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The design of highly electron-active and stable heterogeneous catalysts for the ambient nitrogen reduction reaction is challenging due to the inertness of the N

The rational design of efficient and stable catalysts for the oxygen reduction reaction and oxygen evolution reaction (ORR/OER) is the key to improving Li-O 2 battery performance. Here, we report the construction of ORR/OER bifunctional cathode catalysts in a covalent organic framework (COF) platform by simultaneously incorporating Ni-bis(dithiolene) and Co-porphyrin units. The resulting bimetallic Ni/Co-COF exhibits high surface area, fairly good electrical conductivity, and excellent chemical stability. Li-O 2 batteries with the Ni/Co-COF–based cathode show a low discharge/charge potential gap (1.0 V) and stable cycling (200 cycles) at a current density of 500 mA g −1 , rivaling that of PtAu nanocrystals. Density functional theory computations and control experiments using nonmetal or single metal–based isostructural COFs reveal the critical role of Ni and Co sites in reducing the discharge/charge overpotentials and regulating the Li 2 O 2 deposition. This work highlights the advantage of bimetallic COFs in the rational design of efficient and stable Li-O 2 batteries.

Chiral boron/nitrogen doped multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters are promising for highly efficient and color-pure circularly polarized organic light-emitting diodes (CP-OLEDs). Herein, we report two pairs of MR-TADF materials (Czp-tBuCzB, Czp-POAB) based on planar chiral paracyclophane with photoluminescence quantum yields of up to 98%. The enantiomers showed symmetric circularly polarized photoluminescence spectra with dissymmetry factors |gPL| of up to 1.6 × 10-3 in doped films. Meanwhile, the sky-blue CP-OLEDs with (R/S)-Czp-tBuCzB showed an external quantum efficiency of 32.1% with the narrowest full-width at half-maximum of 24 nm among the reported CP-OLEDs, while the devices with (R/S)-Czp-POAB displayed the first nearly pure green CP electroluminescence with |gEL| factors at the 10-3 level. These results demonstrate the incorporation of planar chirality into MR-TADF emitter is a reliable strategy for constructing of efficient CP-OLEDs.

Controlled synthesis of hydrogen-bonded organic frameworks (HOFs) remains challenging, because the self-assembly of ligands is not only directed by weak hydrogen bonds, but also affected by other competing van der Waals forces. Herein, we demonstrate the coordination-bond-directed synthesis of HOFs using a preformed metal–organic framework (MOF) as the template. A MOF (CuI-TTFTB) based on two-coordinated CuI centers and tetrathiafulvalene-tetrabenzoate (TTFTB) ligands was initially synthesized. CuI-TTFTB was subsequently oxidized to the intermediate (CuII-TTFTB) and hydrated to the HOF product (TTFTB-HOF). Single-crystal-to-single-crystal (SC-SC) transformation was realized throughout the MOF-to-HOF transformation so that the evolution of structures was directly observed by single-crystal X-ray diffraction. The oxidation and hydration of the CuI center are critical to breaking the Cu–carboxylate bonds, while the synergic corbelled S⋯S and π⋯π interactions in the framework ensured stability of materials during post-synthetic modification. This work not only provided a strategy to guide the design and discovery of new HOFs, but also linked the research of MOFs and HOFs., The MOF-to-HOF transformation was realized in a single-crystal-to-single-crystal manner by the oxidation and hydration of the CuI center in CuI-TTFTB. The corbelled S⋯S and π⋯π interactions ensured the framework stability during transformation.

Inspired by the exciting physical/chemical properties in metal-organic frameworks (MOFs) of the redox-active tetrathiafulvalene (TTF) ligands, nickel bis(dithiolene-dibenzoic acid), [Ni(C2S2(C6H4COOH)2)2], has been designed and developed as an inorganic analogue of the corresponding TTF-type donors (such as tetrathiafulvalene-tetrabenzoate, TTFTB), where a metal site (Ni) replaces the central C═C bond. In this work, [Ni(C2S2(C6H4COOH)2)2] and In3+ have been successfully assembled into a three-dimensional MOF, (Me2NH2+){InIII-[Ni(C2S2(C6H4COO)2)2]}·3DMF·1.5H2O (1, DMF = N,N-dimethylformamide), with satisfying chemical and thermal stabilities. With the combination of reversible redox activity and unsaturated metal sites originated from [Ni(C2S2(C6H4COOH)2)2], 1 showed a significantly enhanced performance in electrocatalytic CO2 reduction compared with the isomorphic MOF, (Me2NH2+)[InIII-(TTFTB)]·0.7C2H5OH·DMF (2, with TTFTB ligand). More importantly, by mimicking the active [NiS4] sites of formate dehydrogenase and CO-dehydrogenase, a prominently higher conversion rate and Faradaic efficiency (FE), with FEHCOO- increasing from 54.7% to 89.6% (at -1.3 V vs RHE, jHCOO- = 36.0 mA cm-2), were achieved in 1. Mechanistic investigations further confirm that [NiS4] can serve as a CO2 binding site and efficient catalytic center. This unprecedented effect of redox-active nickel dithiolene-based MOF catalysts on the performance of electroreduction of CO2 provides an important strategy for designing stable and efficient crystalline enzyme-mimicking catalysts for the conversion of CO2 into high-value chemical stocks.

Ammonia production plays a central role in modern industry and agriculture with a continuous surge in its demand, yet the current industrial Haber-Bosch process suffers from low energy efficiency and accounts for high carbon emissions. Direct electrochemical conversion of nitrate to ammonia therefore emerges as an appealing approach with satisfactory sustainability while reducing the environmental impact from nitrate pollution. To this end, electrocatalysts for efficient conversion of eight-electron nitrate to ammonia require collective contributions at least from high-density reactive sites, selective reaction pathways, efficient multielectron transfer, and multiproton transport processes. Here, we report a catalytic metal-organic framework (two-dimensional (2D) In-MOF In8) catalyst integrated with multiple functional motifs with atomic precision, including uniformly dispersed, high-density, single-atom catalytic sites, high proton conductivity (efficient proton transport channel), high electron conductivity (promoted by the redox-active ligands), and confined microporous environments. These eventually lead to a direct and efficient electrochemical reduction of nitrate to ammonia and record high yield rate, FE, and selectivity for NH

Herein, we report two multiple-resonance thermally activated delayed fluorescence emitters (VTCzBN and TCz-VTCzBN) based on indolo[3,2,1-jk]carbazole unit and boron-nitrogen skeletons, whose emissions peaking at 496 and 521 nm with full width at half maximum of 34 and 29 nm, respectively. Meanwhile, fast rate constants of reverse intersystem crossing of above 10

Thermal conducting materials may be damaged during long-term use, resulting in the increase of thermal resistance and therefore inefficient heat dissipation. The introduction of self-healing ability may solve this problem, but the realization of fast and room-temperature self-healing in thermal conducting composites is quite challenging. Herein, we choose a flexible poly(dimethylsiloxane) polymer material (PDMS-COOH) as the matrix and graphene nanosheets as the thermal conductive filler to prepare a new kind of thermal conductive polymer composite (PDMS-COOH-CG) that can quickly self-heal at room temperature. The thermal conductivity of PDMS-COOH-CG10 with 10% of graphene content is 0.48 W·m−1·K−1, which is 16 times that of PDMS-COOH (0.03 W·m−1·K−1). At room temperature, self-healing efficiency of PDMS-COOH-CG10 based on tensile strength can be 53.8% for 30 s and 84.6% for 24 h. Dynamic infrared thermal imaging dipicted that after 2 min of self-healing at room temperature, the thermal conduction temperature near the damage was basically restored to the level of the pristine sample.

Organic long persistent luminescence (OLPL) materials with afterglow duration in the scale of minutes or even hours are still rare. Most OLPL systems are based on exciplexes, which require complicated multi-component system in order to realize white afterglow but with slightly compromised duration and color stability. In this work, OLPLs lasting from 20 to 40 minutes are realized in a simple binary system based on two-photon ionization mechanism, which can simultaneously harvest excitons from both singlet and triplet excited states, making it potentially one of the most promising candidates to achieve stable white OLPL. Through modulation and optimization of dopant molecules in dibenzo[b,d]thiophen-2-yldiphenyl phosphine oxide host, the emission profiles of afterglow can be readily tuned from cyan (0.19, 0.22), cold white (0.31, 0.35), standard white (0.33, 0.33) to warm white (0.31, 0.46), with excellent color consistency.

Functionalizing the redox-active tetrathiafulvalene (TTF) core with groups capable of coordination to metals provides new perspectives on the modulation of architectures and electronic properties of organic-inorganic hybrid materials. With a view to extending this concept, we have now synthesized nickel bis(dithiolene-dibenzoic acid), [Ni(C2S2(C6H4COOH)2)2], which can be considered as the inorganic analogue of the organic tetrathiafulvalene-tetrabenzoic acid (H4TTFTB). Likewise, [Ni(C2S2(C6H4COOH)2)2] is a redox-active linker for new functional metal-organic frameworks, as demonstrated here with the synthesis of [Mn2{Ni(C2S2(C6H4COO)2)2}(H2O)2]·2DMF, (1, DMF = N,N-dimethylformamide). 1 is isomorphic to the reported [Mn2(TTFTB)(H2O)2] (2) but is a better electrochemical glucose sensor due to the multiple oxidation-reduction states of the [NiS4] core, which allow glucose to be oxidized to glucolactone by the high oxidation state [NiS4] center. As a non-enzymatic glucose sensor, 1 on Cu foam (CF), 1-CF, was synthesized by a one-step hydrothermal method and exhibited an excellent electrochemical performance. The fabricated 1-CF electrode offers a high sensitivity of 27.9 A M-1 cm-2, with a wide linear detection range from 2.0 × 10-6 to 2.0 × 10-3 M, a low detection limit of 1.0 × 10-7 M (signal/noise = 3), and satisfactory stability and reproducibility.

Combining the chemistry of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) can bring new opportunities for the design of advanced materials with enhanced tunability and functionality. Herein, we constructed two COFs based on Ni-bis(dithiolene) units and imine bonds, representing a bridge between traditional MOFs and COFs. The Ni-bis(dithiolene)tetrabenzaldehyde as the 4-connected linker was initially synthesized, which was further linked by 4-connected tetra(aminophenyl)pyrene (TAP) or 3-connected tris(aminophenyl)amine (TAA) linkers into two COFs, namely, Ni-TAP and Ni-TAA. Ni-TAP shows a two-dimensional sql network, while TAA is a twofold interpenetrated framework with an ffc topology. They both exhibit a high Brunauer-Emmett-Teller surface area (324 and 689 m

In this study, we report the first circularly polarized white organic light-emitting diodes (CP-WOLEDs) based on all thermally activated delayed fluorescence (TADF) materials. Two pairs of spiro-type TADF enantiomers, (R/S)-SPOCN (5,5'-((2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diyl)bis(oxy))bis(4-(10H-phenoxazin-10-yl)phthalonitrile)) and (R/S)-OSFSO (2'-(trifluoromethyl)-spiro[quinolino[3,2,1-kl]phenoxazine-9,9'-thioxanthene]-10',10'-dioxide), serve as emitters with complementary emission. The CP-OLEDs exhibit warm white emission with a CIE coordinate of (0.35, 0.46). Besides, decent device performances are observed with an external quantum efficiency of up to 21.6 % at maximum and 11.8 % at 1000 cd m

Metal-organic frameworks (MOFs) provide broad prospects for the development of new photothermal conversion materials, while their design and synthesis remain challenging. A new Zn-MOF (

To activate electronic and optical functions of the redox-active metal-organic framework, (Me2 NH2 )[InIII (TTFTB)]⋅0.7 C2 H5 OH⋅DMF (Me2 NH2 @1, TTFTB=tetrathiafulvalene-tetrabenzoate, DMF=N,N-dimethylformamide), has been exchanged by tetrathiafulvalenium (TTF.+ ) and N,N'-dimethyl-4,4'-bipyridinium (MV2+ ). These cations provide electron carriers and photosensitivity. The exchange retains the crystallinity allowing single-crystal to single-crystal post-synthetic transformation to TTF@1 and MV@1. Both TTF.+ and MV2+ enhance the electrical conductivity by a factor of 102 and the visible light induced photocurrent by 4 and 28 times, respectively. EPR evidences synergetic effect involving charge transfer between the framework redox-active TTFTB bridges and MV2+ . The results demonstrate that functionalization of MOF by cation exchange without perturbing the crystallinity extends possibilities to achieve switchable materials.

Development of simple chiral materials with tunable circularly polarized photoluminescence (CPPL) and circularly polarized electroluminescence (CPEL) for efficient circularly polarized organic light-emitting diodes (CP-OLEDs) is the key toward future 3D displays. In this study, four pairs of chiral 1,2-diaminocyclohexane-based fluorescence enantiomers were efficiently prepared with high yields (up to 92%) and enantiomeric excesses (ee >99%). By the introduction of N-methyl, carbazole, and diphenylamine-donating groups, these materials showed multicolor CPPL and CPEL from blue (420 nm) to red (610 nm) with good thermal and conformational stability. The multilayer CP-OLEDs based on these enantiomers show high external quantum efficiency of up to 5.5% with low-efficiency roll-off and microimage circularly polarized electroluminescence with a dissymmetry factor (gEL) of up to -1.4 × 10-3/+1.3 × 10-3. These results push forward the development of future multicolor circularly polarized electroluminescent materials.

Click chemistry focuses on the development of highly selective reactions using simple precursors for the exquisite synthesis of molecules. Undisputedly, the CuI -catalyzed azide-alkyne cycloaddition (CuAAC) is one of the most valuable examples of click chemistry, but it suffers from some limitations as it requires additional reducing agents and ligands as well as cytotoxic copper. Here, we demonstrate a novel strategy for the azide-alkyne cycloaddition reaction that involves a photoredox electron-transfer radical mechanism instead of the traditional metal-catalyzed coordination process. This newly developed photocatalyzed azide-alkyne cycloaddition reaction can be performed under mild conditions at room temperature in the presence of air and visible light and shows good functional group tolerance, excellent atom economy, high yields of up to 99 %, and absolute regioselectivity, affording a variety of 1,4-disubstituted 1,2,3-triazole derivatives, including bioactive molecules and pharmaceuticals. The use of a recyclable photocatalyst, solar energy, and water as solvent makes this photocatalytic system sustainable and environmentally friendly. Moreover, the azide-alkyne cycloaddition reaction could be photocatalyzed in the presence of a metal-free catalyst with excellent regioselectivity, which represents an important development for click chemistry and should find versatile applications in organic synthesis, chemical biology, and materials science.

Summary Two-dimensional (2D) conductive metal-organic frameworks (MOFs), whose advanced electrical properties accompany their intrinsic structural characteristics, represent an exciting new class of 2D atomic crystals for the van der Waals integration of novel heterostructures and the development of novel nano/quantum devices. Guided by topology, we report two 2D MOFs (1 and 2) constructed via combination of [In(COO)4]− metal nodes and tetratopic tetrathiafulvalene (TTF)-based linkers, with ultrahigh proton conductivity (6.66 × 10−4 and 1.30 × 10−2 S cm−1 for 1 and 2, respectively). Additionally, high electrical conductivity was simultaneously achieved with the pure protonic nature of the 2D MOF 2. The electrical conduction at the MOF-metal interface is enabled by the redox-switchable behavior of the TTF-based ligands. This unique charge-transport mechanism, protonic/pseudo-capacitance coupling, offers a new strategy for utilizing the ionic conductivity from MOFs to construct functional electronic devices.

Lithium–sulfur batteries, which can be applied for portable electronic devices with longer endurance, have received tremendous attention because of their high theoretical capacity and high energy density. However, both electrode volume variation and serious shuttling effects during the charge/discharge process limit the promotion of lithium–sulfur batteries. In this work, a novel self-healing poly(dimethylsiloxane) polymer with dynamic disulfide bonds (2S-PDMS) was designed as a binder for sulfur electrodes. The disulfide bonds in 2S-PDMS molecules can reversibly break and form, facilitating the conversion of polysulfides, as evidenced from both experimental and calculated results. In addition, 2S-PDMS binders with a remarkable self-healing ability and flexibility can keep the sulfur cathode integrated without cracks or damage. Consequently, the 2S-PDMS-based cathode exhibits both high capacity and excellent cycling stability, showing a specific capacity of 545.7 mA h g−1 at 2.0C after 400 cycles (79.6% capacity retention). Moreover, soft-packed Li–S batteries with a high sulfur loading of 6.6 mg cm−2 deliver a high areal capacity of 4.54 mA h cm−2 after 50 cycles, which verifies the good flexibility and stability of the 2S-PDMS-based cathode.

In designing multifunctional materials for potential switches that can be used as memory devices, the high-spin (HS) to low-spin (LS) crossover (SCO) one-dimensional polymer, [FeII(L)(4,4′-bpy)]n, was constructed from a designed redox-active tetrathiafulvalene (TTF) functionalized Schiff-base and the ditopic linker 4,4′-bipyridine (bpy). It exhibits an 8 K hysteretic SCO centred at T1/2 = 325 K which is coupled to changes in its dielectric constant. The crystal structures above and below the transition temperature reveal similar parallel linear ⋯Fe–bpy–Fe–bpy⋯ chains displaying expansion of the FeII octahedron in the HS state. Density functional theory (DFT) calculations reveal a concerted electronic charge and spin change represented by the Mulliken charge of the Fe and the magnitude and direction of the dipole moment which substantiate the experimental observations.

Pure organic materials with intrinsic room-temperature phosphorescence typically rely on heavy atoms or heteroatoms. Two different strategies towards constructing organic room-temperature phosphorescence (RTP) species based upon the through-space charge transfer (TSCT) unit of [2.2]paracyclophane (PCP) were demonstrated. Materials with bromine atoms, PCP-BrCz and PPCP-BrCz, exhibit RTP lifetime of around 100 ms. Modulating the PCP core with non-halogen-containing electron-withdrawing units, PCP-TNTCz and PCP-PyCNCz, successfully elongate the RTP lifetime to 313.59 and 528.00 ms, respectively, the afterglow of which is visible for several seconds under ambient conditions. The PCP-TNTCz and PCP-PyCNCz enantiomers display excellent circular polarized luminescence with dissymmetry factors as high as -1.2×10-2 in toluene solutions, and decent RTP lifetime of around 300 ms for PCP-TNTCz enantiomers in crystalline state.

When the reaction of zinc nitrate with 4′,4‴,4‴″,4‴‴′-(ethene-1,1,2,2-tetrayl)tetrakis[(1,1′-biphenyl-3-carboxylic acid)] (H4tmpe) in dimethylformamide (DMF) under hydrothermal condition is perform...

Near-infrared (NIR) photothermal materials hold great promise for use in several applications, particularly in photothermal therapy, diagnosis, and imaging. However, current NIR responsive materials often show narrow absorption bands and low absorption efficiency, and have long response times. Herein, we demonstrate that the NIR absorption of tetrathiafulvalene-based metal-organic frameworks (MOFs) can be tuned by redox doping and using plasmonic nanoparticles. In this work, a MOF containing redox-active tetrathiafulvalene (TTF) units and Dy-carboxylate chains was constructed, Dy

Recent development of most organic long persistent luminescence (OLPL) systems employed binary or tertiary doping. However, the design strategies towards OLPL materials with hour-long afterglow duration are still quite limited. Here, we propose a novel OLPL system through melt-casting method with 0.1 mol % of CuI complexes: 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl BINAP-CuX (X=Cl, Br and I) doped into the triphenylphosphine (TPP) host. The charge separation was initiated prior to excitation through host coordination with CuI complexes, resulting in semi-free halogen ions and in situ generated CuI cations, which forms TPP + BINAP-CuX ionic pairs and subsequently ionic solids. The OLPL lifetime can be readily modulated by different halogen atoms and the afterglow can last up to more than 3 hours perceivable to human eyes. This is a rare example of OLPL initiated through host-guest coordination that could potentially expand the definition of OLPL systems and design strategies.

Inspired by the exciting physical/chemical properties in metal-organic frameworks (MOFs) of the redox-active tetrathiafulvalene (TTF) ligands, nickel bis(dithiolene-dibenzoic acid), [Ni(C

The realization of luminescent materials with narrowband and circularly polarized luminescence (CPL) is of great significance for the development of future optical and photonic devices. Herein, through a steric-hindrance-assisted dual-core strategy, two pairs of chiral dual-core multiple resonance thermally activated delayed fluorescence (MR-TADF) materials (R/S-DOBN and R/S-DOBNT) are directly constructed by the bonding of two organoboron MR-TADF monocores (SOBN and SOBNT) with carbazole/3,6-di-tert-butyl-9H-carbazole and phenol derivative as donors, realizing obvious CPL and narrowband emissions. Furthermore, the dual-core effect in the prepared R/S-DOBN and R/S-DOBNT increases the transition oscillator strength two times more than that of a monocore structure, while maintaining the ultrapure blue emissions peaking at 453 and 459 nm with a narrower full-width at half-maximum of 21 nm through reorganization energy reduction. The circularly polarized organic light-emitting diodes based on the enantiomers exhibit ultrapure blue emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.14, 0.10) and (0.13, 0.12), high maximum external quantum efficiencies of 23.9% and 25.6%, and obvious circularly polarized electroluminescence with dissymmetry factors (|g