Visible light responsive spiropyran derivatives based on dynamic coordination bonds

Spiropyrans(SPs) are a well-known class of photochromic compounds and have found widespread application due to their unique properties. However, for many conventional SPs, high energy ultraviolet(UV)light is commonly essential to drive photoisomerization, leading to poor fatigue resistance. Moreover, the practical application of spiropyrans is hindered by their fast fading speed due to the instability of closed forms(SP) or open forms(MC). Herein, we disclose a novel strategy to address these challenges through introducing both electron-donating substituents to stabilize the SP and dynamic coordination bonds to stabilize the MC. The resulting new spiropyrans complexes exhibit negative photochromic properties, with fast visible light response, good stability of both SP and MC, and significantly improved fatigue resistance.

Noncovalent cross-linked engineering hydrogel with low hysteresis and high sensitivity for flexible self-powered electronics

In this study,the hydrogel network was reinforced by covalent-like hydrogen bonding,and the strong binding ability of boron-nitrogen coordination served as the main driving force.Among them,acrylamide(AM)and 3-acrylamidophenylboronic acid(AAPBA)were the main body,and the numerous hydroxyl groups in the trehalose(Treh)molecule and other polymer groups formed strong hydrogen bonding interactions to improve the mechanical properties of the PAM/PAAPBA/Treh(PAAT)hydrogel and ensured the simplicity of the synthesis process.The hydrogel possessed high strain at break(1239%),stress(64.7 kPa),low hysteresis(100%to 500%strain,corresponding to dissipation energy from 1.37 to 7.80 kJ/m^(3)),and outstanding cycling stability(retained more than 90%of maximum stress after 200 ten-sile cycles).By integrating carbon nanotubes(CNTs)into PAAT hydrogel(PAATC),the PAATC hydrogel with excellent strain response performance was successfully constructed.The PAATC conductive hydro-gel exhibited high sensitivity(gauge factor(GF)=10.58 and sensitivity(S)=0.304 kPa^(-1)),wide strain response range(0.5%-1000%),fast response time(450 ms),and short recovery time(350 ms),excellent fatigue resistance,and strain response stability.Furthermore,the PAATC-based triboelectric nanogener-ator(TENG)displayed outstanding energy harvesting performance,which shows its potential for appli-cation in self-powered electronic devices.

Pyridine terminated polyurethane dendrimer/chlorinated butyl rubber nanocomposites with excellent mechanical and damping properties

Due to the special viscoelastic property, traditional rubber with high performance has been widely used in human life and production. However, it is challenging to improve the damping property without sacrificing the extensibility. In this work, a novel type of second-generation polyurethane dendrimer terminated with pyridine(G2-Py) was synthesized by using thiolactone chemistry and subsequently complexed with Zn ions. The structure and morphology of G2-Py were characterized. G2-Py-Zn2+was then mixed with chlorinated butyl rubber(CIIR) by a two-roll mill. A series of CIIR/G2-Py-Zn2+elastomers were obtained through vulcanization. CIIR/G2-Py-Zn2+elastomers could achieve high stretchability(a strain of ~1035%), high mechanical strength(a tensile stress of 7.64 MPa). This was benefitted from the friction between G2-Py and CIIR as well as variety of non-covalent bonds provided by G2-Py-Zn2+,which can dissipate energy to further improve the strength and extensibility. The coordination of Zn2+-pyridine was confirmed by Fourier transform infrared spectroscopy, stress relaxation and cycle tensile test. To further investigate the morphology and damping properties of the elastomers, scanning electron microscopy and dynamic mechanical analysis were performed. CIIR-5 showed the best damping performance with higher tan δ_(max) and wider effective damping temperatures. Therefore, this dendrimer modification technology provides wider applications for CIIR elastomers in daily life.

A functionalized separator enables dendrite-free Zn anode via metal-polydopamine coordination chemistry

Designing a multifunctional separator with abundant ion migration paths is crucial for tuning the ion transport in rocking-chair-type batteries.Herein,a polydopamine-functionalized PVDF(PVDF@PDA)nanofibrous membrane is designed to serve as a separator for aqueous zinc-ion batteries(AZIBs).The functional groups(OH and NH)in PDA facilitate the formation of Zn O and Zn N coordination bonds with Zn ions,homogenizing the Zn-ion flux and thus enabling dendrite-free Zn deposition.Moreover,the PVDF@PDA separator effectively inhibits the shuttling of V-species through the formation of V-O coordination bonds.As a result,the Zn/NH_(4)V_(4)O_(10) battery with the PVDF@PDA separator exhibits enhanced cycling stability(92.3%after 1000 cycles at 5 A g^(-1))and rate capability compared to that using a glass fiber separator.This work provides a new avenue to design functionalized separators for high-performance AZIBs.

STUDY ON THE CARDANOL-ALDEHYDE CONDENSATION POLYMER CONTAINING BORON-NITROGEN COORDINATE BOND

Cardanol-aldehyde condensation polymer containing boron-nitrogen coordinate bond (CFBN) has been synthesized and characterized by IR, XPS, HPLC and DTA-TG. Its properties were also investigated. The results show that the coating film of CFBN has excellent physico-mechanical properties, good anticorrosive properties and stable at high temperature. (Author abstract) 8 Refs.

Switchable Dielectric Materials Based on 2-Methylimidazole

Two novel coordination polymers with molecular structures（2MI）＋[Zn（2MI）Cl3]-（1） and（2MI）＋NO3-（2） based on ligand 2-methylimidazole（2MI） were synthesized under solution method. Compound 1 crystallizes in the monoclinic system, space group Cc with a=7.489（2）, b=13.448（4）, c=13.983（4） , β=98.402（2）°, Z=4 and V=102.246（2） 3. Compound 2 crystallizes in the orthorhombic system, space group pnma with a=14.296（3）, b=6.3180（12）, c=7.3862（13） , β=90°, Z=4 and V=667.1（2） 3. Dielectric measurements show compounds 1 and 2 have reversible dielectric anomalous behaviors with variation frequencies at different temperature.

Improving the electrochemical stability of AZ31 Mg alloy in a 3.5wt.%NaCl solution via the surface functionalization of plasma electrolytic oxidation coating

The unique interactions between hexadecanoic acid(HA)and albumin(ALB)molecules on the surface of the porous layer of AZ31 Mg alloy were exploited to fabricate a novel hybrid composite film with excellent electrochemical stability in a 3.5 wt.%Na Cl solution.Herein,the inorganic layer(IL)obtained by plasma electrolytic oxidation of AZ31 Mg alloy in an alkaline-phosphate-WO_(3)electrolyte was soaked in an organic solution composed of ALB and HA for 10 and 24 h at 60℃.Although albumin and HA may coexist on the same surface of IL,the higher reactivity of ALB molecules would prevent the formation of a thick layer of HA.The donor-acceptor complexes formed due to the unique interactions between ALB and/or HA and IL surface would reduce the area exposed to the corrosive species which in turn would efficiently protect the substrate from corrosion.The porous structure of the IL would provide preferable sites for the physical and chemical locking triggered by charge-transfer phenomena,leading to the inhomogeneous nucleation and crystal growth of a flowery flakes-like organic layer.DFT calculations were performed to reveal the primary bonding modes between the ALB,HA,and IL and to assess the mechanistic insights into the formation of such novel hybrid composites.

Grain Boundary Passivation Modulated by Molecular Doping for High-Performance Perovskite Solar Cells

Aiming to reduce the defects of perovskite film and improve carrier transport,an organic small molecule,benzo[d]isothiazol-3(2H)-one 1,1-dioxide(OBS),is introduced as an additive in the solution-processing of perovskite and prepare uniform perovskite films with a continuous distribution of OBS at grain boundaries.Fourier trans-form infrared spectroscopy and X-ray photoelectron spectroscopy are conducted to reveal the interactions of hydrogen bonding and coordina tion bonding between OBS and perovskite.Various characterizations(including X-ray diffraction,UV-vis spectroscopy,electrochemical impedance spectroscopy,etc.)are conducted to uncover the effect of OBS on device performance.Consequently,high efficiency of 23.26%is obtained for the OBS-treated device,while the control device shows only a companion efficiency of 21.60%.

CHARACTERIZATION AND PROPERTIES OF URUSHIOL POLYMER CONTAINING BORON-NITROGEN COORDINATE BOND

Urushiol polymer containing B-N bond (PUBN) was synthesized with urushiol-boron polymer and diethylene triamine. Its structure was characterized by XPS, IR, UV, HPLC, DTA-TG and elemental analysis. The physico-mechanical and anticorrosive properties of the polymer were also investigated. The results show that the coating of PUBN can be hardened in 2 h at room temperature and its film has excellent physico-mechanical properties and good anticorrosive properties.

AROMATIC BOND INCLUDING METALLIC ATOM IN COORDINATE COMPOUNDS AND SOME OF ITS PROPERTIES

Aromatic bond including metallic atom (Ni) is investigated by EHMO calculation.The NMR spectra and the mechanism for hydrolysis are discussed on the ground of results of computation.

A 3D Nickel(Ⅱ) Complex Constructed by Bis(2-dimethylaminoethyl)Ether:Solvothermal Synthesis,Crystal Structure and Catalytic Properties

Treatment of bis（2-dimethylaminoethyl） ether（BDMAE） with nickel acetate afforded a novel 3D nickel（Ⅱ） complex [Ni（BDMAE）（H2O）3·（CH3COO）2·（H2O）2] under solvothermal conditions. Its crystal structure was characterized by elemental analysis, IR spectrum, PXRD and single-crystal X-ray diffraction analysis. The complex belongs to the orthorhombic system, space group C2221 with a=8.823（2）, b=13.932（3）, c=17.563（4） , V=2158.9（8） 3, Z=4, C（12）H（36）N2NiO（10）, Mr=427.14, Dc=1.314 g/cm3, F（000）=920 and μ=0.944 mm（-1）. Single-crystal X-ray diffraction reveals that the mononuclear nickel（Ⅱ） ion is six-coordinated to one oxygen, two nitrogen atoms of the BDMAE ligand and three oxygen atoms of coordinated water molecules. The complex exhibits a 3D supramolecular structure through a variety of intermolecular and intramolecular hydrogen bonding interactions. In addition, the complex has been investigated for catalytic properties towards the Henry reaction of nitromethane with p-nitrobenzaldehyde, and the results indicated that the 1-p-nitrophenyl-2-nitroethanol product was obtained in excellent yield under optimum conditions with the complex as the catalyst.

Coordination-responsive drug release inside gold nanorod @ metal-organic framework core-shell nanostructures for near-infrared-induced synergistic chemo-photothermal therapy

Multifunctional core-shell nanostructures formed by integration of distinct components have received wide attention as promising biological platforms in recent years. In this work, crystalline zeolitic imidazolate framework-8 （ZIF-8）, a typical metal-organic framework （MOF）, is coated onto single gold nanorod （AuNR） core for successful realization of synergistic photothermal and chemotherapy triggered by near-infrared （NIR） light. Impressivel）~ high doxorubicin hydrochloride （DOX） loading capacity followed by pH and NIR light dual stimuli-responsive DOX release can be easily implemented through formation and breakage of coordination bonds in the system. Moreover, under NIR laser irradiation at 808 nm, these novel AuNR@MOF core-shell nanostructures exhibit effective synergistic chemo-photothermal therapy both in vitro and in vivo, confirmed by cell treatment and tumor ablation via intravenous injection.

A Strong and Rigid Coordination Adaptable Network that Can Be Reprocessed and Recycled at Mild Conditions

The investigation of covalent adaptable networks(CANs)is expanding rapidly due to the growing demand for sustainable materials,as CANs show thermoset-like behavior and yet can be reprocessed,recycled,and healed.However,most of the CANs reported so far have a trade-off between mechanical strength and reversible properties and often show performance reduction after reprocessing and/or recycling.Herein,we designed and synthesized a coordination adaptable network(CoAN)by crosslinking low-molecular-weight monomers with abundant coordination bonds.Owning to its excellent variable-stiffness property,leading to high stiffness at ambient conditions and low viscosity at elevated temperature,the as-prepared CoAN showed high mechanical rigidity but could be reprocessed rapidly and recycled at mild conditions.After reprocessing or recycling,the mechanical properties of the samples showed no performance reduction,compared with a pristine sample.Density functional theory calculations showed that free thiol ligands played a key role in reducing the activation energy for bond exchange.When used as binders for composites,the embedded carbon fibers could be recycled rapidly and still maintain the original microstructure.The material also showed temperature-sensitive dielectric and conductive properties due to the release of metal ions upon heating.Overall,such performances are superior among the CANs reported previously.

Writing and Erasing Encryption Information Based on Frustrated Lewis Pair Chemistry

Lewis acid−base adducts resulting from instantaneous interactions provide a cost-effective strategy for color tuning and anticounterfeiting information.Herein,we report the construction of luminescent Lewis acid−base adducts via inkjet printing.Due to the unique weak coordination bond of B→N,it is feasible to construct anticounterfeiting information that is easy to erase.The in situ postsynthesis of the luminescent quick response codes via inkjet printing facilitates precision chemistry control to change the emission ranging from deep-blue(peaking at 407 nm)to orange-red(peaking at 597 nm).The encrypted information can be quickly erased either by modulating the temperature to dissociate the weak coordination or strong Lewis base to promote a neutralization reaction.

An Alternating Polymer of Two Building Blocks Based on B←N Unit:Non-fullerene Acceptor for Organic Photovoltaics

B-N coordination bond can be used to develop polymer electron acceptors for efficient all-polymer solar cells （all-PSCs）. Here, we report a new alternating conjugated polymer containing two building blocks based on B-N unit. The polymer exhibits strong light absorption in the visible range, low-lying LUMO/HOMO energy levels and moderate electron mobility. The resulting all-PSC devices exhibit power conversion efficiencies of 1.50%-2.47%.

A homopolymer based on double B←N bridged bipyridine as electron acceptor for all-polymer solar cells

Polymer electron acceptors for all-polymer solar cells （all-PSCs） are usually conjugated copolymers, which contain alternating electron-rich units and electron-deficient units. In this manuscript, we report a conjugated homopolymer （P-BNBP） based on an electron-deficient unit of double B,--N bridged bipyridine, which can be used as electron acceptor for all-polymer solar cells. P-BNBP shows low-lying LUMO energy level of -3.59eV, high absorption coefficient of 1.6 ×10^5Lmo1^-1 cm^-1 at 626nm and moderate electron mobility of 4.37 ×10^-6cm^2V^-1s^-1. AII-PSC devices exhibit power conversion efficiencies of 2.44%-3.04%. These results demonstrate that conjugated homopolymers are promising as electron acceptor materials for alI-PSCs.

Hybridized valence electrons of 4f^(0-14)5d^(0-1)6s^2:the chemical bonding nature of rare earth elements

The chemical bonding nature of rare earth（RE） elements can be studied by a quantitative analysis of electron domain of an atom. The outer electrons of RE elements are within the valence shell 4f^（0-14）5d^（0-1）6s^2, which are involved in all chemical bonding features. We in this work found that the chemical bonding characteristics of 4f electrons are a kind of hybridizations, and classified them into three types of chemical bonding of 4f^（0-14）5d^（0-1）6s^2, furthermore, the coordination number ranging from 2 to 16 could thus be determined. We selected Y（NO_3）_3, La（NO_3）_3, Ce（NO_3）_3, YCl_3, LaCl_3, and CeCl_3 as examples to in-situ observe their IR spectra of chemical bonding behaviors of Y^（3＋）, La^（3＋） and Ce^（3＋） cations, which could show different chemical bonding modes of 4f and 5d electrons. In the present study, we obtained the direct criterion to confirm whether 4f electrons can participate in chemical bonding, that is, only when the coordination number of RE cations is larger than 9.

Exploring electronic-level principles how size reduction enhances nanomaterial surface reactivity through experimental probing and mathematical modeling

Size reduction can generally enhance the surface reactivity of inorganic nanomaterials.The origin of this nano-effect has been ascribed to ultrasmall size,large specific surface area,or abundant defects,but the most intrinsic electronic-level principles are still not fully understood yet.By combining experimental explorations and mathematical modeling,herein we propose an electronic-level model to reveal the physicochemical nature of size-dependent nanomaterial surface reactivity.Experimentally,we reveal that competitive redistribution of surface atomic orbitals from extended energy band states into localized surface chemical bonds is the critical electronic process of surface chemical interactions,using H_(2)O_(2)-TiO_(2)chemisorption as a model reaction.Theoretically,we define a concept,orbital potential(G),to describe the electronic feature determining the tendency of orbital redistribution,and deduce a mathematical model to reveal how size modulates surface reactivity.We expose the dual roles of size reduction in enhancing nanomaterial surface reactivity-inversely correlating to orbital potential and amplifying the effects of other structural factors on surface reactivity.

B←N-containing azaacenes with propynyl groups on boron atoms

For organnoboron co mpounds,the substituents on boron atoms are very important because they not only impact on the molecular stability but also significantly modulate the electronic structu res and prope rties.In this manuscript,we synthesized two new B←N-co ntaining azaacenes with propynyl groups on boron atoms through one-step Grignard reaction.Replacing fluorine atoms by propynyl groups greatly impacts on the electronic energy levels,especially enhancing the HOMO levels,thus leading to the narrowed HOMO-LUMO bandgaps.These B←N-containing azaacenes exhibit the NIR light-absorption(λabs=706 nm for 2 a and 762 nm for 2 b)and fluorescence properties(λem=740 nm for 2 a and802 nm for 2 b),as well as multiple reversible redox behaviors,which are significantly different from the analogs with fluorine atoms.This study thus provides a functional substituent of boron atom,which may lead to new organoboron materials with fascinating properties.

15%Efficiency All-Polymer Solar Cells Based on a Polymer Acceptor Containing B←N Unit

The development of new polymer acceptors strongly paves the power conversion efficiency(PCE)improvement of all polymer solar cells(all-PSCs).Herein,we develop a new polymer acceptor PBN26,which is the alternating copolymer of 2,2′-((2Z,2′Z)-((12,13-bis(2-octyldodecyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1 H-indene-2,1-diylidene))dimalononitrile and B←N bridged thienylthiazole(BNTT).The optimized all-PSCs device based on PBN26 exhibits a PCE of 15.09%,which is the highest value of the all-PSCs based on B←N-based polymer acceptors at present.Moreover,we also fabricate an all-PSC module with active area of 10 cm2 by blade coating,which exhibits a PCE of 8.78%.These results prove that polymer acceptors containing B←N units are promising for all-PSC device applications.