A simple 4-aniline boron-dipyrromethene (BODIPY) dye (1) was developed as a highly sensitive acidic pH fluorescent probe excitable with visible light based on a photoinduced electron transfer (PeT) mechanism. The pH titration indicates that the fluorescence intensity increases more than 500-fold within the pH range of 4.12-1.42 with a pKa value of 3.24 in methanol-water (1 : 1, v/v) solution, which is valuable for studying strongly acidic conditions. Density functional theory (DFT) calculations reproduce the fluorescence off-on behavior. 1 has also been used as a fluorescent chemosensor for the visual detection of dissolved carbon dioxide (CO2) gas. The underlying mechanism of the sensing process is rationalized. This probe can be recovered by bubbling nitrogen (N2) gas into CO2-treated solutions for over 10 cycles. In addition, two logic gates (OR and INH) have been achieved at the molecular level by changing the initial states of system 1 and chemical inputs.
In this study we report about two novel azomethine–BODIPY dyads 1 and 2. The two dyads have been, respectively, synthesized by covalent tethering of tautomeric ortho-hydroxy aromatic azomethine moieties including N-salicylideneaniline (SA) and N-naphthlideneaniline (NA) to a BODIPY fluorophore. Both of the two dyads 1 and 2 show enol-imine (OH) structures dominating in the crystalline state. Dyad 1 in the enol state is the most stable form at room temperature in most media, while enol–keto prototropic tautomerism of the NA moiety in solution is preserved in dyad 2, which can be reversibly converted between enol and keto forms in the environment's polarity. Visible illumination of dyad 2 in the enol state excites selectively the BODIPY fragment and then deactivates radiatively by emitting green light in the form of fluorescence, while the emission intensity of 2 in the keto state is quenched on the basis of the proton-coupled photoinduced electron transfer (PCPET) mechanism. This allows large fluorescence modulation between the two states of dyad 2 and generates a novel tautomerisable fluorescent switch. Theoretical calculations including calculated energies, potential energy surfaces (PESs) and intrinsic reaction coordinate (IRC) analysis further support that the single proton transfer reaction from an enol form to a transition state (TS) and from the TS to a keto form for 2 is easier to occur than that for 1, which accounts for the fluorescence quenching of 2 in methanol. The agreement of the experimental results and theoretical calculations clearly suggests that fluorescent and tautomeric components can be paired within the same molecular skeleton and the proton tautomerization of the latter can be designed to regulate the emission of the former. In addition, preliminary experiments revealed that 1 can be potentially used as a simple on/off fluorescent chemosensor which exhibited higher selectivity for Cu(2+) over other common cations.
Conceptually mimicking biomolecules' ability to construct multiple-helical aggregates with emergent properties and functions remains a long-standing challenge. Here we report an atom-precise 18-copper nanocluster (NC), Cu 18 H(PET) 14 (TPP) 6 (NCS) 3 (Cu 18 H) which contains a pseudo D 3 -symmetrical triple-helical Cu 15 core. Structurally, Cu 18 H may be also viewed as sandwich type of sulfur-bridged chiral copper cluster units [Cu 6 À Cu 6 À Cu 6 ], endowing three-layered 3D chirality. More importantly, the chiral NCs are aggregated into an infinite double-stranded helix supported by intra-strand homonuclear CÀ H•••HÀ C dihydrogen contacts and inter-strand CÀ H/π and CÀ H/S interactions. The unique multi-layered 3D chirality and the doublehelical assembly of Cu 18 H are evocative of DNA. Moreover, the collective behaviours of the aggregated NCs not only exhibit crystallization-induced emission enhancement (CIEE) and aggregation-induced emission enhancement (AIEE) effects in the deep-red region, but also efficiently catalyze electron transfer (ET) reaction. This study thus presents that hierarchical assemblies of atomically defined copper NCs could be intricate as observed for important biomolecules like DNA with emergent properties arising from aggregated behaviours.
Accurate identifying and in‐depth understanding of the defect sites in a working nanomaterial could hinge on establishing specific defect‐activity relationships. Yet, atomically precise coinage‐metal nanoclusters (NCs) possessing surface vacancy defects are scarce primarily owing to challenges in the synthesis and isolation of such defective NCs. Herein we report a mixed‐ligand strategy to synthesizing an intrinsically chiral and metal‐deficient copper hydride‐rich NC [Cu57H20(PET)36(TPP)4]+ (Cu57H20). Its total structure (including hydrides) and electronic structure are well established by combined experimental and computational results. Crystal structure reveals Cu57H20 features a cube‐like Cu8 kernel embedded in a corner‐missing metal‐ligand shell of Cu49(PET)36(TPP)4. Single Cu vacancy defect site occurs at one corner of the shell, evocative of mono‐lacunary polyoxometalates. Theoretical calculations demonstrate that the above‐mentioned point vacancy causes one surface hydride exposed as an interfacial capping μ3‐H−, which is accessible in chemical reaction, as proved by deuterated experiment. Moreover, Cu57H20 shows catalytic activity in the hydrogenation of nitroarene. The success of this work opens the way for the research on well‐defined chiral metal‐deficient Cu and other metal NCs, including exploring their application in asymmetrical catalysis.
Inspired by the metal active sites of [NiFeSe]-hydrogenases, a dppf-supported nickel(II) selenolate complex (dppf=1,1'-bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme-like H evolution turnover frequency (TOF) of 7838 s under an Ar atmosphere, which markedly surpasses the activity of a dppf-supported nickel(II) thiolate analogue with a low TOF of 600 s . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio-inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O and H tolerance. Our results should encourage the development of the design of highly efficient oxygen-tolerant Ni selenolate molecular catalysts.
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