Transition metal coordination polymers with flexible dicarboxylate ligand:Synthesis,characterization,and photoluminescence property

Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.

A theoretical model for impact protection of flexible polymer material

The relationship between the protective performance of flexible polymer material and material parameters(elasticmodulus,viscosity coefficient)is explored,an impact collision motion equation between two bodies is establishedfrom the viscoelastic material constitutive,and the relationship between the kinematic response and the materialparameters is obtained.Based on the Kelvin constitutive model,a theoretical model for impact between the pro-tective body and the protected body is established,then the dynamic response is obtained.The feasibility of themodel was verified by drop hammer experiment,and the material parameters(elastic modulus,viscosity coeffi-cient)were obtained by formula.The model is discretized and the relationship between local impact response andmaterial parameters is analyzed.The discussion results on the relationship between the impact response and theprotective material performance indicate that adjusting the elastic modulus,viscosity coefficient,and thicknessof the protective material can effectively improve protective effect.

Fibrous gel polymer electrolyte for an ultrastable and highly safe flexible lithium-ion battery in a wide temperature range

Replacement of flammable liquid electrolytes with gel polymer electrolytes(GPEs)is a promising route to improve the safety of lithium-ion batteries(LIBs).However,polymer-based electrolytes have limited suitability at low/high temperatures due to the instability of the polymer at high temperatures and the low ionic conductivity of the gel state at low temperatures.Herein,an integrated design of electrodes/fibrous GPEs modified with graphene oxide(GO)is reported.Due to the integrated structure of electrodes/GPEs,the strong interface affinity between electrodes and GPEs ensures that the GPEs spun on electrodes do not shrink at high temperatures(160-180℃),thus preventing a short circuit of electrodes.Moreover,after GO modification,oxygen-containing functional groups of GO can accelerate Li^(+)transport of GO-GPEs even at a low temperature of−15℃.When these GPEs are applied to flexible LIBs,the LIBs show excellent electrochemical performance,with satisfactory cycling stability of 82.9%at 1 C after 1000 cycles at 25℃.More importantly,at a high temperature of 160℃,the LIBs can also discharge normally and light the green light-emitting diode.Furthermore,at a low temperature of−15℃,92.7%of its room-temperature capacity can be obtained due to the accelerated Li^(+)transport caused by GO modification,demonstrating the great potential of this electrolyte and integrated structure for practical gel polymer LIB applications.

Effects of Flexible Conjugation-Break Spacers of Non-Conjugated Polymer Acceptors on Photovoltaic and Mechanical Properties of All-Polymer Solar Cells

All-polymer solar cells(all-PSCs)possess attractive merits including superior thermal stability and mechanical flexibility for large-area roll-to-roll processing.Introducing flexible conjugation-break spacers(FCBSs)into backbones of polymer donor(P_(D))or polymer acceptor(P_(A))has been demonstrated as an efficient approach to enhance both the photovoltaic(PV)and mechanical properties of the all-PSCs.However,length dependency of FCBS on certain all-PSC related properties has not been systematically explored.In this regard,we report a series of new non-conjugated P_(A)s by incorporating FCBS with various lengths(2,4,and 8 carbon atoms in thioalkyl segments).Unlike com-mon studies on so-called side-chain engineering,where longer side chains would lead to better solubility of those resulting polymers,in this work,we observe that the solubilities and the resulting photovoltaic/mechanical properties are optimized by a proper FCBS length(i.e.,C2)in P_(A) named PYTS-C2.Its all-PSC achieves a high efficiency of 11.37%,and excellent mechanical robustness with a crack onset strain of 12.39%,significantly superior to those of the other P_(A)s.These results firstly demonstrate the effects of FCBS lengths on the PV performance and mechanical properties of the all-PSCs,providing an effective strategy to fine-tune the structures of P_(A)s for highly efficient and mechanically robust PSCs.

Incorporation of flexible ionic polymers into a Lewis acid-functionalized mesoporous silica for cooperative conversion of CO2 to cyclic carbonates

A rational integration of multiple reactive centers into a combined unit to facilitate their cooperative effects is a smart approach for accelerating the catalytic activity.Here,to achieve this goal,linear imidazolium-based ionic polymers were confined into the nanopores of mesoporous silica nanospheres anchored with homogeneously distributed zinc salts.Owing to the flexible character and the reinforced cooperative effects of the ionic liquid(nucleophile)and zinc species(Lewis acid)in the confined mesoporous structure,the resultant composite exhibited dramatically improved catalytic performance in the cycloaddition of CO2 with epoxides to form cyclic carbonates.This was in contrast to that observed for the individual catalytic components.Moreover,such a solid catalyst could be easily recovered and reused four times without a significant loss of activity.

Supramolecular Polymer Intertwined Free-Standing Bifunctional Membrane Catalysts for All-Temperature Flexible Zn-Air Batteries

Rational construction of flexible free-standing electrocatalysts featuring long-lasting durability,high efficiency,and wide temperature tolerance under harsh practical operations are fundamentally significant for commercial zinc-air batteries.Here,3D flexible free-standing bifunctional membrane electrocatalysts composed of covalently cross-linked supramolecular polymer networks with nitrogen-deficient carbon nitride nanotubes are fabricated(referred to as PEMAC@NDCN)by a facile self-templated approach.PEMAC@NDCN demonstrates the lowest reversible oxygen bifunctional activity of 0.61 V with exceptional long-lasting durability,which outperforms those of commercial Pt/C and RuO_(2).Theoretical calculations and control experi-ments reveal the boosted electron transfer,electrolyte mass/ion transports,and abundant active surface site preferences.Moreover,the constructed alkaline Zn-air battery with PEMAC@NDCN air-cathode reveals superb power density,capacity,and discharge-charge cycling stability(over 2160 cycles)compared to the reference Pt/C+RuO_(2).Solid-state Zn-air batteries enable a high power density of 211 mW cm^(−2),energy density of 1056 Wh kg^(−1),stable charge-discharge cycling of 2580 cycles for 50 mA cm^(−2),and wide temperature tolerance from−40 to 70℃with retention of 86%capacity compared to room-temperature counterparts,illustrating prospects over harsh operations.

Polymer Hydrogel Electrolytes for Flexible and Multifunctional Zinc-Ion Batteries and Capacitors

Flexibility and multifunctionality are now becoming inevitable worldwide tendencies for electronic devices to meet modern life's convenience,efficiency,and quality demand.To that end,developing flexible and wearable energy storage devices is a must.Recently,aqueous zinc-ion batteries(ZIBs)and zinc-ion capacitors(ZICs)stand out as two of the most potent candidates for wearable electronics due to their excellent electrochemical performance,intrinsic safety,low cost,and functional controllability.Simultaneously,polymer electrolytes'introduction and rational design,especially various hydrogels,have endowed conventional ZIBs and ZICs with colorful functions,which has been regarded as a perfect answer for energy suppliers integrated into those advanced wearable electronic devices.This review focuses on the functional hydrogel electrolytes(HEs)and their application for ZIBs and ZICs.Previously reported HEs for ZIBs and ZICs were classified and analyzed,from the flexibility to mechanical endurance,temperature adaptability,electrochemical stability,and finally cell-level ZIBs and ZICs based on multifunctional HEs.Besides introducing the diverse and exciting functions of HEs,working principles were also analyzed.Ultimately,all the details of these examples were summarized,and the related challenges,constructive solutions,and futural prospects of functional ZIBs and ZICs were also dedicatedly evaluated.

MOLECULAR FIELD THEORY FOR NEMATIC LIQUID CRYSTAL POLYMER COMPRISING FLEXIBLE SPACER

Basea on the new model and concept of mtramolecular orientational order parameter, a molecular field theory was built up for main chain liquid crystalline polymer (MC-LCPs) with flexible spacers. The theory takes account of orientational correlation among all mesogens in a polymer chain and the relationship between the intramolecular orientation and spatial orientation of the mesogens. The free energy, temperature and entropy of the nematic-isotropic transition were determined with the theory and compared with experiments in current work. It was found that many unique transition properties of the MC-LCPs comprising flexible spacer are correctly predicted by the theory and the agreement of the theory with the experiments is impressive.

A Mn(Ⅱ) Coordination Polymer with the Flexible Tripodal Ligand 1,3,5-Tris-(imidazol-1-ylmethyl)benzene

A new Mn（Ⅱ） coordination polymer {[Mn（timb）2（H2O）2]·（Cl）2·（H2O）2}n（1,timb = 1,3,5-tris-（imidazol-1-ylmethyl）benzene） has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=9.0774（13）,b=9.8720（15）,c=11.4898（16）A,α=93.378（3）,β= 95.471（3）,γ=101.101（3）°,V=1002.6（3）A^3,Mr=834.67,Dc=1.382 g/cm^3,μ（MoKα）=0.517mm^-1,F（000）=435,GOF=0.986,Z=1,the final R=0.0506 and wR=0.1139 for 3517 observed reflections I〉2σ（I）.It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands,and these chains are further connected to yield a 3D supramolecular framework by hydrogen bonding interactions and π…π stacking interactions.

Syntheses,Structures,and Properties of Three New Polymers Based on Flexible and Rigid Ligands

Three new supramolecular polymers, [（IP）（H2SO4）（H2O）]（1）, [（H2SDC）（BPA）]（2） and [Mn（SDC）（IP）2]n （3）, have been constructed by three modes（rigid IP, rigid SDC ＋ flexible BPA, rigid IP ＋ rigid SDC）. Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π···π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π···π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.

Syntheses,Structures and Properties of Two New Coordination Polymers with Flexible Ligands as Linkers

Two new coordination polymers,[ZnL1]n（1,H2L1 = 5-（4-pyridyl）-methoxyl isophthalic acid） and[Ni（L2）2（H2O）4]n（2,HL2 = 4-（pyridin-4-ylmethoxy）benzolic acid）,have been synthesized and characterized by elemental analysis,PXRD,IR spectra,and single-crystal X-ray diffraction.Compound 1 has a three-dimensional framework constructed by 6-bridged L1^2- anions connecting the Zn2（O2C）4 paddlewheel-like units.Compound 2 contains a mononuclear molecular unit,and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2^- ligands and four oxygen atoms from water molecules.These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimensional（3D） supramolecular network.The thermal and photoluminescent properties of 1 and 2 have also been investigated.

Flexible piezoresistive pressure sensor based on a graphene-carbon nanotube-polydimethylsiloxane composite

Flexible sensors are used widely in wearable devices, specifically flexible piezoresistive sensors, which are common and easy to manipulate.However, fabricating such sensors is expensive and complex, so proposed here is a simple fabrication approach involving a sensor containing microstructures replicated from a sandpaper template onto which polydimethylsiloxane containing a mixture of graphene and carbon nanotubes is spin coated. The surface morphologies of three versions of the sensor made using different grades of sandpaper are observed, and the corresponding pressure sensitivities and linearity and hysteresis characteristics are assessed and analyzed. The results show that the sensor made using 80-mesh sandpaper has the best sensing performance. Its sensitivity is 0.341 kPa-1in the loading range of 0–1.6 kPa, it responds to small external loading of 100 Pa with a resistance change of 10%, its loading and unloading response times are 0.126 and 0.2 s, respectively,and its hysteresis characteristic is ~7%, indicating that the sensor has high sensitivity, fast response, and good stability. Thus, the presented piezoresistive sensor is promising for practical applications in flexible wearable electronics.

Flexible Polydimethylsiloxane Composite with Multi-Scale Conductive Network for Ultra-Strong Electromagnetic Interference Protection

Highly conductive polymer composites(CPCs) with excellent mechanical flexibility are ideal materials for designing excellent electromagnetic interference(EMI) shielding materials,which can be used for the electromagnetic interference protection of flexible electronic devices.It is extremely urgent to fabricate ultra-strong EMI shielding CPCs with efficient conductive networks.In this paper,a novel silver-plated polylactide short fiber(Ag@PL ASF,AAF) was fabricated and was integrated with carbon nanotubes(CNT) to construct a multi-scale conductive network in polydimethylsiloxane(PDMS) matrix.The multi-scale conductive network endowed the flexible PDMS/AAF/CNT composite with excellent electrical conductivity of 440 S m-1and ultra-strong EMI shielding effectiveness(EMI SE) of up to 113 dB,containing only 5.0 vol% of AAF and 3.0 vol% of CNT(11.1wt% conductive filler content).Due to its excellent flexibility,the composite still showed 94% and 90% retention rates of EMI SE even after subjected to a simulated aging strategy(60℃ for 7 days) and 10,000 bending-releasing cycles.This strategy provides an important guidance for designing excellent EMI shielding materials to protect the workspace,environment and sensitive circuits against radiation for flexible electronic devices.

A comprehensive review on material selection for polymer matrix composites subjected to impact load

Polymer matrix composites(PMC)are extensively been used in many engineering applications.Various natural fibers have emerged as potential replacements to synthetic fibers as reinforcing materials composites owing to their fairly better mechanical properties,low cost,environment friendliness and biodegradability.Selection of appropriate constituents of composites for a particular application is a tedious task for a designer/engineer.Impact loading has emerged as the serious threat for the composites used in structural or secondary structural application and demands the usage of appropriate fiber and matrix combination to enhance the energy absorption and mitigate the failure.The objective of the present review is to explore the composite with various fiber and matrix combination used for impact applications,identify the gap in the literature and suggest the potential naturally available fiber and matrix combination of composites for future work in the field of impact loading.The novelty of the present study lies in exploring the combination of naturally available fiber and matrix combination which can help in better energy absorption and mitigate the failure when subjected to impact loading.In addition,the application of multi attributes decision making(MADM)tools is demonstrated for selection of fiber and matrix materials which can serve as a benchmark study for the researchers in future.

Highly Flexible Fabrics/Epoxy Composites with Hybrid Carbon Nanofillers for Absorption-Dominated Electromagnetic Interference Shielding

Epoxy-based nano-composites can be ideal electromagnetic interference(EMI)-shielding materials owing to their lightness,chemical inertness,and mechanical durability.However,poor conductivity and brittleness of the epoxy resin are challenges for fast-growing portable and flexible EMI-shielding applications,such as smart wristband,medical cloth,aerospace,and military equipment.In this study,we explored hybrid nanofillers of single-walled carbon nanotubes(SWCNT)/reduced graphene oxide(rGO)as conductive inks and polyester fabrics(PFs)as a substrate for flexible EMI-shielding composites.The highest electrical conductivity and fracture toughness of the SWCNT/rGO/PF/epoxy composites were 30.2 S m^(−1)and 38.5 MPa m^(1/2),which are~270 and 65%enhancement over those of the composites without SWCNTs,respectively.Excellent mechanical durability was demonstrated by stable electrical conductivity retention during 1000 cycles of bending test.An EMI-shielding effectiveness of~41 dB in the X-band frequency of 8.2-12.4 GHz with a thickness of 0.6 mm was obtained with an EM absorption-dominant behavior over a 0.7 absorption coefficient.These results are attributed to the hierarchical architecture of the macroscale PF skeleton and nanoscale SWCNT/rGO networks,leading to superior EMI-shielding performance.We believe that this approach provides highly flexible and robust EMI-shielding composites for next-generation wearable electronic devices.

Fiber-Reinforced Polymer Bridge Design in the Netherlands： Architectural Challenges toward Innovative, Sustainable, and Durable Bridges

This paper reviews the use of fiber-reinforced polymers （FRPs） in architectural and structural bridge design in the Netherlands. The challenges and opportunities of this relatively new material, both for the architect and the engineer, are discussed. An inventory of recent structural solutions in FRP is included, followed by a discussion on architectural FRP applications derived from the architectural practice of the author and of other pioneers.

Review and perspective of materials for flexible solar cells

Thin-film flexible solar cells are lightweight and mechanically robust.Along with rapidly advancing battery technology,flexible solar panels are expected to create niche products that require lightweight,mechanical flexibility,and moldability into complex shapes,such as roof-panel for electric automobiles,foldable umbrellas,camping tents,etc.In this paper,we provide a comprehensive assessment of relevant materials suitable for making flexible solar cells.Substrate materials reviewed include metals,ceramics,glasses,and plastics.For active materials,we focus primarily on emerging new semiconductors including small organic donor/acceptor molecules,conjugated donor/acceptor polymers,and organometal halide perovskites.For electrode materials,transparent conducting oxides,thin metal films/nanowires,nanocarbons,and conducting polymers are reviewed.We also discuss the merits,weaknesses,and future perspectives of these materials for developing next-generation flexible photovoltaics.

A symmetric MnO_2/MnO_2 flexible solid state supercapacitor operating at 1.6V with aqueous gel electrolyte

The demand of microelectronic devices postulated high energetic flexible energy storage devices. Flexible solid state supercapacitor is flawless possible candidate to fulfill the requirement of microelectronic devices. This investigation provides practical evidence of the use of flexible solid state supercapacitors based on MnOelectrodes with polyvinylpyrrolidone(PVP)-Li ClOgel electrolyte. Initially, different acid mediated growths of MnOhave been carried. Later, the electrochemical performances of MnOelectrodes have been carried out. Impressively, the fabricated symmetric flexible solid state supercapacitor(FSS-SC) device demonstrates the highest operating potential window of 1.6 V with extended cycling stability. Moreover, the cell exhibits high energy density of 23 Wh/kg at power density of 1.9 k W/kg. It is interesting to note that the device shows excellent flexibility upon bending at angle of 180° for number of times. These results clearly evidenced those symmetric FSS-SC devices based on MnOelectrodes are promising energy storage devices for microelectronic applications.

Syntheses and Crystal Structures of Three Cadmium（II） Coordination Complexes Based on Flexible 1,2-Bis（imidazol-1~ˊ-yl）ethane

Three Cd（II） coordination complexes,{[Cd（bime）3]（NO3）2·（H2O）3}n（1）,[Cd（bime）Br2]n（2） and [（H2bime）（CdBr4）（H2O）]n（3）（bime = 1,2-bis（imidazol-1-yl）ethane）,have been prepared and characterized.Single-crystal X-ray diffraction analysis reveals that 1~3 crystallize in the trigonal space group P-3,monoclinic space group C2/c and triclinic space group P1,respectively.In 1,bime bridges six-coordinated Cd（II） to generate a two-fold interpenetrating 3D coordination polymer,in which NO3- is not involved in coordination,but serves as a void filler to balance the charge of the 3D framework.The six NO3- and six uncoordinated water molecules form an unprecedented 24-membered macrocycle through hydrogen bonding interaction.In 2,bime in an anti-conformation links the CdBr2 units into a zigzag chain.In 3,bime does not take part in coordination,but is protonated to act as a counter cation of [CdBr4 ]2-.The hydrogen bonds between H2bime and [CdBr4]2- result in the formation of a supramolecular chain.

Anion Directed Assembly of Cu(Ⅱ)Complexes Formed by a Flexible Ligand

Coordination polymers,consisting of metal,anion and organic ligands,have attracted much attention.The structure of coordination polymers is affected by various factors.To investigate the effects of anion,syntheses and structures of four Cu(II)complexes,namely[(Cu LCl)(PF)](1),[(Cu LCl)(ClO)](2),[(Cu LCl)?CHOH](3)and Cu LCl(4),are reported based on a flexible ligand,1,3-bis(2-pyridylmethyl)imidazolium(L).The ligand is accommodative to kinds of anions,and forms 1-D chains generally upon reaction with Cu(II)salts.The effect is measured by the conformational variation through the dihedral angles between different aromatic rings of the ligand.In order to further investigate the effect of anion,a protonated sample of L,namely,LH(ClO)?HO(5)is also synthesized and structurally characterized,showing an intriguing hydrogen bonded helix.