small difference between the LE and CT states owing to the inherent CS characteristics of the opposing resonance effect. Afterglow displays of these composite materials are fabricated to demonstrate their considerable potential in encryption patterns and emergency lights, which take advantage of their excellent processability, visible light activation, and tunable luminescence properties.

Excited-State Charge Transfer Coupling from Quasiparticle Energy Density Functional Theory.

The recently developed Quasiparticle Energy (QE) scheme, based on a DFT calculation with one more (or less) electron, offers a good description of excitation energies, even with charge transfer characters. In this work, QE is further extended to calculate electron transfer (ET) couplings involving two excited states. We tested it with a donor-acceptor complex, consisting of a furan and a 1,1-dicyanoethylene (DCNE), in which two low lying charge transfer and local excitation states are involved. With generalized Mülliken-Hush and fragment charge-difference schemes, couplings from the QE approach generally agree well with those obtained from TDDFT, except that QE couplings exhibit better exponential distance dependence. Couplings from half-energy gaps with an external field are also calculated and reported. Our results show that the QE scheme is robust in calculating ET couplings with greatly reduced computational time.

Efficient Blue Photo- and Electroluminescence from CF3-Decorated Cu(I) Complexes.

Luminescent organometallic complexes of earth-abundant copper(I) have long been studied in organic light-emitting diodes (OLED). Particularly, Cu(I)-based carbene-metal-amide (CMA) complexes have recently emerged as promising organometallic emitters. However, blue-emitting Cu(I) CMA complexes have been rarely reported. Here we constructed two blue-emitting Cu(I) CMA emitters, MAC*-Cu-CF3Cz and MAC*-Cu-2CF3Cz, by introducing one or two CF3 substitutes into carbazole ligands. Both complexes exhibited high thermal stability and blue emission colors. Moreover, two complexes exhibited different emission origins rooting from different donor ligands: a distinct thermally activated delayed fluorescence (TADF) from ligand-to-ligand charge transfer excited states for MAC*-Cu-CF3Cz or a dominant phosphorescence nature from local triplet excited state of the carbazole ligand for MAC*-Cu-2CF3Cz. Inspiringly, MAC*-Cu-CF3Cz had high photoluminescence quantum yields of up to 94 % and short emission lifetimes of down to 1.2 μs in doped films, accompanied by relatively high radiative rates in the 105 s-1 order. The resultant vacuum-deposited OLEDs based on MAC*-Cu-CF3Cz delivered pure-blue electroluminescence at 462 nm together with a high external quantum efficiency of 13.0 %.

Controlled Self‐Assembly of Zn–Tetraphenylporphyrins for Efficient Photocatalytic Solar H2 Production and Simultaneous Organic Transformation to Valuable Chemicals

Herein, we have designed aqueous dispersed self‐assembled nanostructures with diverse morphologies from the zinc tetraphenyl porphyrin (ZnTPP) monomer employing a simple solution‐based coprecipitation methods. Detail morophological studies have been carried out by various electron microscopy techniques. Finally, the structural features were correlated with the underpinning photophysical processes using steady‐state and time‐resolved spectroscopy. Detailed studies suggest that control morphology and highly defined intermolecular interactions affect the overall photoinduced charge transfer process. Based on the fundamental investigations, all these different types of nanostructures have been utilized as photocatalysts for solar hydrogen production, without using any cocatalysts, and it was found that the spherical nanostructure exhibits significantly higher H2 production rates of ~1682 m mole/ g, which is few folds higher than other 1D and 2D nanostructured materials. The experimental findings were further supported by the TD‐DFT study. Furthermore, the detailed computational studies suggest that the spherical aggregates exhibited a more vital interaction between the ZnTPP molecules, causes significant electronic coupling between bright local excited and charge transfer states, which supports our experimental findings. Finally, we have selectively utilized the oxidative half‐reaction for the simultaneous transformation of glycerol to valuable chemicals along with photocatalytic H2 production through reductive half‐reaction.