Efficient Intramolecular Charge Transfer in Oligoyne‐Linked Donor–π–Acceptor Molecules

Studies are reported on a series of triphenylamine–(C?C)_n–2,5‐diphenyl‐1,3,4‐oxadiazole dyad molecules (n=1–4, 1 , 2 , 3 and 4 , respectively) and the related triphenylamine‐C₆H₄–(C?C)₃–oxadiazole dyad 5 . The oligoyne‐linked D–π–A (D=electron donor, A=electron acceptor) dyad systems have been synthesised by palladium‐catalysed cross‐coupling of terminal alkynyl and butadiynyl synthons with the corresponding bromoalkynyl moieties. Cyclic voltammetric studies reveal a reduction in the HOMO–LUMO gap in the series of compounds 1 – 4 as the oligoyne chain length increases, which is consistent with extended conjugation through the elongated bridges. Photophysical studies provide new insights into conjugative effects in oligoyne molecular wires. In non‐polar solvents the emission from these dyad systems has two different origins: a locally excited (LE) state, which is responsible for a π*→π fluorescence, and an intramolecular charge transfer (ICT) state, which produces charge‐transfer emission. In polar solvents the LE state emission vanishes and only ICT emission is observed. This emission displays strong solvatochromism and analysis according to the Lippert–Mataga–Oshika formalism shows significant ICT for all the luminescent compounds with high efficiency even for the longer more conjugated systems. The excited‐state properties of the dyads in non‐polar solvents vary with the extent of conjugation. For more conjugated systems a fast non‐radiative route dominates the excited‐state decay and follows the Engelman–Jortner energy gap law. The data suggest that the non‐radiative decay is driven by the weak coupling limit.     

Femtosecond Excitonic Relaxation Dynamics of Perovskite on Mesoporous Films of Al2O3 and NiO Nanoparticles

The excitonic relaxation dynamics of perovskite adsorbed on mesoporous thin films of Al₂O₃ and NiO upon excitation at 450 nm were investigated with femtosecond optical gating of photoluminescence (PL) via up‐conversion. The temporal profiles of emission observed in spectral region 670–810 nm were described satisfactorily with a composite consecutive kinetic model and three transient components representing one hot and two cold excitonic relaxations. All observed relaxation dynamics depend on the emission wavelength, showing a systematic time–amplitude correlation for all three components. When the NiO film was employed, we observed an extent of relaxation proceeding through the non‐emissive surface state larger than through the direct electronic relaxation channel, which quenches the PL intensity more effectively than on the Al₂O₃ film. We conclude that perovskite is an effective hole carrier in a p‐type electrode for NiO‐based perovskite solar cells showing great performance.     

Unravelling the Quenching Mechanisms of a Luminescent RuII Probe for CuII

We have investigated the photophysical and photochemical features of a luminescent heteroleptic Ru^II‐polypyridyl probe and of its corresponding Ru^II‐Cu^II dinuclear complex formed upon the analyte binding through extensive density functional theory (DFT) and time‐dependent DFT (TD‐DFT) calculations. The molecular probe contains the tailored imidazo[4,5‐f]‐1,10‐phenanthroline (IIP) ligand for simultaneously binding the Ru^II core and the target metal ion in aqueous solution. We have rationalized the static photoluminescence quenching observed upon the Cu^II coordination, on the grounds of distinct excited state deactivation mechanisms which are absent in the free Ru^II complex probe. Additionally, the emission quenching found upon increasing the solution pH has also been investigated. When coordinated IIP deprotonates, the nature of the lowest excited state of its complex changes from ³MLCT to ³LLCT/³IL. The strong base‐induced emission quenching can be understood in terms of both the energy‐gap law, since the ³LLCT/³IL states lie at a significantly lower energy than the ³MLCT state increasing the contribution of non‐radiative mechanisms, and the expected slower radiative rates from such ³LLCT/³IL states. After Cu^II binding, the lowest triplet excited state is similar to the analyte‐free probe in both energy and electronic nature. However, Cu‐centered non‐radiative excited states, populated after photoinduced electron transfer and intersystem crossing processes, are responsible for the population drainage of the emissive state.     

Localization and Dynamics of Long‐Lived Excitations in Colloidal Semiconductor Nanocrystals with Dual Quantum Confinement

Semiconductor nanocrystals consisting of a quantum dot (QD) core and a quantum well (QW) shell, where the QD and QW are separated by a tunneling barrier, offer a unique opportunity to engineer the photophysical properties of individual nanostructures. Using the thicknesses of the corresponding layers, the excitons of the first and second excited states can be separated spatially, localizing one state to the QD and the other to the QW. Thus the wave function overlap of the two states can be minimized, suppressing non‐radiative thermalization between the two wells, which in turn leads to radiative relaxation from both states. The molecular analogy to such dual emission would be the inhibition of internal conversion, a special case that violates Kasha′s rule. Using nanosecond time‐resolved spectroscopy of QDQW CdSe/ZnS onion‐like nanocrystals, an intermediate regime of exciton separation and suppressed thermalization is identified where the non‐radiative relaxation of the higher‐energy state is slowed, but not completely inhibited. In this intermediate thermalization regime, the temporal evolution of the delayed emission spectra resulting from trapped carriers mimic the dynamics of such states in nanocrystals that consist of only a QD core. In stark contrast, when a higher‐energy metastable state exists in the QW shell due to strongly suppressed interwell thermalization, the spectral dynamics of the long‐lived excitations in the QD and QW, which are spectrally distinct, are amplified and differ from each other as well as from those in the core‐only nanocrystals. This difference in spectral dynamics demonstrates the utility of exploiting well‐defined exciton localization to study the nature and spatial dependence of the intriguing photophysics of colloidal semiconductor nanocrystals, and illustrates the power of nanosecond gated luminescence spectroscopy in illuminating complex relaxation dynamics which are entirely masked in steady‐state or ultrafast spectroscopy.     

Boosting Non‐Radiative Decay to Do Useful Work: Development of a Multi‐Modality Theranostic System from an AIEgen

The efficient utilization of energy dissipating from non‐radiative excited‐state decay of fluorophores was only rarely reported. Herein, we demonstrate how to boost the energy generation of non‐radiative decay and use it for cancer theranostics. A novel compound (TFM) was synthesized which possesses a rotor‐like twisted structure, strong absorption in the far red/near‐infrared region, and it shows aggregation‐induced emission (AIE). Molecular dynamics simulations reveal that the TFM aggregate is in an amorphous form consisting of disordered molecules in a loose packing state, which allows efficient intramolecular motions, and consequently elevates energy dissipation from the pathway of thermal deactivation. These intrinsic features enable TFM nanoparticles (NPs) to display a high photothermal conversion efficiency (51.2 %), an excellent photoacoustic (PA) effect, and effective reactive oxygen species (ROS) generation. In vivo evaluation shows that the TFM NPs are excellent candidates for PA imaging‐guided phototherapy.     

Estimation of the degree of ionization and the proportion of excited atoms in flame atomic spectrometry: a steady state approach

Summary A model is presented for the ionization of elements during flame atomic spectrometry, based on successive excitation of the electron to higher energy levels and finally the ionized state. The model is discussed in terms of a steady state involving thermal excitation, ionization, collisional excitation and collisional charge transfer interactions within the flame. Expressions are derived for the fraction ionized, and the fraction excited in terms of the rate constants for thermal excitation and radiative relaxation of the excited state. Data are presented showing good agreement between calculated and literature values for the fraction ionized for representative Group I and Group II elements.     

Mechanistic Understanding of Oxidation of Tin-based Perovskite Solar Cells and Mitigation Strategies

Tin (Sn)-based perovskites as the most promising absorber materials for lead-free perovskite solar cells (PSCs) have achieved the record efficiency of over 14 %. Although suppressing the oxidation of Sn-based perovskites is a frequently concerned topic for Sn-based PSCs, many studies have given vague explanations and the mechanisms are still under debate. This is in principal due to the lack of an in-depth understanding of various and complex intrinsic and extrinsic factors causing the oxidation process. In this context, we critically review the chemical mechanism of facile oxidation of Sn-based perovskites and differentiate its detrimental effects at material- and device-level. More importantly, we classify and introduce the intrinsic factors (raw materials and solvent of perovskite precursors) and extrinsic factors (exposure to neutral oxygen and superoxide) causing the oxidation with their corresponding anti-oxidation improvement methods. The presented comprehensive understanding and prospect of the oxidation provide insightful guidance for suppressing the oxidation in Sn-based PSCs “from the beginning to the end”.     

Metal bacteriochlorins which act as dual singlet oxygen and superoxide generators

A series of stable free-base, Zn(II) and Pd(II) bacteriochlorins containing a fused six- or five-member diketo- or imide ring have been synthesized as good candidates for photodynamic therapy sensitizers, and their electrochemical, photophysical, and photochemical properties were examined. Photoexcitation of the palladium bacteriochlorin affords the triplet excited state without fluorescence emission, resulting in formation of singlet oxygen with a high quantum yield due to the heavy atom effect of palladium. Electrochemical studies revealed that the zinc bacteriochlorin has the smallest HOMO-LUMO gap of the investigated compounds, and this value is significantly lower than the triplet excited-state energy of the compound in benzonitrile. Such a small HOMO-LUMO gap of the zinc bacteriochlorin enables intermolecular photoinduced electron transfer from the triplet excited state to the ground state to produce both the radical cation and the radical anion. The radical anion thus produced can transfer an electron to molecular oxygen to produce superoxide anion which was detected by electron spin resonance. The same photosensitizer can also act as an efficient singlet oxygen generator. Thus, the same zinc bacteriochlorin can function as a sensitizer with a dual role in that it produces both singlet oxygen and superoxide anion in an aprotic solvent (benzonitrile).     

Stable Blue Luminescent CsPbBr3 Perovskite Nanocrystals Confined in Mesoporous Thin Films

Creating CsPbBr₃ perovskite nanocrystals with bright blue emission is challenging because their optical properties depend sensitively on structure. Growing perovskites in mesoporous templates bypasses some of these purification issues because the size of the nanocrystal is governed by the dimensions of the pores. Mesoporous silica consisting of aligned channels with tunable diameter can be easily synthesized and used as a template. When the perovskite solution evaporates and retreats, some of the liquid remains trapped in the interconnecting pores by discontinuous dewetting. The precursor crystallizes, generating stable ca. 3.1 nm blue‐emitting perovskite nanocrystals. The mesoporous template also serves as a protective barrier to preserve the optical properties of the CsPbBr₃ from atmospheric conditions. Compared to the bulk crystals and the powder composite, the strong blue‐shift of the emission peak in the film is accompanied by a decrease in the longer lifetime component and an 8‐fold increase in the external quantum efficiency.     

Cocrystals Strategy towards Materials for Near‐Infrared Photothermal Conversion and Imaging

A cocrystal strategy with a simple preparation process is developed to prepare novel materials for near‐infrared photothermal (PT) conversion and imaging. DBTTF and TCNB are selected as electron donor (D) and electron acceptor (A) to self‐assemble into new cocrystals through non‐covalent interactions. The strong D–A interaction leads to a narrow band gap with NIR absorption and that both the ground state and lowest‐lying excited state are charge transfer states. Under the NIR laser illumination, the temperature of the cocrystal sharply increases in a short time with high PT conversion efficiency (η=18.8 %), which is due to the active non‐radiative pathways and inhibition of radiative transition process, as revealed by femtosecond transient absorption spectroscopy. This is the first PT conversion cocrystal, which not only provides insights for the development of novel PT materials, but also paves the way of designing functional materials with appealing applications.     

Simultaneous Long‐Persistent Blue Luminescence and High Quantum Yield within 2D Organic–Metal Halide Perovskite Micro/Nanosheets

Molecular solid‐state materials with long‐lived luminescence (such as thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) systems) are promising for display, sensoring, and bio‐imaging applications. However, the design of such materials that exhibit both long luminescent lifetime and high solid‐state emissive efficiency remains an open challenge. Two‐dimensional (2D) organic–metal halide perovskite materials have a high blue‐emitting quantum yield of up to 63.55 % and ultralong TADF lifetime of 103.12 ms at ambient temperature and atmosphere. Our design leverages the combined influences of a 2D space/electronic confinement effect and a modest heavy‐atom tuning strategy. Photophysical studies and calculations reveal that the enhanced quantum yield is due to the rigid laminate structure of perovskites, which can effectively inhibit the non‐radiative decay of excitons.     

Photophysical studies of dipolar organic dyes that feature a 1,3-cyclohexadiene conjugated linkage: the implication of a twisted intramolecular charge-transfer state on the efficiency of dye-sensitized solar cells

A detailed study of the synthesis and photophysical properties of a new series of dipolar organic photosensitizers that feature a 1,3‐cyclohexadiene moiety integrated into the π‐conjugated structural backbone has been carried out. Dye‐sensitized solar cells (DSSCs) based on these structurally simple dyes have shown appreciable photo‐to‐electrical energy conversion efficiency, with the highest one up to 4.03 %. Solvent‐dependent fluorescence studies along with the observation of dual emission on dye 4 b and single emission on dyes 4 a and 32 suggest that dye 4 b possesses a highly polar emissive excited state located at a lower‐energy position than at the normal emissive excited state. A detailed photophysical investigation in conjunction with computational studies confirmed the twisted intramolecular charge‐transfer (TICT) state to be the lowest emissive excited state for dye 4 b in polar solvents. The relaxation from higher‐charge‐injection excited states to the lowest TICT state renders the back‐electron transfer process a forbidden one and significantly retards the charge recombination to boost the photocurrent. The electrochemical impedance under illumination and transient photovoltage decay studies showed smaller charge resistance and longer electron lifetime in 4 b ‐based DSSC compared to the DSSCs with reference dyes 4 a and 32 , which further illustrates the positive influence of the TICT state on the performance of DSSCs.     

Cyano Analogues of 7‐Azaindole: Probing Excited‐State Charge‐Coupled Proton Transfer Reactions in Protic Solvents

The interplay between excited‐state charge and proton transfer reactions in protic solvents is investigated in a series of 7‐azaindole (7AI) derivatives: 3‐cyano‐7‐azaindole (3CNAI), 5‐cyano‐7‐azaindole (5CNAI), 3,5‐dicyano‐7‐azaindole (3,5CNAI) and dicyanoethenyl‐7‐azaindole (DiCNAI). Similar to 7AI, 3CNAI and 3,5CNAI undergo methanol catalyzed excited‐state double proton transfer (ESDPT), resulting in dual (normal and proton transfer) emission. Conversely, ESDPT is prohibited for 5CNAI and DiCNAI in methanol, as supported by a unique normal emission with high quantum efficiency. Instead, the normal emission undergoes prominent solvatochromism. Detailed relaxation dynamics and temperature dependent studies are carried out. The results conclude that significant excited‐state charge transfer (ESCT) takes place for both 5CNAI and DiCNAI. The charge‐transfer specie possesses a different dipole moment from that of the proton‐transfer tautomer species. Upon reaching the equilibrium polarization, there exists a solvent‐polarity induced barrier during the proton‐transfer tautomerization, and ESDPT is prohibited for 5CNAI and DiCNAI during the excited‐state lifespan. The result is remarkably different from 7AI, which is also unique among most excited‐state charge/proton transfer coupled systems studied to date.     

Thiophene Cation Intercalation to Improve Band‐Edge Integrity in Reduced‐Dimensional Perovskites

The insertion of large organic cations in metal halide perovskites with reduced‐dimensional (RD) crystal structures increases crystal formation energy and regulates the growth orientation of the inorganic domains. However, the power conversion performance is curtailed by the insulating nature of the bulky cations. Now a series of RD perovskites with 2‐thiophenmethylammonium (TMA) as the intercalating cation are investigated. Compared with traditional ligands, TMA demonstrates improved electron transfer in the inorganic framework. TMA modifies the near‐band‐edge integrity of the RD perovskite, improving hole transport. A power conversion efficiency of 19 % is achieved, the highest to date for TMA‐based RD perovskite photovoltaics; these TMA devices provide a 12 % relative increase in PCE compared to control RD perovskite devices that use PEA as the intercalating ligand, a result of the improved charge transfer from the inorganic layer to the organic ligands.     

Synthesis and Localized Photoluminescence Blinking of Lead‐Free 2D Nanostructures of Cs3Bi2I6Cl3 Perovskite

Two‐dimensional (2D) lead‐free halide perovskites have generated enormous perception in the field of optoelectronics due to their fascinating optical properties. However, an in‐depth understanding on their shape‐controlled charge‐carrier recombination dynamics is still lacking, which could be resolved by exploring the photoluminescence (PL) blinking behaviour at the single‐particle level. Herein, we demonstrate, for the first time, the synthesis of nanocrystals (NCs) and 2D nanosheets (NSs) of layered mixed halide, Cs₃Bi₂I₆Cl₃, by solution‐based method. We applied fluorescence microscopy and super‐resolution optical imaging at single‐particle level to investigate their morphology‐dependent PL properties. Narrow emission line widths and passivation of non‐radiative defects were evidenced for 2D layered nanostructures, whereas the activation of shallow trap states was recognized at 77 K. Interestingly, individual NCs were found to display temporal intermittency (blinking) in PL emission. On the other hand, NS showed temporal PL intensity fluctuations within localized domains of the crystal. In addition, super‐resolution optical image of the NS from localization‐based method showed spatial inhomogeneity of the PL intensity within perovskite crystal.     

How a Small Structural Difference Can Turn Optical Properties of π‐Extended Coumarins Upside Down: The Role of Non‐Innocent Saturated Rings

The fluorescence properties of two new families of heterocycles possessing either a seven‐ or five‐membered ring attached at the core molecule are entirely different in solution and in the solid state. Crystallization has the effect of inhibiting non‐radiative excited‐state deactivation pathways, operative in solution for the seven‐membered ring compounds, thus leading to significant fluorescence efficiency in the solid state, with quantum yields ranging from 0.10 to 0.36. Conversely, the five‐membered ring derivatives, which display notable emission properties in solution, are almost non‐emissive in the crystalline state, characterized by a long‐range π‐stacked arrangement. When embedded in polymeric films, both series show fluorescence features similar to the solution case, with remarkable fluorescence quantum yields ranging from 0.09 to 0.41. According to quantum chemical calculations, 3H‐chromeno[3,4‐c]pyridine‐4,5‐diones show the specific mechanism of fluorescence quenching. The derivatives bearing the seven‐membered ring undergo, in solution, a significant structural deformation in the excited state, resulting in a large decrease of the energy gap between S₁ and S₀ and hence to a substantial contribution of the internal conversion in the relaxation process. The fluorescence quenching of the five‐membered ring derivatives is in turn related to the intermolecular interaction between adjacent molecules prevailing to a greater extent in the crystal lattice.     

Theoretical insight into the photodeactivation pathway of the tetradentate Pt (II) complex with different inductive substituents

Density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) both were used to explore the impacts of different inductive substituents on the photophysical properties, radiative/nonradiative processes and photodeactivation mechanism for the Pt (II) complex with novel spiro‐arranged tetradentate ligand. Spectrum simulations show that the electron donor methoxyl (‐OCH₃) group can cause the emission wavelength to red‐shift but have little effect on the absorption spectrum. In the simulation of the radiative decay process for the tetradentate Pt (II) complex, the singlet‐triplet splitting energy is reduced by the introduction of substituents with strong electron‐releasing capability (i.e., from the original trifluoromethyl (‐CF₃) group to ‐OCH₃ group), accompanied with a lower radiative rate constant (k_r). The analyses of non‐radiative decay processes show that the substitution of ‐OCH₃ group on azole rings reduces the energy barriers of thermally activated non‐radiative photodeactivation pathway, which in turn increases the temperature‐dependent non‐radiative rate constants (k_nr(T)). In addition, the substitution of ‐CF₃ by ‐OCH₃ group slightly weakens molecular rigidity and enhances the Huang‐Rhys factor, but decreases the SOC between the triplex excited (T) state and the ground (S₀) state. Thereby, the two complexes may have the similar temperature‐independent non‐radiative rate constant (k_nr’). This work offers theoretical guidance for the design and optimization of the efficient organic light emitting diode (OLED) materials based on the structure of tetradentate Pt (II) complexes.     

Photoinduced Electron‐Transfer Oxidation of Olefins with Molecular Oxygen Sensitized by Tetrasubstituted Dimethoxybenzenes: A Non‐Singlet‐Oxygen Mechanism

α‐Methylstyrene ( 1 ) was photo‐oxidized in the presence of a series of alkylated dimethoxybenzenes as sensitizers in an oxygen‐saturated MeCN solution to afford the cleaved ketone 2 , epoxide 3 , as well as a small amount of the ene product 4 in ca. 1 : 1 : 0.04 ratio. The relative rate of conversion was well‐correlated with the fluorescence quantum yield of sensitizers. Thus, a non‐singlet‐oxygen mechanism is proposed, in which an excited sensitizer is quenched by (ground‐state) molecular oxygen to produce a sensitizer radical cation and a superoxide ion (O), the former of which oxidizes the substrate, while the latter reacts with the resulting olefin radical cation ( 1 ^{+ .}) to give the major oxidation products. Photodurability of such electron‐donating sensitizers is dramatically improved by substituting four aromatic H‐atoms in 1,4‐dimethoxybenzene with Me or fused alkyl groups, which provides us with an environmentally friendly, clean method of photochemical functionalization with molecular oxygen, alternative to the ene reaction via singlet oxygenation.     

Emergence of Uranium as a Distinct Metal Center for Building Intrinsic X‐ray Scintillators

The combination of high atomic number and high oxidation state in U^VI materials gives rise to both high X‐ray attenuation efficiency and intense green luminescence originating from ligand‐to‐metal charge transfer. These two features suggest that U^VI materials might act as superior X‐ray scintillators, but this postulate has remained substantially untested. Now the first observation of intense X‐ray scintillation in a uranyl–organic framework ( SCU‐9 ) that is observable by the naked eye is reported. Combining the advantage in minimizing the non‐radiative relaxation during the X‐ray excitation process over those of inorganic salts of uranium, SCU‐9 exhibits a very efficient X‐ray to green light luminescence conversion. The luminescence intensity shows an essentially linear correlation with the received X‐ray intensity, and is comparable with that of commercially available CsI:Tl. SCU‐9 possesses an improved X‐ray attenuation efficiency (E>20 keV) as well as enhanced radiation resistance and decreased hygroscopy compared to CsI:Tl.