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Efficient photocatalytic solar-to-H2 conversion is pivotal to zero-carbon energy supply.

Acetoxy-1,2,2-tri(aryl)ethanone (

Long-persistent luminescence (LPL), also known as afterglow, is a phenomenon in which the material shows long-lasting luminescence after the cessation of the excitation source. The research of LPL continues to attract much interest due to its fundamental nature and its potential in the development of the next generation of functional materials. However, most of the current LPL materials are multicomponent inorganic systems obtained after harsh synthetic procedures and often use rare-earth metals. Recently, metal free organic long-persistent luminescence (OLPL) has gained much interest because it can bypass many of the disadvantages of inorganic systems. To date, the most successful method to generate OLPL systems is to access charge-separated states through binary donor-acceptor exciplex systems. However, it has been reported that the ratios of the binary systems affect OLPL properties, complicating the reproducibility and large-scale production of OLPL materials. Simpler OLPL systems can overcome these issues for the benefit of the development and adoption of OLPL systems. Here, we report on the rational design and synthesis of a single-component OLPL system with detectable afterglow for at least 12 min under ambient conditions. This work exemplifies an easy design principle for new OLPL materials. The investigation of the material provides valuable insights toward the generation of OLPL from a single-component system.

A new Ir-complex conjugated porphyrin exhibits AIE property for the Ir-complex unit, inhibition of ACQ of the porphyrin unit and efficient energy transfer from the Ir-complex to the porphyrin, therefore, enhanced photocatalytic H2 evolution.

Both molecular conformations and hole–electron distribution impacted by the solvent polarity, can cause an enhanced or reduced emission of TPP structures, which provides a general intramolecular charge transfer rule and guidelines for PEE.

Positioning basic/acid groups near molecular catalyst has been become a popular strategy to modulate proton-coupled electron transfer (PCET) reactions in energy conversion and storage. However, the detailed understanding of the real role played by basic/acid groups remains lacking. Here, we report the immobilization of a novel copper (II) dipicolylamine, CuL, catalyst bearing a phosphonic anchor on metal oxide electrode to investigate the activity of oxygen reduction reaction (ORR) in aqueous solution. The catalytic current of ORR by CuL catalyst was significantly enhanced by 3 times as a carboxylate-terminated ligand was integrated onto metal oxide surfaces acting as a co-catalyst. Extensive experimental and theoretical studies reveal that hydrogen bond formed between proximal carboxylate of co-catalyst and Cu-OOH intermediate generated via protonation of Cu-O2 adduct by bulk buffer solution aids O-O bond cleavage, thereby promoting the four-electron four-proton reduction of dioxygen into water reaching a Faradaic efficiency of 97.6%. Our finding is in stark contrast to the typical assignment on the role of basic groups near catalyst that features proton shuttling to facilitate protonation of metal-O2 intermediate forming metal-OOH intermediate. This work offers a new strategy to enhance simultaneously the activity and selectivity of surface-supported non-precious metal electrocatalysts that are important toward realizing alternative energy conversion schemes.

Excited state intramolecular proton transfer (ESIPT) has drawn much attention for its important applications in a variety of areas. Here, the steady-state and time-resolved absorption spectroscopic experiments as well as DFT/TD-DFT calculations are employed to study the photophysical properties and photochemical reaction mechanisms of 2-(2'-hydroxyphenyl) benzoxazole (HBO) and selected derivatives (compounds 1-3). Because of their larger π-conjugation framework, compounds 1-3 display red-shifted absorbance but blue-shifted fluorescence compared with HBO. A fast ESIPT process is observed directly for HBO while compound 3 has an enol/keto equilibrium type of ESIPT that exhibits dual emission. Interestingly, only the emission of the enol form is observed for compounds 1 and 2 which suggests that the ESIPT process is strongly inhibited. These results indicate the decoration with electron-withdrawing groups such as thiadiazol and pyrazine on the hydroxyphenyl ring (compounds 1 and 2) apparently suppresses the proton-transfer processes in their excited states. Whereas the ESIPT process is rarely increased for compound 3 that modified with the phenanthrol ring, because the effective conjugation is reduced for compound 3 compared with HBO. The work here provides fundamental insights that may be useful for designing novel ESIPT molecules in the future.

Newly designed push-pull ligands (L1 and L2) with bithiophene (bth) as a donor and phenazine (phz) or quinoxalino[2,3-b]quinoxaline (qxq) as acceptors were synthesized and also incorporated with a bipyridyl Ru(II) complex to give Ru1 and Ru2, respectively. The ultrafast photophysical dynamics of the ligand and their respective Ru(II) complexes were well-characterized using time-resolved spectroscopies and quantum chemical calculations. Photoinduced charger transfer (CT) and intersystem crossing (ISC) processes were directly observed for L1 and L2. In addition, the interplay of three different triplet excited states was directly observed in the related Ru(II) complexes. The lowest-lying triplet excited states of the ligands and their respective Ru(II) complexes were both attributed to the CT transitions from donor (bth) to acceptor (phz or qxq) and result in 3ICT (intramolecular charge transfer) and 3ILCT (intraligand charge transfer) excited states, respectively. The lifetimes of the lowest-lying triplet excited states of L1, L2, Ru1, and Ru2 were measured to be 21.3, 50.4, 2.75, and 4.16 μs, respectively.

Femtosecond laser flash photolysis of 3-(1a,9b-dihydro-1H-cyclopropa[l]phenanthren-1-ylidene)tetrahydrofuran produces singlet 3-oxacyclopentylidenecarbene which reacts with acetonitrile solvent to form an ylide. This is the first direct detection of ylide formation by an alkylidenecarbene. This new type of ylide was observed to have a broad absorption band in the visible region with λmax ∼450 nm and a lifetime of ∼13.5 ps. As with other "conventional" carbenes (the divalent carbon atom is separately bound to two substituents), this ylide formation method could be also useful for detecting alkylidenecarbenes, especially those that do not absorb at wavelengths suitable for direct observation. Furthermore, the mechanisms by which 3-oxacyclopentylidenecarbene forms the ylide and the overall favorability of ylide formation, vis-a-vis ring expansion of the carbene to strained 3-oxacyclohexyne, were supported by results from density functional theory calculations.

The self-assembled fluorogen activating protein (FAP)- malachite green (MG) complex is a well-established protein-ligand system, which can realize binding-caused fluorescence turn-on of MG and singlet oxygen ( 1 O 2 ) generation by MG iodination. To clarify the mechanism of fluorescence activation and the 1 O 2 generation, the photodynamics of different halogen-substituted MG derivatives and their corresponding MG-FAP complexes were studied by femtosecond transient absorption spectroscopy and theoretical computation. The results show that the rotation of MG was restricted by FAP binding, which preventing the rapid internal conversion and allowing a long lifetime for the excited MG to undergo fluorescence emission and intersystem crossing. Moreover, these MG-FAP complexes exhibit obviously varied fluorescence quantum yields ( Φ FL ) and 1 O 2 yields. The study on the decay pathways indicates that such an anti-heavy atom effect predominately stems from the lifetimes of the excited-state species. The photodynamic mechanism study here will lead to more advanced FAP-MG systems with high spatiotemporal resolution.

Solid-state molecular motions (SSMM) play a critical role in adjusting behaviors and properties of materials. However, research on SSMM, especially for multicomponent systems, suffers from various problems and is rarely explored. Herein, through collaboration with cocrystal engineering, visualization and manipulation of SSMM in two-component systems, namely, FSBO ((E)-2-(4-fluorostyryl)benzo[d]oxazole)/TCB (1,2,4,5-tetracyanobenzene) and PVBO ((E)-2-(2-(pyridin-4-yl)vinyl)benzo[d]oxazole)/TCB, were realized. The obtained yellow-emissive F/T (FSBO/TCB) cocrystal displayed turn-on fluorescence, and the green-emissive P/T (PVBO/TCB) cocrystal presented redder emission, both of which exhibited an aggregation-induced emission property. At varied pressure and temperature, the grinding mixtures of FSBO/TCB and PVBO/TCB displayed different molecular motions that were readily observed through the fluorescence signal. Notably, even without grinding, FSBO and TCB molecules could move over for 4 mm in a 1D tube. The unique emission changes induced by SSMM were applied in information storage and dynamic anticounterfeiting. This work not only visualized and manipulated SSMM but offered more insights for multicomponent study in aggregate science.

HNO is a highly reactive molecule that shows promise in treating heart failure. Molecules that rapidly release HNO with precise spatial and temporal control are needed to investigate the biology of this signaling molecule. (Hydroxynaphthalen-2-yl)methyl-photocaged N-hydroxysulfonamides are a new class of photoactive HNO generators. Recently, it was shown that a (6-hydroxynaphthalen-2-yl)methyl (6,2-HNM)-photocaged derivative of N-hydroxysulfonamide incorporating the trifluoromethanesulfonamidoxy group (1) quantitatively generates HNO. Mechanistic studies have now been carried out on this system and reveal that the ground state protonation state plays a key role in whether concerted heterolytic C-O/N-S bond cleavage to release HNO occurs versus undesired O-N bond cleavage. N-Deprotonation of 1 can be achieved by adding an aqueous buffer or a carboxylate salt to an aprotic solvent. Evidence is presented for C-O/N-S bond heterolysis occurring directly from the singlet excited state of the N-deprotonated parent molecule on the picosecond time scale, using femtosecond time-resolved transient absorption spectroscopy, to give a carbocation and 1NO-. This is consistent with the observation of significant fluorescence quenching when HNO is generated. The carbocation intermediate reacts rapidly with nucleophiles including water, MeOH, or even (H)NO in the absence of a molecule that reacts rapidly with (H)NO to give an oxime.

Developing a suitable initiation for the energetic materials that respond to a low-power near-infrared laser can aid in replacing the current expensive and bulky laser-initiation systems. Here, we report on a system of molecularly tailored 1:1 donor-acceptor (D-A) charge-transfer (CT) cocrystals that manifest ultrabroad absorption (200-2500 nm) characteristics as well as noteworthy very fast self-assembly behaviors. The very narrow highest occupied molecular orbital-lowest unoccupied molecular orbital gap enables

Defects have been observed in graphene and are expected to play a key role in its optical, electronic, and magnetic properties. However, because most of the studies focused on the structural characterization, the implications of topological defects on the physicochemical properties of graphene remain poorly understood. Here, we demonstrate a bottom-up synthesis of three novel nanographenes (1-3) with well-defined defects in which seven-five-seven (7-5-7)-membered rings were introduced to their sp2 carbon frameworks. From the X-ray crystallographic analysis, compound 1 adopts a nearly planar structure. Compound 2, with an additional five-membered ring compared to 1, possesses a slightly saddle-shaped geometry. Compound 3, which can be regarded as the "head-to-head" fusion of 1 with two bonds, features two saddles connected together. The resultant defective nanographenes 1-3 were well-investigated by UV-vis absorption, cyclic voltammetry, and time-resolved absorption spectra and further corroborated by density functional theory (DFT) calculations. Detailed experimental and theoretical investigations elucidate that these three nanographenes 1-3 exhibit an anti-aromatic character in their ground states and display a high stability under ambient conditions, which contrast with the reported unstable biradicaloid nanographenes that contain heptagons. Our work reported herein offers insights into the understanding of structure-related properties and enables the control of the electronic structures of expanded nanographenes with atomically precise defects.

Tetrazolium salts (TZs) are pervasively utilized as precursors in the dye industry, colorimetric probes in enzyme assays and for exploring nanomaterial toxicity, but its own toxicity is not investigated enough so far. Using femtosecond transient absorption spectroscopy, nanosecond pulse radiolysis (ns-PRL), western blotting and UV-vis absorption spectroscopy, here we characterized a neutral tetrazolinyl radical (with the same maximum absorption at 420 nm and different lifetimes of 5.0 and 9.0 μs for two selected TZs), the key intermediate of TZs reduction, and noticed TZs-formazan production under UV light irradiation accompanied by 41% increase in the cross-linking of lysozyme (Lyso, model protein) compared to TZs-free sample, which uncovered the photoenhanced oxidation of TZs towards Lyso. The ns-PRL in a reductive atmosphere simulated the electron/proton donors of amino acid residues in Lyso upon photoexcitation and revealed the reduction mechanism of TZs, as that first followed one-electron-transfer and then probably proton-coupled electron transfer. This is the first time to report on the photoenhanced oxidation mechanism of TZs, which would provide new insights into the applications of TZs in cell biology, "click" chemistry and nanotoxicology.

The creation of efficient artificial systems that mimic natural photosynthesis represents a key current challenge. Here, we describe a high-performance recyclable photocatalytic core–shell nanofibre system that integrates a cobalt catalyst and a photosensitizer in close proximity for hydrogen production from water using visible light. The composition, microstructure and dimensions—and thereby the catalytic activity—of the nanofibres were controlled through living crystallization-driven self-assembly. In this seeded growth strategy, block copolymers with crystallizable core-forming blocks and functional coronal segments were coassembled into low-dispersity, one-dimensional architectures. Under optimized conditions, the nanofibres promote the photocatalytic production of hydrogen from water with an overall quantum yield for solar energy conversion to hydrogen gas of ~4.0% (with a turnover number of >7,000 over 5 h, a frequency of >1,400 h−1 and a H2 production rate of >0.327 μmol h−1 with 1.34 μg of catalytic polymer (that is, >244,300 μmol h−1 g−1 of catalytic polymer)). Artificial systems capable of photocatalytic hydrogen production are not typically based on precisely controlled scaffolds. Now, statistical seeded crystallization of block copolymers—bearing either a pendant cobalt catalyst or a photosensitizer—from solution has been shown to yield recyclable, colloidally stable nanofibres that can be tailored to promote photocatalytic hydrogen production from water.

In this review, noncovalent functionalization of single-wall carbon nanotubes (SWCNTs) is briefly reviewed. The functional materials summarized here include metalloporphyrin derivatives, biomolecules and conjugated polymers. Notably, time-resolved spectroscopic techniques such as time-resolved fluorescence and transient absorption were employed to directly investigate the electron transfer and recombination processes between the functionalities and the SWCNTs. In addition, Raman spectroscopy is also useful to identify the interaction and the electron transfer direction between both the functionalities and the SWCNTs. An improved understanding of the mechanisms of these SWCNT-based nanohybrids in terms of their structural and photophysical properties can provide more insights into the design of new electronic materials.

In this work, 2,4'-dichlorobiphenyl (1) yielded 4'-chloro-2-hydroxybiphenyl (2) after photolysis in neutral acetonitrile aqueous (ACN-H2O) solutions. Ultrafast spectroscopic measurements and density functional theory (DFT) computations were performed for 2 in ACN and ACN-H2O (v/v, 1:1). These results were compared with previously published results for 2-hydroxybiphenyl (3). The counterparts 2 and 3 went through a singlet excited state intramolecular proton transfer (ESIPT) in ACN but behaved differently in ACN-H2O with a dehydrochlorination process occurring for 2 and an ESIPT taking place for 3. Computational results indicate that the phenol O-H bond elongates after photoexcitation to induce a concerted asynchronous process with the C-Cl bond increasing first followed by HCl elimination. A biradical intermediate (IM1) is then formed with some spin located at the phenyl 4'-C radical that appears to favor a hydrogen atom transfer (HAT) process and some spin located on phenoxyl that appears to prefer a subsequent •CH2CN radical rebound. The hydrogen bond promotes HCl elimination, while this is disfavored for ESIPT, making 4'-Cl extrusion the predominant process in ACN-H2O solutions. The mechanistic investigations have fundamental and significant implications for the understanding of polychlorinated biphenyl photolysis in an aqueous environment and hence the photodegradation of these kinds of pollutants in the natural environment.

Understanding the factors affecting the intersystem-crossing (ISC) rate constant (kISC) of transition-metal complexes is crucial to material design with tailored photophysical properties. Most of t...