Showing papers on "Intramolecular force published in 2022"

Independent gradient model based on Hirshfeld partition: A new method for visual study of interactions in chemical systems

Abstract: The powerful independent gradient model (IGM) method has been increasingly popular in visual analysis of intramolecular and intermolecular interactions in recent years. However, we frequently observed that there is an evident shortcoming of IGM map in graphically studying weak interactions, that is its isosurfaces are usually too bulgy; in these cases, not only the graphical effect is poor, but also the color on some areas on the isosurfaces is inappropriate and may lead to erroneous analysis conclusions. In addition, the IGM method was originally proposed based on promolecular density, which is quite crude and does not take actual electronic structure into account. In this article, we propose an improvement version of IGM, namely IGM based on Hirshfeld partition of molecular density (IGMH), which replaces the free-state atomic densities involved in the IGM method with the atomic densities derived by Hirshfeld partition of actual molecular electron density. This change makes IGM have more rigorous physical background. A large number of application examples in this article, including molecular and periodic systems, weak and chemical bond interactions, fully demonstrate the important value of IGMH in intuitively understanding interactions in chemical systems. Comparisons also showed that the IGMH usually has markedly better graphical effect than IGM and overcomes known problems in IGM. Currently IGMH analysis has been supported in our wavefunction analysis code Multiwfn (http://sobereva.com/multiwfn). We hope that IGMH will become a new useful method among chemists for exploring interactions in wide variety of chemical systems.

Acceptor Planarization and Donor Rotation: A Facile Strategy for Realizing Synergistic Cancer Phototherapy via Type I PDT and PTT.

Abstract: Tumor hypoxia seriously impairs the therapeutic outcomes of type II photodynamic therapy (PDT), which is highly dependent upon tissue oxygen concentration. Herein, a facile strategy of acceptor planarization and donor rotation is proposed to design type I photosensitizers (PSs) and photothermal reagents. Acceptor planarization can not only enforce intramolecular charge transfer to redshift NIR absorption but also transfer the type of PSs from type II to type I photochemical pathways. Donor rotation optimizes photothermal conversion efficiency (PCE). Accordingly, three 3,6-divinyl-substituted diketopyrrolopyrrole (DPP) derivatives, 2TPAVDPP, TPATPEVDPP, and 2TPEVDPP, with different number of rotors were prepared. Experimental results showed that three compounds were excellent type I PSs, and the corresponding 2TPEVDPP nanoparticles (NPs) with the most rotors possessed the highest PCE. The photophysical properties of 2TPEVDPP NPs are particularly suitable for in vivo NIR fluorescence imaging-guided synergistic PDT/PTT therapy. The proposed strategy is helpful for exploiting type I phototherapeutic reagents with high efficacy for synergistic PDT and PTT.

Asymmetric Catalytic Rearrangements with α-Diazocarbonyl Compounds.

Abstract: Conspectusα-Diazocarbonyl compounds serve as nucleophiles, dipoles, carbene precursors, and rare electrophiles, enabling a vast array of organic transformations under the influence of metal catalysts. Among them, rearrangement processes are attractive and provide straightforward and efficient accesses to one-carbon extension adducts or heteroatom-containing molecules. The reactions occur upon the release of dinitrogen after nucleophilic addition or before ylide formation. Although significant progress has been made for these two types of rearrangement reactions, the issue of enantiocontrol is challenging because the final optically enriched products are generated via multistep transformations and the inherent spacial arrangement of the intermediates has more or less influence on the regio- and enantioselectivity.In this Account, we collected several rearrangements of α-diazocarbonyl compounds, showcasing the efficient catalysts and tailored strategies for tackling enantioselective varieties of these two types of rearrangement reactions. Our research group initiated the catalytic asymmetric reactions of α-diazocarbonyl compounds during the development of chiral Feng N,N'-dioxide-metal complex catalysts and others. As a kind of useful chiral Lewis acid catalyst chiral N,N'-dioxide-metal complexes are favorable for the activation of various carbonyl compounds, accelerating the diastereo- and enantioselective nucleophilic addition of α-diazoesters and the sequential rearrangements in either an intermolecular or intramolecular manner. Aldehydes, acyclic and cyclic ketone derivatives, and α,β-unsaturated ketones could participate in efficient asymmetric homologation reactions, and an obvious ligand-acceleration effect is observed in these processes. For example, the Roskamp-Feng reaction of aldehydes gives optically active β-ketoesters through a H-shift, overwhelming the aryl group shift or oxygen attack. The shift preference and enantiocontrol in the homologation of acyclic and cyclic ketone derivatives could be under excellent control of the chiral catalysts. An unusual electrophilic α-amination of aryl/alkyl ketones and even a complicated homologation/dyotropic rearrangement/interconversion/[3 + 2] cycloaddition cascade used to construct dimeric polycyclic compounds were discovered as a result of the selection of chiral ligands and additives. On the basis of the understanding of the interaction of the functional group with N,N'-dioxide-metal complexes in catalysis and the key enantio-determining issues in ylide-based rearrangements, we designed new α-diazocarbonyl compounds by introducing a pyrazole-1-carboxyl group as the acceptor unit, which could benefit the formation of both carbenoid species and the chiral catalyst-bound ylides to deliver stereoselectivity. Taking advantage of Ni(II) or Co(II) complexes of Feng N,N'-dioxide ligands, we realized several kinds of enantioselective [2,3]-sigmatropic rearrangements, such as the Doyle-Kirmse reaction with allylic sulfides or selenides, [2,3]-Stevens rearrangements of vinyl-substituted α-diazo pyrazoleamides with thioacetates, Sommelet-Hauser rearrangements of aryl-substituted α-diazo pyrazoleamides with thioamides, and thio-Claisen rearrangements of 2-thio-indoles as well. Moreover, this strategy was shown to be applicable to highly γ-selective and enantioselective insertion into N-H bonds of secondary amines with vinyl-substituted α-diazo pyrazoleamides.

Photoelectron Transfer Mediated by the Interfacial Electron Effects for Boosting Visible-Light-Driven CO2 Reduction

Abstract: Imine-linked covalent organic frameworks (COFs) are popular candidates for photocatalytic CO2 reduction, but high polarization of the imine bond is less efficient for π-electron delocalization between the linked building units, leading to low intramolecular electron transfer and poor photocatalytic efficiency. Herein, we present a structural and electronic engineering strategy through integrating the imine-linked COF consisting of Zn–porphyrin and Co–bipyridyl units with cadmium sulfide (CdS) nanowires to form a CdS@COF core–shell structure. The experimental and theoretical results have validated that CdS serves as the electron transfer channel through the interfacial electron effects, which induces photoelectron transfer from Zn–porphyrin to CdS and subsequent injection into Co–bipyridyl units for CO2 reduction. The as-prepared CdS@COF generates 4057 μmol g–1 CO in 8 h under visible-light irradiation, which is considerably higher than those of its neat CdS and imine-linked COF counterparts. This work provides protocols to tackle intramolecular charge transfer across polar linkages between photosensitizers and active sites for solar-to-chemical energy conversion.

Achieving Record-Efficiency Organic Solar Cells upon Tuning the Conformation of Solid Additives

Abstract: Volatile solid additives (SADs) are considered as a simple yet effective approach to tune the film morphology for high-performance organic solar cells (OSCs). However, the structural effects of the SADs on the photovoltaic performance are still elusive. Herein, two volatilizable SADs were designed and synthesized. One is SAD1 with twisted conformation, while the other one is planar SAD2 with the S···O noncovalent intramolecular interactions (NIIs). The theoretical and experimental results revealed that the planar SAD2 with smaller space occupation can more easily insert between the Y6 molecules, which is beneficial to form a tighter intermolecular packing mode of Y6 after thermal treatment. As a result, the SAD2-treated OSCs exhibited less recombination loss, more balanced charge mobility, higher hole transfer rate, and more favorable morphology, resulting in a record power conversion efficiency (PCE) of 18.85% (certified PCE: 18.7%) for single-junction binary OSCs. The universality of this study shed light on understanding the conformation effects of SADs on photovoltaic performances of OSCs.

Can electric fields drive chemistry for an aqueous microdroplet?

Abstract: Reaction rates of common organic reactions have been reported to increase by one to six orders of magnitude in aqueous microdroplets compared to bulk solution, but the reasons for the rate acceleration are poorly understood. Using a coarse-grained electron model that describes structural organization and electron densities for water droplets without the expense of ab initio methods, we investigate the electric field distributions at the air-water interface to understand the origin of surface reactivity. We find that electric field alignments along free O-H bonds at the surface are ~16 MV/cm larger on average than that found for O-H bonds in the interior of the water droplet. Furthermore, electric field distributions can be an order of magnitude larger than the average due to non-linear coupling of intramolecular solvent polarization with intermolecular solvent modes which may contribute to even greater surface reactivity for weakening or breaking chemical bonds at the droplet surface.

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

Abstract: The application of plain cycloalkanes and heterocyclic derivatives in the synthesis of valuable natural products and pharmacologically active intermediates has increased tremendously in recent times with much attention being paid to the lower cycloalkane members. The structural and molecular properties of higher seven-membered and nonaromatic heterocyclic derivatives are less known despite their stable nature and vast application; thus, an insight into their structural and electronic properties is still needed. Appropriate quantum chemical calculations utilizing the ab initio (MP2) method, meta-hybrid (M06-2X) functional, and long-range-separated functionals (ωB97XD) have been utilized in this work to investigate the structural reactivity, stability, and behavior of substituents on cycloheptane (CHP) and its derivatives: azepane, oxepane, thiepane, fluorocycloheptane (FCHP), bromocycloheptane (BrCHP), and chlorocycloheptane (ClCHP). Molecular global reactivity descriptors such as Fukui function, frontier molecular orbitals (FMOs), and molecular electrostatic potential were computed and compared with lower members. The results of two population methods CHELPG and Atomic Dipole Corrected Hirshfeld Charges (ADCH) were equally compared to scrutinize the charge distribution in the molecules. The susceptibility of intramolecular interactions between the substituents and cycloalkane ring is revealed by natural bond orbital analysis and intramolecular weak interactions by the independent gradient model (IGM). Other properties such as atomic density of states, intrinsic bond strength index (IBSI), and dipole moments are considered. It is acclaimed that the strain effect is a major determinant effect in the energy balance of cyclic molecules; thus, the ring strain energies and validation of spectroscopic specificities with reference to the X-ray crystallographic data are also considered.

Intramolecular hydroxyl nucleophilic attack pathway by a polymeric water oxidation catalyst with single cobalt sites

Abstract: Abstract Exploration of efficient water oxidation catalysts (WOCs) is the primary challenge in conversion of renewable energy into fuels. Here we report a molecularly well-defined heterogeneous WOC with Aza-fused, π-conjugated, microporous polymer (Aza-CMP) coordinated single cobalt sites (Aza-CMP-Co). The single cobalt sites in Aza-CMP-Co exhibited superior activity under alkaline and near-neutral conditions. Moreover, the molecular nature of the isolated catalytic sites makes Aza-CMP-Co a reliable model for studying the heterogeneous water oxidation mechanism. By a combination of experimental and theoretical results, a pH-dependent nucleophilic attack pathway for O-O bond formation was proposed. Under alkaline conditions, the intramolecular hydroxyl nucleophilic attack (IHNA) process with which the adjacent -OH group nucleophilically attacks Co 4+ =O was identified as the rate-determining step. This process leads to lower activation energy and accelerated kinetics than those of the intermolecular water nucleophilic attack (WNA) pathway. This study provides significant insights into the crucial function of electrolyte pH in water oxidation catalysis and enhancement of water oxidation activity by regulation of the IHNA pathway.

Synthesis of a Möbius carbon nanobelt

Abstract: Abstract Technologies for the creation of topological carbon nanostructures have greatly advanced synthetic organic chemistry and materials science. Although simple molecular nanocarbons with a belt topology have been constructed, analogous carbon nanobelts with a twist—more specifically, Möbius carbon nanobelts (MCNBs)—have not yet been synthesized owing to their high intrinsic strain. Here we report the synthesis, isolation and characterization of a MCNB. Calculations of strain energies suggest that large MCNBs are synthetically accessible. Designing a macrocyclic precursor with an odd number of repeat units led to a successful synthetic route via Z -selective Wittig reactions and nickel-mediated intramolecular homocoupling reactions, which yielded (25,25)MCNB over 14 steps. NMR spectroscopy and theoretical calculations reveal that the twist moiety of the Möbius band moves quickly around the MCNB molecule in solution. The topological chirality that originates from the Möbius structure was confirmed experimentally using chiral HPLC separation and circular dichroism spectroscopy.

Autonomous fuelled directional rotation about a covalent single bond

Abstract: Biology operates through autonomous chemically fuelled molecular machinery1, including rotary motors such as adenosine triphosphate synthase2 and the bacterial flagellar motor3. Chemists have long sought to create analogous molecular structures with chemically powered, directionally rotating, components4-17. However, synthetic motor molecules capable of autonomous 360° directional rotation about a single bond have proved elusive, with previous designs lacking either autonomous fuelling7,10,12 or directionality6. Here we show that 1-phenylpyrrole 2,2'-dicarboxylic acid18,19 (1a) is a catalysis-driven20,21 motor that can continuously transduce energy from a chemical fuel9,20-27 to induce repetitive 360° directional rotation of the two aromatic rings around the covalent N-C bond that connects them. On treatment of 1a with a carbodiimide21,25-27, intramolecular anhydride formation between the rings and the anhydride's hydrolysis both occur incessantly. Both reactions are kinetically gated28-30 causing directional bias. Accordingly, catalysis of carbodiimide hydration by the motor molecule continuously drives net directional rotation around the N-C bond. The directionality is determined by the handedness of both an additive that accelerates anhydride hydrolysis and that of the fuel, and is easily reversed additive31. More than 97% of fuel molecules are consumed through the chemical engine cycle24 with a directional bias of up to 71:29 with a chirality-matched fuel and additive. In other words, the motor makes a 'mistake' in direction every three to four turns. The 26-atom motor molecule's simplicity augurs well for its structural optimization and the development of derivatives that can be interfaced with other components for the performance of work and tasks32-36.

Dynamic timing control over multicolor molecular emission by temporal chemical locking.

Abstract: Dynamic control over molecular emission, especially in a time-dependent manner, holds a great promise for the development of smart luminescent materials. Here we report a series of dynamic multicolor fluorescent systems based on the time-encoded locking and unlocking of individual vibrational emissive units. The intramolecular cyclization reaction driven by adding chemical fuel acts as a chemical lock to decrease the conformational freedom of the emissive units, thus varying the fluorescence wavelength, while the resulting chemically locked state can be automatically unlocked by the hydrolysis reaction with water molecules. The dynamic molecular system can be driven by adding chemical fuels for multiple times. The emission wavelength and lifetime of the locking states can be readily controlled by elaborating the molecular structures, indicating this strategy as a robust and versatile way to modulate multi-color molecular emission in a time-encoded manner.

Promoting intramolecular charge transfer of graphitic carbon nitride by donor–acceptor modulation for visible‐light photocatalytic H2 evolution

Abstract: To satisfy the requirements of substantial green development, it is urgent to explore an innovative eco‐friendly semiconductor photocatalyst to efficiently achieve visible‐light‐driven photocatalytic H2 evolution (PHE). The strategy of promoting the spatial separation efficiency of photoinduced carriers can essentially enhance the PHE performance of a photocatalyst. Herein, a graphitic carbon nitride (g‐C3N4)‐based donor–acceptor (D‐A) copolymer (CNDMx) is constructed by simple one‐pot thermal polycondensation, using urea and 5,8‐DibroMoquinoxaline (as an electron donor) as precursors. The electron D‐A modulation consequently creates an internal electric field to facilitate the intramolecular charge transfer within the copolymer. A series of experimental characterizations and density functional theory calculations are applied to elucidate the variation and correlation of the structure and PHE performance of the as‐prepared catalysts. It is found that the best average PHE rate of 3012.5 μmol g−1 h−1 can be achieved over the optimal D‐A copolymer under visible‐light (400 < λ < 800 nm) irradiation, which is ~3.3 times that of pure urea‐derived g‐C3N4. The corresponding apparent quantum efficiency is 1.3% at 420 nm. This study provides a protocol for designing effective visible‐light photocatalysts via D‐A modulation of polymeric semiconductors.

Exploiting the Twisted Intramolecular Charge Transfer Effect to Construct a Wash-Free Solvatochromic Fluorescent Lipid Droplet Probe for Fatty Liver Disease Diagnosis.

Abstract: The prominent pathological feature of fatty liver disease lesions is excessive fat accumulation in lipid droplets in hepatocytes. Thus, developing fluorescent lipid droplet-specific probes with high permeability and a high imaging contrast provides a robust tool for diagnosing fatty liver diseases. Herein, we rationally developed a novel donor-acceptor lipophilic fluorescent probe ANI with high photostability for wash-free visualization of lipid droplets and fatty liver disease characteristics. ANI showed a typical twisted intramolecular charge transfer effect with very faint fluorescence in high-polar solvents, but dramatically boosted emissions in low-polar environments. The solvatochromic probe can selectively light up lipid droplets with a high contrast in a wash-free manner. Further use of ANI to reveal the excessive accumulation of lipid droplets with a significantly large size in the liver tissues from the fatty liver disease model mice was successfully demonstrated. The remarkable imaging performances rendered ANI an alternative tool for accurately evaluating fatty liver disease in intraoperative diagnosis.

Highly stable photomultiplication type organic photodetectors with single-polymer containing intramolecular traps as active layer

Abstract: Photomultiplication type organic photodetectors (PM-OPDs) have attracted enormous interests owing to the high sensitivity on weak light, especially for excellent parasitic stability with single-polymer as active layers. Herein, three kinds...

Rational preparation of cocoon-like g-C3N4/COF hybrids: accelerated intramolecular charge delivery for photocatalytic hydrogen evolution

Abstract: In virtue of the pliable structure and ample pendent amine groups, the metal-free graphic carbon nitride (g-C 3 N 4 , abbreviated as CN) in two-dimensional (2D) morphology could be covalently modified by organic materials to modulate its photoelectrical characteristics. In this work, CN is covalently wrapped by a 2D Schiff-base covalent organic framework (COF, denoted as TMP), which is composed of 2,4,6-tris(4-aminophenyl)− 1,3,5-triazine (TAPT), melem and 1,3,5-triformyl phloroglucinol (TP), by means of “one-pot” solvothermal method with a cocoon-like morphology presented (CN/TMP). Given the significant distinction of charge densities between the two constituent units, viz., melem and TAPT, the resultant acceleration of the intramolecular charge transfer (ICT) within the TMP shroud endows the formed integrate with a significantly raised charge delivery and lowered band gap energy (E g ) in comparison to a structure-analogous COF (TM) incorporated hybrid, CN/TM, in which the TAPT monomer is not involved in the TM COF construction. The photocatalytic water-splitting evaluation indicates CN/TMP conducted photocatalysis could provide the hydrogen (H 2 ) production of 102.88 μmol·h −1 , about 5.6 and 11.6 times greater than that of CN/TM and CN, respectively. Our modulation strategy at molecular level proffers a new opportunity for the construction of the carbon nitride based hybrids and the regulation in their photoelectric behaviors. Due to the distinction of charge densities between the two units in TMP, the accelerated ICT within CN/TMP contributes to its improved photocatalytic H 2 evolution. • A COF is in-situ grown on CN by Schiff-base reaction giving a cocoon-like composite (CN/TMP). • The ICT between the TAPT and TP moieties within the TMP shroud of CN/TMP contributes to the accelerated charge delivery. • The photocatalytic H 2 evolution conducted by CN/TMP is 102.88 μmol·h −1 , obviously higher than that of TMP, CN, or TM/CN.

Organocatalytic cycloaddition of alkynylindoles with azonaphthalenes for atroposelective construction of indole-based biaryls

Abstract: The axially chiral indole-aryl motifs are present in natural products and biologically active compounds as well as in chiral ligands. Atroposelective indole formation is an efficient method to construct indole-based biaryls. We report herein the result of a chiral phosphoric acid catalyzed asymmetric cycloaddition of 3-alkynylindoles with azonaphthalenes. A class of indole-based biaryls were prepared efficiently with excellent yields and enantioselectivities (up to 98% yield, 99% ee). Control experiment and DFT calculations illustrate a possible mechanism in which the reaction proceeds via a dearomatization of indole to generate an allene-iminium intermediate, followed by an intramolecular aza-Michael addition. This approach provides a convergent synthetic strategy for enantioselective construction of axially chiral heterobiaryl backbones.

An investigation of a relatively rigid acyclic salamo-type ligand and its square planar Cu(II) complex

Abstract: Abstract A relatively rigid acyclic salamo-type ligand H2L and its square planar Cu(II) complex, [Cu(L)]·CH3OH, were synthesized and characterized by X-ray crystallography, as well as Fourier-transform infrared spectra, UV–Vis spectra, Hirshfeld surface analyses and DFT calculations. The ligand crystallizes in monoclinic space group P 21/c and has pairs of intramolecular hydrogen bonds between the oxime nitrogen atoms and the hydroxyl groups. The Cu(II) complex crystallizes in the monoclinic space group P 21/c. The Cu(II) ion is located in the N2O2 cavity of the fully deprotonated salamo-type ligand (L)2− unit, thus forming a four-coordinate distorted square planar geometry. At the same time, a belt-like, 2-D supramolecular structure is formed by the interaction of intermolecular hydrogen bonds, and the intermolecular interaction force is quantitatively analyzed by Hirshfeld surfaces. Significantly, fluorescence properties of the ligand and its Cu(II) complex were also studied. The coordination ratio of the Cu(II) complex was proved by UV–Vis and fluorescence titration experiments. Graphical Abstract

Organocatalytic cycloaddition of alkynylindoles with azonaphthalenes for atroposelective construction of indole-based biaryls

Abstract: The axially chiral indole-aryl motifs are present in natural products and biologically active compounds as well as in chiral ligands. Atroposelective indole formation is an efficient method to construct indole-based biaryls. We report herein the result of a chiral phosphoric acid catalyzed asymmetric cycloaddition of 3-alkynylindoles with azonaphthalenes. A class of indole-based biaryls were prepared efficiently with excellent yields and enantioselectivities (up to 98% yield, 99% ee). Control experiment and DFT calculations illustrate a possible mechanism in which the reaction proceeds via a dearomatization of indole to generate an allene-iminium intermediate, followed by an intramolecular aza-Michael addition. This approach provides a convergent synthetic strategy for enantioselective construction of axially chiral heterobiaryl backbones.

Through-Space Interaction of Tetraphenylethylene: What, Where, and How.

Abstract: Electronic conjugation through covalent bonds is generally considered as the basis for the electronic transition of organic luminescent materials. Tetraphenylethylene (TPE), an efficient fluorophore with aggregation-induced emission character, fluoresces blue emission in the aggregate state, and such photoluminescence is always ascribed to the through-bond conjugation (TBC) among the four phenyl rings and the central C═C bond. However, in this work, systematic spectroscopic studies and DFT theoretical simulation reveal that the intramolecular through-space interaction (TSI) between two vicinal phenyl rings generates the bright blue emission in TPE but not the TBC effect. Furthermore, the evaluation of excited-state decay dynamics suggests the significance of photoinduced isomerization in the nonradiative decay of TPE in the solution state. More importantly, different from the traditional qualitative description for TSI, the quantitative elucidation of the TSI is realized through the atoms-in-molecules analysis; meanwhile, a theoretical solid-state model for TPE and other multirotor systems for studying the electronic configuration is preliminarily established. The mechanistic model of TSI delineated in this work provides a new strategy to design luminescent materials beyond the traditional theory of TBC and expands the quantum understanding of molecular behavior to the aggregate level.

Fused-Ring-Linked Covalent Organic Frameworks.

Abstract: The development of linkage chemistry in the research area of covalent organic frameworks (COFs) is fundamentally important for creating robust structures with high crystallinity and diversified functionality. We reach herein a new level of complexity and controllability in linkage chemistry by achieving the first synthesis of fused-ring-linked COFs. A series of bicyclic pyrano[4,3-b]pyridine COFs have been constructed via a cascade protocol involving Schiff-base condensation, intramolecular [4 + 2] cycloaddition, and dehydroaromatization. With a broad scope of Brønsted or Lewis acids as the catalyst, the designed monomers, that is, O-propargylic salicylaldehydes and multitopic anilines, were converted into the fused-ring-linked frameworks in a one-pot fashion. The obtained COFs exhibited excellence in terms of purity, stability, and crystallinity, as comprehensively characterized by solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction, high-resolution transmission electron microscopy, and so on. Specifically, the highly selective formation (>94%) of pyrano[4,3-b]pyridine linkage was verified by quantitative NMR measurements combined with 13C-labeling synthesis. Moreover, the fused-ring linkage possesses fully locked conformation, which benefits to the high crystallinity observed for these COFs. Advancing the linkage chemistry from the formation of solo bonds or single rings to that of fused rings, this study has opened up new possibilities for the concise construction of sophisticated COF structures with high controllability.

Intramolecular modulation of iron-based metal organic framework with energy level adjusting for efficient photocatalytic activity

Abstract: Efficient photocatalytic activity is always pressingly expected for photocatalytic technology on removing organic water contaminations. Modulating the intrinsic electronic properties is one of the most effective approaches to improve photocatalytic efficiency. Herein, we developed a promising photocatalyst through modulation electronic properties of iron-based metal organic framework by sulfur (S-MIL-53(Fe)), in which the sulfur particles were intramolecularly in-suite inserted into MIL-53(Fe) through annealing treatment process. The constructed S3-MIL-53(Fe) crystal with regular spindle-shaped polyhedron morphology exhibited superior higher apparent quantum efficiency (AQE) of 27.82% which was over 30 times than that of pure MIL-53(Fe) (0.903%) indicating the significantly enhanced photoactivity. A computational study was conducted to reveal the electronic structure changes and the resulted charge transfer induced by the sulfur modulation. The experimental and computational analyses suggest that intramolecular modulation MIL-53(Fe) with sulfur to engineer band structure for promoting charge transfer is a promising approach to improve the photocatalytic efficiency.

Constructing Stable Chromenoquinoline-Based Covalent Organic Frameworks via Intramolecular Povarov Reaction.

Abstract: Chemically stable chromenoquinoline (CQ)-based covalent organic frameworks (COFs) were constructed by postsynthetic conversion of imine COFs. The key step of an intramolecular Povarov reaction can transform a preintegrated alkyne group to bridge the benzene rings on both sides of the imine linkage via chemical bonds, affording a ladder-type CQ linkage. This novel approach achieves a high cyclization degree of 80-90%, which endows the CQ-COFs with excellent chemical stability toward strong acid, base, and redox reagents. The synthetic approach can be applied to various monomers with different symmetries and functional core moieties. The absorption and fluorescence intensities of CQ-COFs are sensitive to acid, which allows for dual-mode sensing of strongly acidic environments.