Although organic compounds are considered to be promising electrode materials with their remarkable characteristics such as diverse structures,design controllability,and environmental friendliness,their low charge-tra...Although organic compounds are considered to be promising electrode materials with their remarkable characteristics such as diverse structures,design controllability,and environmental friendliness,their low charge-transfer capability and limited cycling durability hinder their application in aqueous proton batteries.Herein,we prepared a noncovalent phenazine-based graphene aerogel(H/G)composite for aqueous proton storage,which is realized by redox-active Hexaazatrinaphthalene(HATN)organic compound combined with conductive reduced graphene oxide(rGO).The integration of rGO into HATN not only effectively optimizes the electronic structure of the H/G composite to enhance its electrochemical activity,but also the favorable noncovalent π-π interaction existed between HATN and rGO provides a stable structure for fast electron transportation.The obvious electron transfer in the aerogel composite promotes fast and reversible redox reactions occurred with the imino-active HATN in the composite electrode for proton uptake/removal in an aqueous acidic electrolyte,which are demonstrated by in-situ Fourier transform infrared(FTIR)investigation,theoretical calculations and experimental measurements.Therefore,it can deliver a fast,stable and efficient aqueous proton storage behavior with a large specific capacity of 274 mA·h·g^(-1) and considerable calendar life with~100%capacity retention after 3000 cycles,surpassing previously reported proton-based organic electrodes in aqueous acidic electrolytes.Furthermore,an outstanding soft-package aqueous proton(APB)has been fabricated with considerable long-term cycling stability.展开更多
Nonfused ring electron acceptors(NFREAs)have attracted much attention due to their concise synthetic routes and low cost.However,developing high-performance NFREAs with simple structure remains a great challenge.In th...Nonfused ring electron acceptors(NFREAs)have attracted much attention due to their concise synthetic routes and low cost.However,developing high-performance NFREAs with simple structure remains a great challenge.In this work,a simple building block(POBT)with noncovalently conformational locks(No CLs)was designed and synthesized.Single-crystal X-ray study indicated the presence of S…O NOCLs in POBT,thus enabling it to possess a coplanar conformation comparable to that of fused-ring CPT.Two novel NFREAs based on CPT and POBT were developed,namely TT-CPT and TT-POBT,respectively.Besides,TT-POBT possessed a smaller Stokes shift and a reduced reorganization energy compared with TT-CPT,indicating the introduction of S…O No CLs can enhance the molecular rigidity even if simplifying the molecular structure.As a result,the TT-POBT-based PSC device afforded an impressive power conversion efficiency of 11.15%,much higher than that of TT-CPT counterpart(7.03%),mainly resulting from the tighterπ-πstacking,improved and balanced charge transport,and more favorable film morphology.This work demonstrates the potential of the simple building block POBT with No CLs towards constructing low-cost and highperformance NFREAs.展开更多
Noncovalent interfaces play a vital role in inelastic deformation and toughening mechanisms in layered nanocomposites due to their dynamical recoverability. When interfacial engineering is applied to design layered na...Noncovalent interfaces play a vital role in inelastic deformation and toughening mechanisms in layered nanocomposites due to their dynamical recoverability. When interfacial engineering is applied to design layered nanocomposites, shear-lag analysis is usually implemented to evaluate the capability of interfacial loading transfer. Here, we introduce a multiscale shear-lag model that correlates macroscale mechanical properties with the molecular mechanisms to quantify the effects of interfacial configuration in graphene oxide(GO) layered nanocomposites. By investigating the mechanical responses of commensurate and incommensurate interfaces, we identify that the commensurate interface exhibits a pronounced size effect due to the nucleation and propagation of interfacial defects, whereas the incommensurate interface displays uniform deformation. Our predictions are further validated through large-scale molecular dynamics simulations for GO layered nanocomposites. This work demonstrates how size effects and interfacial configurations can be exploited to fabricate layered nanocomposites with superior mechanical properties despite relying on weak noncovalent interfaces.展开更多
Due to their environmentally friendly nature and high energy density,direct ethanol fuel cells have attracted extensive research attention in recent decades.However,the actual Faraday efficiency of the ethanol oxidati...Due to their environmentally friendly nature and high energy density,direct ethanol fuel cells have attracted extensive research attention in recent decades.However,the actual Faraday efficiency of the ethanol oxidation reaction(EOR)is much lower than its theoretical value and the reaction kinetics of the EOR is sluggish due to insufficient active sites on the electrocatalyst surface.Pt/C is recognized as one of the most promising electrocatalysts for the EOR.Thus,the microscopic interfacial reaction mechanisms of the EOR on Pt/C were systematically studied in this work.In metal hydroxide solutions,hydrated alkali cations were found to bind with OH_(ad)through noncovalent interactions to form clusters and occupy the active sites on the Pt/C electrocatalyst surface,thus resulting in low Faraday efficiency and sluggish kinetics of the EOR.To reduce the negative effect of the noncovalent interactions on the EOR,a shield was made on the electrocatalyst surface using 4-trifluoromethylphenyl,resulting in twice the EOR catalytic reactivity of Pt/C.展开更多
This study reveals that the noncovalent complexation betweenβ-CD and Cu（HMTA）^（2＋） makes a positive contribution to the coordination interaction between Cu^（2＋） and HMTA in a tricomponent system.Besides,mono-...This study reveals that the noncovalent complexation betweenβ-CD and Cu（HMTA）^（2＋） makes a positive contribution to the coordination interaction between Cu^（2＋） and HMTA in a tricomponent system.Besides,mono- and binuclear complexes：[β-CDCu]~＋ and[Cu·β-CDCu]~＋ were observed under the condition of ESI-MS.展开更多
The versatility and flexibility of organic photoelectric materials endow organic photovoltaic cells fine function modulation and huge commercial potential. In this work, a new noncovalent fused-ring small molecule acc...The versatility and flexibility of organic photoelectric materials endow organic photovoltaic cells fine function modulation and huge commercial potential. In this work, a new noncovalent fused-ring small molecule acceptor(SMA) BID-4 F has been synthesized for high-efficient organic solar cells(OSCs). BID-4 F consists of a diflurobenzothiadiazole(DFBT) core, ladder-like indacenodithiophene(IDT) spacers, and dicyanoindanone electron-withdrawing end groups, which are supposed to be conformationally interlocked by noncovalent interactions, leading to good molecular planarity. In addition, compact solid state stacking was revealed by UV–vis–NIR absorption spectrum. The optimized PM6:BID-4 F based device delivers an eminent power conversion efficiency(PCE) of 12.30% with a high open-circuit voltage(Voc) of 0.92 V and a high fill factor(FF) of 74.3%. Most importantly, the PCE and FF are among one of the highest values reported for the OSCs based on the unfused-ring SMAs. Overall, our work demonstrates that the unfused ring central framework with high molecular planarity through noncovalent interactions provides a good strategy to construct highly efficient SMAs.展开更多
Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide g...Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide generation is limited by the competitive four-electron pathway.In this work,we report a noncovalent modulation strategy for the isolated CoN_(4) sites by metal-phthalocyanine molecules confinement,which boosts the two-electron oxygen reduction towards generating hydrogen peroxide.The confined Co-phthalocyanine molecules on CoN_(4) sites through π-π interactions induce the competitive*OOH adsorption between the two Co sites formed nanochannel.This noncovalent modulation contributes to the weakened*OOH binding on CoN_(4) sites and thus suppresses its further dissociation,achieving the maximum selectivity of 95% with high activity for H_(2)O_(2)production.This work shows that tailoring noncovalent interactions beyond the binding sites is a promising approach to modulate the local structure of isolated metal sites and related catalytic performance.展开更多
CONSPECTUS:Controlling self-assembled peptide nanostructures has emerged as a significant area of research,offering versatile tools for developing functional materials for various applications.This Account emphasizes ...CONSPECTUS:Controlling self-assembled peptide nanostructures has emerged as a significant area of research,offering versatile tools for developing functional materials for various applications.This Account emphasizes the essential role of noncovalent interactions,particularly in peptide-based materials.Key forces,such as aromatic stacking and hydrogen bonding,are crucial for promoting molecular aggregation and stabilizing supramolecular structures.Numerous studies demonstrate how these interactions influence the phase transitions and the morphology of self-assembled structures.Recent advances in computational methodologies,including molecular dynamics simulations and machine learning,have significantly enhanced our understanding of self-assembly processes.These tools enable researchers to predict how molecular properties,such as hydrophobicity,charge distribution,and aromaticity,affect assembly behavior.Simulations uncover the energetic landscapes governing peptide aggregation,providing insights into the kinetic pathways and thermodynamic stabilities.Meanwhile,machine learning facilitates the rapid screening of peptide libraries,identifying sequences with optimal self-assembly characteristics,and accelerating material design with tailored functionalities.Beyond their structural and physicochemical properties,self-assembled peptide nanostructures hold immense potential in biological applications due to their versatility and biocompatibility.By manipulating molecular interactions,researchers have engineered responsive systems that interact with cellular environments to elicit specific biological responses.These peptide nanostructures can mimic extracellular matrices,facilitating cell adhesion,proliferation,and differentiation.They also show promise in modulating immune responses,recruiting immune cells,and regulating signaling pathways,making them valuable tools in immunotherapy and regenerative medicine.Moreover,their ability to disrupt bacterial membranes positions them as innovative alternatives to conventional antibiotics,addressing the urgent need for solutions to antimicrobial resistance.Despite its promise,peptide self-assembly faces several challenges.The assembly process is highly sensitive to environmental conditions,such as pH,temperature,and ionic strength,leading to variability in the morphology and properties.Furthermore,peptide aggregation can result in heterogeneous and poorly defined assemblies,complicating the reproducibility and scalability.Designing peptides with predictable self-assembly behavior remains a significant hurdle.Looking ahead,integrating computational predictions with experimental validations will be crucial in discovering novel peptide sequences with tailored self-assembly properties.Machine learning,combined with high-throughput screening techniques,will enable the rapid identification of optimal peptide sequences.In situ characterization tools,such as cryoelectron microscopy and advanced spectroscopy,will provide deeper insights into assembly mechanisms,aiding the rational design of peptide materials.As research progresses,the dynamic and reversible nature of noncovalent interactions can be leveraged to create adaptive responsive to environmental stimuli.Self-assembled peptide nanostructures are poised for impactful applications in biomedicine including targeted drug delivery,tissue repair,and advanced therapeutic strategies.Ultimately,these nanostructures represent a powerful platform for addressing complex challenges in biomedicine and beyond,paving the way for transformative breakthroughs in science and technology.展开更多
The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy ...The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy has not yet been explored in-depth to reach its full potential.In this work,we demonstrate that by directing noncovalent interactions to the central rotating bond of indigo-based photoswitches,their thermal relaxation dynamics were altered in two opposite directions(either slowed down or sped up)allowing for modulating the relaxation half-lives across four orders of magnitude.More importantly,our work established two distinct and orthogonal working mechanisms of noncovalent control over isomerization:(1)Thermodynamic stabilization of photoisomers;and(2)Facilitating an alternative reaction pathway through Brønsted/Lewis acid catalysis.This two-directional modulation(resembling agonists and inverse agonists in biological systems)via two orthogonal working mechanisms will enable more delicate manipulation of photoswitches for advanced applications.展开更多
Intramolecular noncovalent conformational locks(NoCLs)have emerged as an important strategy for developing high-performance organic/polymeric semiconductors(OPSs)via suppressing the non-radiative decay.Despite extensi...Intramolecular noncovalent conformational locks(NoCLs)have emerged as an important strategy for developing high-performance organic/polymeric semiconductors(OPSs)via suppressing the non-radiative decay.Despite extensive investigation into the impact of NoCLs on small molecules,elucidating their influence on the physicochemical properties of conjugated polymers(CPs)remains a critical challenge.By employing a combination of theoretical and experimental methods,it is revealed that the incorporation of NoCLs increases the rigidity of the polymer chain,enhances intermolecular interactions,promotes the formation of pre-aggregates of optimal length,and improves charge transport,providing valuable insights for designing high-performance CPs.展开更多
Main observation and conclusion Recently,the asymmetric nonfullerene acceptors(NFAs)with acceptor-donor-acceptor(A-D-A)structure have been developed rapidly,especially for the modification of asymmetric core,asymmetri...Main observation and conclusion Recently,the asymmetric nonfullerene acceptors(NFAs)with acceptor-donor-acceptor(A-D-A)structure have been developed rapidly,especially for the modification of asymmetric core,asymmetric side chains and asymmetric end groups.In this work,a novel asymmetric A-D-π-A type NFA with a noncovalently fused-ring core named PIST-4F is synthesized,containing an indacenodithieno[3,2-b]dithiophene(IDT),two strong electron-withdrawing end groups and an alkylthio-substituted thiopheneπ-bridge.Benefiting from the S···S noncovalent interaction between the sulfur atom onπ-bridge and the adjacent thiophene in IDT,the PIST-4F presents nearly planar geometry and extended conjugated area,resulting in the optimized electronic properties,charge transport,and film morphology compared to the symmetric NFA PI-4F.As a result,PM6:PIST-4F-based devices achieve a higher power conversion efficiency(PCE)of 13.8%,while the PM6:PI-4F-based devices only show a PCE of 7.1%.Notably,the PM6:PIST-4F-based devices processed with nonhalogen solvent toluene exhibit an excellent PCE as high as 13.1%.These results indicate that PIST-4F is an effective acceptor for high-efficiency organic solar cells.展开更多
The polymerization of fused-ring acceptors(FRAs) to afford their corresponding polymeric acceptors for high-performance all-polymer solar cells(all-PSCs) has achieved remarkable progress in the past few years.However,...The polymerization of fused-ring acceptors(FRAs) to afford their corresponding polymeric acceptors for high-performance all-polymer solar cells(all-PSCs) has achieved remarkable progress in the past few years.However,due to the high degree of synthetic complexity for the monomer,the high-cost of these polymeric acceptors may limit their commercial applications.Thus,it is urgent to develop inexpensive and high-performance polymeric acceptors for all-PSCs.Herein,two novel polymeric acceptors(PBTzO and PBTzO-2F) have been designed and synthesized by copolymerization of noncovalently fused ring acceptors(NFRAs),which were employed in all-PSCs for the first time.Upon introducing the “noncovalently conformational locks(NoCLs)” in the backbone and selective fluorination of the end-group,photophysical and electrical properties,and solidstate packing properties of the NFRAs have been rationally tuned.As a result,the PBDB-T:PBTzO-2F based devices presented an excellent power conversion efficiency(PCE) of 11.04%,much higher than that of PBTzO based ones due to the increased charge generation and extraction,improved hole transfer and carrier mobilities,and reduced energy loss.More importantly,PBTzO-2F exhibited a much lower synthetic complexity(SC) index and higher figure-of-merit(FOM) values than the high-performance fused-ring acceptor based polymer acceptors(FRA-PAs) due to the simpler structures and more effective synthesis.This contribution provided a novel idea to achieve low-cost and high-performance all-PSCs.展开更多
Highly planar conformation is considered to be one of the most important properties for high performance organic semiconductors. Among all kinds strategies for designing highly performing materials, noncovalent confor...Highly planar conformation is considered to be one of the most important properties for high performance organic semiconductors. Among all kinds strategies for designing highly performing materials, noncovalent conformational locks （NCLs） have been widely used to increase the planarity and rigidity for x-conjugated systems. This review summarizes π-conjugated small molecules and polymers by employing various NCLs for controlling molecular conformation in the past two years. The optoelectronic properties of the conjugated materials, together with their applications on organic field-effect transistors （OFETs） and organic photovoltaics （OPVs） are discussed. Besides, the outlook and challenges in this field are also presented. It is obvious that NCLs play an important role in the design and synthesis of high-performance organic semiconductors.展开更多
Comprehensive Summary By employing thiazole and 4-chlorothiazole as the A′units,two A-D-A′-D-A type nonfused-ring electron acceptors(NFREAs)Tz-H and Tz-Cl were designed and synthesized.Replacing thiazole in Tz-H wit...Comprehensive Summary By employing thiazole and 4-chlorothiazole as the A′units,two A-D-A′-D-A type nonfused-ring electron acceptors(NFREAs)Tz-H and Tz-Cl were designed and synthesized.Replacing thiazole in Tz-H with 4-chlorothiazole can not only remarkably shorten the synthetic route through C—H direct arylation but also enhance molecular planarity with the simultaneous incorporation of S…N and S…Cl noncovalently conformational locks(NoCLs).The photovoltaic devices based on PM6:Tz-Cl exhibited a power conversion efficiency as high as 11.10%,much higher than that of PM6:Tz-H(6.41%),mainly due to more efficient exciton dissociation,better and more balanced carrier mobility,less charge recombination,and more favorable morphology.These findings demonstrate the great potential of NoCLs in achieving low-cost and high-performance NFREAs.展开更多
The power conversion efficiencies(PCEs)of organic solar cells(OSCs)have improved considerably in recent years with the development of fused-ring electron acceptors(FREAs).Currently,FREAs-based OSCs have achieved high ...The power conversion efficiencies(PCEs)of organic solar cells(OSCs)have improved considerably in recent years with the development of fused-ring electron acceptors(FREAs).Currently,FREAs-based OSCs have achieved high PCEs of over 19%in single-junction OSCs.Whereas the relatively high synthetic complexity and the low yield of FREAs typically result in high production costs,hindering the commercial application of OSCs.In contrast,noncovalently fused-ring electron acceptors(NFREAs)can compensate for the shortcomings of FREAs and facilitate large-scale industrial production by virtue of the simple structure,facile synthesis,high yield,low cost,and reasonable efficiency.At present,OSCs based on NFREAs have exceeded the PCEs of 15%and are expected to reach comparable efficiency as FREAs-based OSCs.Here,recent advances in NFREAs in this review provide insight into improving the performance of OSCs.In particular,this paper focuses on the effect of the chemical structures of NFREAs on the molecule conformation,aggregation,and packing mode.Various molecular design strategies,such as core,side-chain,and terminal group engineering,are presented.In addition,some novel polymer acceptors based on NFREAs for all-polymer OSCs are also introduced.In the end,the paper provides an outlook on developing efficient,stable,and low-cost NFREAs for achieving commercial applications.展开更多
Mechanical performances are among the most fundamental properties that dictate the applicability and durability of polymeric materials.Reinforcement of polymeric materials is eternally pursued to broaden the applicati...Mechanical performances are among the most fundamental properties that dictate the applicability and durability of polymeric materials.Reinforcement of polymeric materials is eternally pursued to broaden the applications of polymers with light-weight,low-cost and easy-processing advantages.Noncovalent aggregates of biomacromolecules have been found to play a significant role in the mechanical properties of many natural materials,such as the spider silk.Increasing numbers of reports have demonstrated that the in situ formed noncovalent aggregates of polymer chains in polymeric systems are highly effective for enhancing the mechanical properties of artificial polymeric materials,in terms of strength,stiffness,toughness,and/or elasticity.The in situ formed noncovalent aggregates act as additional crosslinking domains and well-dispersed“hard”nanofillers in the polymer networks,significantly strengthening,stiffening and/or toughening the polymeric materials.Moreover,the noncovalent crosslinking of polymer chains favors the development of healable and recyclable polymeric materials,thanks to the reversible and dynamic properties of noncovalent bonds.This review provides an overview of the recent advances on the enhancement of the mechanical properties of different polymeric materials by the in situ formed noncovalent aggregates of polymer chains.It is expected to arouse inspirations for the development of novel polymeric materials with extraordinary mechanical performances and functionalities.展开更多
Short chain chlorinated paraffins （SCCPs） are not only research focus of environmental issues but also interesting model mol- ecules for organic chemistry which exhibit diverse conformation preference and intramolec...Short chain chlorinated paraffins （SCCPs） are not only research focus of environmental issues but also interesting model mol- ecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions （NCIs）. A systematic study was conducted to reveal the conlk）rmation preference and the related intramolecular NCIs in two C^-isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-1etrachlorodecane. The overall conformation profile was deter- mined on the basis of relative energies calculated at the MP2/6-311＋＋G（d,p） level with the geometries optimized by B3LYP/6-31 l＋＋G（d,p） method. Then, quantum theory of atoms in molecules （QTAIM） has been adopted to identify the NCls in the selected conformers of the model molecules at both B31~YP/6-31 l＋＋G（d,p） and M06-2X/aug-cc-pvdz level. Different chlorine substitution modes result in varied conformation preference. No obvious gauche effect can be observed tk）r the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane （tTt） has its three dihedral angles in the T configuration, and there is no intramolecular N（3s found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configmation for the H C C CI axis. Not only inlramolecular H-..CI contacts but also H---H interactions have been identified as driving forces to compensate the instability from steric crowding ot the gauche configuration. The gggg and g＇g＇g＇g＇ conformers are the most popular ones, while the populations of tggg and tg＇g＇g＇ conformer are second to those of the gggg and g＇g＇g＇g＇ conformers. Meanwhile, the M06-2X method with large basis sets is preferred for identification of subtle intramolecular NCIs in large molecules like SCCPs.展开更多
Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen...Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen)Cl 2 and BzPheH 2 in water at pH～9, with their structures determined by X ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe= N benzoyl β phenylalaninate dianion). In the complex \[Pd(phen)(BzPhe N,O)\]·4H 2O, the side chain of phenylalanine is located above and approximately parallels to the coordination plane. Both the aromatic aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion aromatic interaction between the phenyl ring of phenylalanine and Pd(II) were observed. \[Pd(bipy)(BzPhe N,O)\] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested.展开更多
Glass materials play a vital role in scientific research and engineering applications.Biomolecular noncovalent glasses(BNG),based on amino acids and peptides,have been proposed as the next-generation glass materials t...Glass materials play a vital role in scientific research and engineering applications.Biomolecular noncovalent glasses(BNG),based on amino acids and peptides,have been proposed as the next-generation glass materials to meet the demand of a sustainability and circular economy.However,bulk BNG with remarkable mechanics and tunable photoluminescence are still rare due to the nature of weak noncovalent interactions and oversimplified molecular structures.Herein,we report the design and creation of metal ion-coordinated BNG(MIBNG)based on a simple amino acid derivative and metal ions.The obtained MIBNG exhibit ceramic-like mechanics,including the hardness,elasticity,and wear resistance,that are unattainable by the pure BNG counterpart.Such remarkable mechanics can be attributed to the enhanced noncovalent crosslinking network connectivity of biomolecules within MIBNG resulting from the incorporation of strong metal coordination interaction with hydrogen bonding and aromatic interactions.Moreover,fluorescence emission of MIBNG can be tuned feasibly through precisely modulating the types of metal ions coordinated.This study sheds light on the crucial role of multiple noncovalent interactions in the construction of BNG and advances the exploration and potential applications of BNG-based functional materials with tunable mechanical and optical properties in such fields as electronics and optics.展开更多
The unfavorable photochemical processes at the molecular level have become a bar-rier limiting the use of aromatic amides as high-performance luminescent materials.Herein,we propose a reliable strategy for manipulatin...The unfavorable photochemical processes at the molecular level have become a bar-rier limiting the use of aromatic amides as high-performance luminescent materials.Herein,we propose a reliable strategy for manipulating noncovalent conformational lock(NCL)via side-chain engineering to burst out eye-catching luminescence at the aggregate level.Contrary to the invisible emission in dilute solutions,dyad OO with a three-centered H-bond gave the wondrous crystallization-induced emis-sion with a quantum yield of 66.8%and clusterization-triggered emission,which were much brighter than those of isomers.Theoretical calculations demonstrate that crystallization-induced planarized intramolecular charge transfer(PICT),con-formation rigidification,and through-space conjugation(TSC)are responsible for aggregate-state luminescence.Robust NCL composed of intramolecular N-H⋅⋅⋅Ointeractions could boost molecular rigidity and planarity,thus greatly facilitating PICT and TSC.This study would inspire researchers to design efficient luminescent materials at the aggregate level via rational conformational control.展开更多
基金financially supported by the National Natural Science Foundation of China(52002157).
文摘Although organic compounds are considered to be promising electrode materials with their remarkable characteristics such as diverse structures,design controllability,and environmental friendliness,their low charge-transfer capability and limited cycling durability hinder their application in aqueous proton batteries.Herein,we prepared a noncovalent phenazine-based graphene aerogel(H/G)composite for aqueous proton storage,which is realized by redox-active Hexaazatrinaphthalene(HATN)organic compound combined with conductive reduced graphene oxide(rGO).The integration of rGO into HATN not only effectively optimizes the electronic structure of the H/G composite to enhance its electrochemical activity,but also the favorable noncovalent π-π interaction existed between HATN and rGO provides a stable structure for fast electron transportation.The obvious electron transfer in the aerogel composite promotes fast and reversible redox reactions occurred with the imino-active HATN in the composite electrode for proton uptake/removal in an aqueous acidic electrolyte,which are demonstrated by in-situ Fourier transform infrared(FTIR)investigation,theoretical calculations and experimental measurements.Therefore,it can deliver a fast,stable and efficient aqueous proton storage behavior with a large specific capacity of 274 mA·h·g^(-1) and considerable calendar life with~100%capacity retention after 3000 cycles,surpassing previously reported proton-based organic electrodes in aqueous acidic electrolytes.Furthermore,an outstanding soft-package aqueous proton(APB)has been fabricated with considerable long-term cycling stability.
基金the National Natural Science Foundation of China(Nos.52103352,51925306 and 52120105006)National Key R&D Program of China(No.2018FYA 0305800)+3 种基金Key Research Program of Chinese Academy of Sciences(No.XDPB08-2)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB28000000)the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.2022165)the Fundamental Research Funds for the Central Universities.
文摘Nonfused ring electron acceptors(NFREAs)have attracted much attention due to their concise synthetic routes and low cost.However,developing high-performance NFREAs with simple structure remains a great challenge.In this work,a simple building block(POBT)with noncovalently conformational locks(No CLs)was designed and synthesized.Single-crystal X-ray study indicated the presence of S…O NOCLs in POBT,thus enabling it to possess a coplanar conformation comparable to that of fused-ring CPT.Two novel NFREAs based on CPT and POBT were developed,namely TT-CPT and TT-POBT,respectively.Besides,TT-POBT possessed a smaller Stokes shift and a reduced reorganization energy compared with TT-CPT,indicating the introduction of S…O No CLs can enhance the molecular rigidity even if simplifying the molecular structure.As a result,the TT-POBT-based PSC device afforded an impressive power conversion efficiency of 11.15%,much higher than that of TT-CPT counterpart(7.03%),mainly resulting from the tighterπ-πstacking,improved and balanced charge transport,and more favorable film morphology.This work demonstrates the potential of the simple building block POBT with No CLs towards constructing low-cost and highperformance NFREAs.
基金jointly supported by the National Natural Science Foundation of China(Nos.11872063 and 12172346)the University of Science and Technology of China(USTC)Research Funds of the Double First-Class Initiative(No.YD2480002002)China Postdoctoral Science Foundation(No.2021TQ0323)。
文摘Noncovalent interfaces play a vital role in inelastic deformation and toughening mechanisms in layered nanocomposites due to their dynamical recoverability. When interfacial engineering is applied to design layered nanocomposites, shear-lag analysis is usually implemented to evaluate the capability of interfacial loading transfer. Here, we introduce a multiscale shear-lag model that correlates macroscale mechanical properties with the molecular mechanisms to quantify the effects of interfacial configuration in graphene oxide(GO) layered nanocomposites. By investigating the mechanical responses of commensurate and incommensurate interfaces, we identify that the commensurate interface exhibits a pronounced size effect due to the nucleation and propagation of interfacial defects, whereas the incommensurate interface displays uniform deformation. Our predictions are further validated through large-scale molecular dynamics simulations for GO layered nanocomposites. This work demonstrates how size effects and interfacial configurations can be exploited to fabricate layered nanocomposites with superior mechanical properties despite relying on weak noncovalent interfaces.
基金National Key R&D Program of China under Grant,Grant/Award Number:2021YFC1910601National Natural Science Foundation of China,Grant/Award Number:52104402HBIS Group Co.,Ltd Key R&D Program under Grant,Grant/Award Numbers:20210032,HG2022111。
文摘Due to their environmentally friendly nature and high energy density,direct ethanol fuel cells have attracted extensive research attention in recent decades.However,the actual Faraday efficiency of the ethanol oxidation reaction(EOR)is much lower than its theoretical value and the reaction kinetics of the EOR is sluggish due to insufficient active sites on the electrocatalyst surface.Pt/C is recognized as one of the most promising electrocatalysts for the EOR.Thus,the microscopic interfacial reaction mechanisms of the EOR on Pt/C were systematically studied in this work.In metal hydroxide solutions,hydrated alkali cations were found to bind with OH_(ad)through noncovalent interactions to form clusters and occupy the active sites on the Pt/C electrocatalyst surface,thus resulting in low Faraday efficiency and sluggish kinetics of the EOR.To reduce the negative effect of the noncovalent interactions on the EOR,a shield was made on the electrocatalyst surface using 4-trifluoromethylphenyl,resulting in twice the EOR catalytic reactivity of Pt/C.
文摘This study reveals that the noncovalent complexation betweenβ-CD and Cu（HMTA）^（2＋） makes a positive contribution to the coordination interaction between Cu^（2＋） and HMTA in a tricomponent system.Besides,mono- and binuclear complexes：[β-CDCu]~＋ and[Cu·β-CDCu]~＋ were observed under the condition of ESI-MS.
基金supported by the National Key Research and Development Program of China (2017YFA0206600)the National Natural Science Foundation of China (21875286)the Science Fund for Distinguished Young Scholars of Hunan Province (2017JJ1029)。
文摘The versatility and flexibility of organic photoelectric materials endow organic photovoltaic cells fine function modulation and huge commercial potential. In this work, a new noncovalent fused-ring small molecule acceptor(SMA) BID-4 F has been synthesized for high-efficient organic solar cells(OSCs). BID-4 F consists of a diflurobenzothiadiazole(DFBT) core, ladder-like indacenodithiophene(IDT) spacers, and dicyanoindanone electron-withdrawing end groups, which are supposed to be conformationally interlocked by noncovalent interactions, leading to good molecular planarity. In addition, compact solid state stacking was revealed by UV–vis–NIR absorption spectrum. The optimized PM6:BID-4 F based device delivers an eminent power conversion efficiency(PCE) of 12.30% with a high open-circuit voltage(Voc) of 0.92 V and a high fill factor(FF) of 74.3%. Most importantly, the PCE and FF are among one of the highest values reported for the OSCs based on the unfused-ring SMAs. Overall, our work demonstrates that the unfused ring central framework with high molecular planarity through noncovalent interactions provides a good strategy to construct highly efficient SMAs.
基金financially supported by the National Natural Science Foundation of China(No.U21A2077)the Natural Science Foundation of Shandong Province(Nos.ZR2022JQ08 and 2023HWYQ-028)+4 种基金the Taishan Scholar Project Foundation of Shandong Province(Nos.tsqn202211028 and tsqn202306080)the City University of Hong Kong(Nos.9020005,9610663,and 7020103)ITF-RTH-Global STEM Professorship(No.9446008)Hong Kong Branch of National Precious Metals Material Engineering Research Center—ITC FundGeneral Research Fund(No.9043720)from the Research Grants Council of Hong Kong SAR,China.
文摘Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide generation is limited by the competitive four-electron pathway.In this work,we report a noncovalent modulation strategy for the isolated CoN_(4) sites by metal-phthalocyanine molecules confinement,which boosts the two-electron oxygen reduction towards generating hydrogen peroxide.The confined Co-phthalocyanine molecules on CoN_(4) sites through π-π interactions induce the competitive*OOH adsorption between the two Co sites formed nanochannel.This noncovalent modulation contributes to the weakened*OOH binding on CoN_(4) sites and thus suppresses its further dissociation,achieving the maximum selectivity of 95% with high activity for H_(2)O_(2)production.This work shows that tailoring noncovalent interactions beyond the binding sites is a promising approach to modulate the local structure of isolated metal sites and related catalytic performance.
基金supported by the National Natural Science Foundation of China(82272145)and the Foundation of Westlake University.
文摘CONSPECTUS:Controlling self-assembled peptide nanostructures has emerged as a significant area of research,offering versatile tools for developing functional materials for various applications.This Account emphasizes the essential role of noncovalent interactions,particularly in peptide-based materials.Key forces,such as aromatic stacking and hydrogen bonding,are crucial for promoting molecular aggregation and stabilizing supramolecular structures.Numerous studies demonstrate how these interactions influence the phase transitions and the morphology of self-assembled structures.Recent advances in computational methodologies,including molecular dynamics simulations and machine learning,have significantly enhanced our understanding of self-assembly processes.These tools enable researchers to predict how molecular properties,such as hydrophobicity,charge distribution,and aromaticity,affect assembly behavior.Simulations uncover the energetic landscapes governing peptide aggregation,providing insights into the kinetic pathways and thermodynamic stabilities.Meanwhile,machine learning facilitates the rapid screening of peptide libraries,identifying sequences with optimal self-assembly characteristics,and accelerating material design with tailored functionalities.Beyond their structural and physicochemical properties,self-assembled peptide nanostructures hold immense potential in biological applications due to their versatility and biocompatibility.By manipulating molecular interactions,researchers have engineered responsive systems that interact with cellular environments to elicit specific biological responses.These peptide nanostructures can mimic extracellular matrices,facilitating cell adhesion,proliferation,and differentiation.They also show promise in modulating immune responses,recruiting immune cells,and regulating signaling pathways,making them valuable tools in immunotherapy and regenerative medicine.Moreover,their ability to disrupt bacterial membranes positions them as innovative alternatives to conventional antibiotics,addressing the urgent need for solutions to antimicrobial resistance.Despite its promise,peptide self-assembly faces several challenges.The assembly process is highly sensitive to environmental conditions,such as pH,temperature,and ionic strength,leading to variability in the morphology and properties.Furthermore,peptide aggregation can result in heterogeneous and poorly defined assemblies,complicating the reproducibility and scalability.Designing peptides with predictable self-assembly behavior remains a significant hurdle.Looking ahead,integrating computational predictions with experimental validations will be crucial in discovering novel peptide sequences with tailored self-assembly properties.Machine learning,combined with high-throughput screening techniques,will enable the rapid identification of optimal peptide sequences.In situ characterization tools,such as cryoelectron microscopy and advanced spectroscopy,will provide deeper insights into assembly mechanisms,aiding the rational design of peptide materials.As research progresses,the dynamic and reversible nature of noncovalent interactions can be leveraged to create adaptive responsive to environmental stimuli.Self-assembled peptide nanostructures are poised for impactful applications in biomedicine including targeted drug delivery,tissue repair,and advanced therapeutic strategies.Ultimately,these nanostructures represent a powerful platform for addressing complex challenges in biomedicine and beyond,paving the way for transformative breakthroughs in science and technology.
文摘The wide application of photoswitches requires control over their isomerization dynamics.Utilizing noncovalent interactions is a promising strategy as it offers active regulation in-situ.However,this control strategy has not yet been explored in-depth to reach its full potential.In this work,we demonstrate that by directing noncovalent interactions to the central rotating bond of indigo-based photoswitches,their thermal relaxation dynamics were altered in two opposite directions(either slowed down or sped up)allowing for modulating the relaxation half-lives across four orders of magnitude.More importantly,our work established two distinct and orthogonal working mechanisms of noncovalent control over isomerization:(1)Thermodynamic stabilization of photoisomers;and(2)Facilitating an alternative reaction pathway through Brønsted/Lewis acid catalysis.This two-directional modulation(resembling agonists and inverse agonists in biological systems)via two orthogonal working mechanisms will enable more delicate manipulation of photoswitches for advanced applications.
基金supported by the National Natural Science Foundation of China(NSFC)(52120105006,52450063,62322115,and U24A20226)Strategic Priority Research Program of Chinese Academy of Sciences(XDB 0520103)+3 种基金National Key R&D Program of China(2024YFB3614300)Project of International Cooperation of Chinese Academy of Sciences(124GJHZ2023079MI)China Postdoctoral Science Foundation funded project(BX20240002,2024M750051)University of Chinese Academy of Sciences。
文摘Intramolecular noncovalent conformational locks(NoCLs)have emerged as an important strategy for developing high-performance organic/polymeric semiconductors(OPSs)via suppressing the non-radiative decay.Despite extensive investigation into the impact of NoCLs on small molecules,elucidating their influence on the physicochemical properties of conjugated polymers(CPs)remains a critical challenge.By employing a combination of theoretical and experimental methods,it is revealed that the incorporation of NoCLs increases the rigidity of the polymer chain,enhances intermolecular interactions,promotes the formation of pre-aggregates of optimal length,and improves charge transport,providing valuable insights for designing high-performance CPs.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.51773142 and 51973146)the Jiangsu Provincial Natural Science Foundation(Grant No.BK20190099)+1 种基金the Collaborative Innovation Center of Suzhou Nano Science&Technologythe Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Main observation and conclusion Recently,the asymmetric nonfullerene acceptors(NFAs)with acceptor-donor-acceptor(A-D-A)structure have been developed rapidly,especially for the modification of asymmetric core,asymmetric side chains and asymmetric end groups.In this work,a novel asymmetric A-D-π-A type NFA with a noncovalently fused-ring core named PIST-4F is synthesized,containing an indacenodithieno[3,2-b]dithiophene(IDT),two strong electron-withdrawing end groups and an alkylthio-substituted thiopheneπ-bridge.Benefiting from the S···S noncovalent interaction between the sulfur atom onπ-bridge and the adjacent thiophene in IDT,the PIST-4F presents nearly planar geometry and extended conjugated area,resulting in the optimized electronic properties,charge transport,and film morphology compared to the symmetric NFA PI-4F.As a result,PM6:PIST-4F-based devices achieve a higher power conversion efficiency(PCE)of 13.8%,while the PM6:PI-4F-based devices only show a PCE of 7.1%.Notably,the PM6:PIST-4F-based devices processed with nonhalogen solvent toluene exhibit an excellent PCE as high as 13.1%.These results indicate that PIST-4F is an effective acceptor for high-efficiency organic solar cells.
基金supported by the National Natural Science Foundation of China (52103352, 52120105006, 21774130, 51925306)the National Key R&D Program of China (2018FYA 0305800)+1 种基金the Key Research Program of the Chinese Academy of Sciences (XDPB082)the Strategic Priority Research Program of Chinese Academy of Sciences (XDB28000000)。
文摘The polymerization of fused-ring acceptors(FRAs) to afford their corresponding polymeric acceptors for high-performance all-polymer solar cells(all-PSCs) has achieved remarkable progress in the past few years.However,due to the high degree of synthetic complexity for the monomer,the high-cost of these polymeric acceptors may limit their commercial applications.Thus,it is urgent to develop inexpensive and high-performance polymeric acceptors for all-PSCs.Herein,two novel polymeric acceptors(PBTzO and PBTzO-2F) have been designed and synthesized by copolymerization of noncovalently fused ring acceptors(NFRAs),which were employed in all-PSCs for the first time.Upon introducing the “noncovalently conformational locks(NoCLs)” in the backbone and selective fluorination of the end-group,photophysical and electrical properties,and solidstate packing properties of the NFRAs have been rationally tuned.As a result,the PBDB-T:PBTzO-2F based devices presented an excellent power conversion efficiency(PCE) of 11.04%,much higher than that of PBTzO based ones due to the increased charge generation and extraction,improved hole transfer and carrier mobilities,and reduced energy loss.More importantly,PBTzO-2F exhibited a much lower synthetic complexity(SC) index and higher figure-of-merit(FOM) values than the high-performance fused-ring acceptor based polymer acceptors(FRA-PAs) due to the simpler structures and more effective synthesis.This contribution provided a novel idea to achieve low-cost and high-performance all-PSCs.
基金supported by the National Natural Science Foundation of China (21774130, 21574135)Beijing Municipal Natural Science Foundation (2162043)+2 种基金the Key Research Program of Frontier Science, Chinese Academy of Sciences (QYZDB-SSW-JSC046)Key Research Program of the Chinese Academy of Sciences (XDPB08-2)One Hundred Talents Program of Chinese Academy of Sciences, and University of Chinese Academy of Sciences
文摘Highly planar conformation is considered to be one of the most important properties for high performance organic semiconductors. Among all kinds strategies for designing highly performing materials, noncovalent conformational locks （NCLs） have been widely used to increase the planarity and rigidity for x-conjugated systems. This review summarizes π-conjugated small molecules and polymers by employing various NCLs for controlling molecular conformation in the past two years. The optoelectronic properties of the conjugated materials, together with their applications on organic field-effect transistors （OFETs） and organic photovoltaics （OPVs） are discussed. Besides, the outlook and challenges in this field are also presented. It is obvious that NCLs play an important role in the design and synthesis of high-performance organic semiconductors.
基金the National Natural Science Foundation of China((52120105006,52103352,and 51925306)National Key R&D Program of China(2018FYA 0305800)+3 种基金Key Research Program of Chinese Academy of Sciences(XDPB08-2)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB28000000)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022165)the Fundamental Research Funds for the Central Universities.DFT results described in this report were obtained from the National Supercomputing Center in Shenzhen(Shenzhen CloudComputing Center).
文摘Comprehensive Summary By employing thiazole and 4-chlorothiazole as the A′units,two A-D-A′-D-A type nonfused-ring electron acceptors(NFREAs)Tz-H and Tz-Cl were designed and synthesized.Replacing thiazole in Tz-H with 4-chlorothiazole can not only remarkably shorten the synthetic route through C—H direct arylation but also enhance molecular planarity with the simultaneous incorporation of S…N and S…Cl noncovalently conformational locks(NoCLs).The photovoltaic devices based on PM6:Tz-Cl exhibited a power conversion efficiency as high as 11.10%,much higher than that of PM6:Tz-H(6.41%),mainly due to more efficient exciton dissociation,better and more balanced carrier mobility,less charge recombination,and more favorable morphology.These findings demonstrate the great potential of NoCLs in achieving low-cost and high-performance NFREAs.
基金Natural Science Foundation for Distinguished Young Scholars of Guangdong Province,Grant/Award Number:2021B1515020027Science and Technology Projects in Guangzhou,Grant/Award Number:202201000002+4 种基金Shenzhen Science and Technology Innovation Commission,Grant/Award Numbers:JCYJ202103243104813035,JCYJ20180504165709042GuangDong Basic and Applied Basic Research Foundation,Grant/Award Number:2021A1515110892China Postdoctoral Science Foundation,Grant/Award Number:2021M700062Open Fund of the State Key Laboratory of Luminescent Materials and Devices,Grant/Award Number:2022-skllmd-17X.G.,H.S.,and Y.J.are thankful for the financial support from the Songshan Lake Materials Laboratory,Grant/Award Number:2021SLABFK03。
文摘The power conversion efficiencies(PCEs)of organic solar cells(OSCs)have improved considerably in recent years with the development of fused-ring electron acceptors(FREAs).Currently,FREAs-based OSCs have achieved high PCEs of over 19%in single-junction OSCs.Whereas the relatively high synthetic complexity and the low yield of FREAs typically result in high production costs,hindering the commercial application of OSCs.In contrast,noncovalently fused-ring electron acceptors(NFREAs)can compensate for the shortcomings of FREAs and facilitate large-scale industrial production by virtue of the simple structure,facile synthesis,high yield,low cost,and reasonable efficiency.At present,OSCs based on NFREAs have exceeded the PCEs of 15%and are expected to reach comparable efficiency as FREAs-based OSCs.Here,recent advances in NFREAs in this review provide insight into improving the performance of OSCs.In particular,this paper focuses on the effect of the chemical structures of NFREAs on the molecule conformation,aggregation,and packing mode.Various molecular design strategies,such as core,side-chain,and terminal group engineering,are presented.In addition,some novel polymer acceptors based on NFREAs for all-polymer OSCs are also introduced.In the end,the paper provides an outlook on developing efficient,stable,and low-cost NFREAs for achieving commercial applications.
基金National Key Research and Development Program of China,Grant/Award Number:2018YFC1105401National Natural Science Foundation of China,Grant/Award Number:21935004。
文摘Mechanical performances are among the most fundamental properties that dictate the applicability and durability of polymeric materials.Reinforcement of polymeric materials is eternally pursued to broaden the applications of polymers with light-weight,low-cost and easy-processing advantages.Noncovalent aggregates of biomacromolecules have been found to play a significant role in the mechanical properties of many natural materials,such as the spider silk.Increasing numbers of reports have demonstrated that the in situ formed noncovalent aggregates of polymer chains in polymeric systems are highly effective for enhancing the mechanical properties of artificial polymeric materials,in terms of strength,stiffness,toughness,and/or elasticity.The in situ formed noncovalent aggregates act as additional crosslinking domains and well-dispersed“hard”nanofillers in the polymer networks,significantly strengthening,stiffening and/or toughening the polymeric materials.Moreover,the noncovalent crosslinking of polymer chains favors the development of healable and recyclable polymeric materials,thanks to the reversible and dynamic properties of noncovalent bonds.This review provides an overview of the recent advances on the enhancement of the mechanical properties of different polymeric materials by the in situ formed noncovalent aggregates of polymer chains.It is expected to arouse inspirations for the development of novel polymeric materials with extraordinary mechanical performances and functionalities.
基金the Chinese Academy of Sciences (KZCX2-YW-BR-25, XDB14030500, YSW2013B01)the National High Technology Research and Development Program of China (2013AA065201)
文摘Short chain chlorinated paraffins （SCCPs） are not only research focus of environmental issues but also interesting model mol- ecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions （NCIs）. A systematic study was conducted to reveal the conlk）rmation preference and the related intramolecular NCIs in two C^-isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-1etrachlorodecane. The overall conformation profile was deter- mined on the basis of relative energies calculated at the MP2/6-311＋＋G（d,p） level with the geometries optimized by B3LYP/6-31 l＋＋G（d,p） method. Then, quantum theory of atoms in molecules （QTAIM） has been adopted to identify the NCls in the selected conformers of the model molecules at both B31~YP/6-31 l＋＋G（d,p） and M06-2X/aug-cc-pvdz level. Different chlorine substitution modes result in varied conformation preference. No obvious gauche effect can be observed tk）r the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane （tTt） has its three dihedral angles in the T configuration, and there is no intramolecular N（3s found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configmation for the H C C CI axis. Not only inlramolecular H-..CI contacts but also H---H interactions have been identified as driving forces to compensate the instability from steric crowding ot the gauche configuration. The gggg and g＇g＇g＇g＇ conformers are the most popular ones, while the populations of tggg and tg＇g＇g＇ conformer are second to those of the gggg and g＇g＇g＇g＇ conformers. Meanwhile, the M06-2X method with large basis sets is preferred for identification of subtle intramolecular NCIs in large molecules like SCCPs.
基金theNaturalScienceFoundationofZhejiangProvince (No .2 980 6 8)
文摘Two palladium(II) complexes, \[Pd(bipy)(BzPhe N,O)\] and \[Pd(phen)(BzPhe N,O)\]·4H 2 O were synthesized by reactions between Pd(bipy)Cl 2 and BzPheH 2( N benzoyl β phenylalanine), Pd(phen)Cl 2 and BzPheH 2 in water at pH～9, with their structures determined by X ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe= N benzoyl β phenylalaninate dianion). In the complex \[Pd(phen)(BzPhe N,O)\]·4H 2O, the side chain of phenylalanine is located above and approximately parallels to the coordination plane. Both the aromatic aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion aromatic interaction between the phenyl ring of phenylalanine and Pd(II) were observed. \[Pd(bipy)(BzPhe N,O)\] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested.
基金financially supported by the National Science Fund for Distinguished Young Scholars of China(grant no.22025207)the National Natural Science Foundation of China(grant nos.22172172,22372174,and 22232006)+1 种基金the Youth Innovation Promotion Association of Chinese Academy of Sciences(grant no.2022049)the Institute of Process Engineering Project for Frontier Basic Research(grant no.QYJC-2022-011).
文摘Glass materials play a vital role in scientific research and engineering applications.Biomolecular noncovalent glasses(BNG),based on amino acids and peptides,have been proposed as the next-generation glass materials to meet the demand of a sustainability and circular economy.However,bulk BNG with remarkable mechanics and tunable photoluminescence are still rare due to the nature of weak noncovalent interactions and oversimplified molecular structures.Herein,we report the design and creation of metal ion-coordinated BNG(MIBNG)based on a simple amino acid derivative and metal ions.The obtained MIBNG exhibit ceramic-like mechanics,including the hardness,elasticity,and wear resistance,that are unattainable by the pure BNG counterpart.Such remarkable mechanics can be attributed to the enhanced noncovalent crosslinking network connectivity of biomolecules within MIBNG resulting from the incorporation of strong metal coordination interaction with hydrogen bonding and aromatic interactions.Moreover,fluorescence emission of MIBNG can be tuned feasibly through precisely modulating the types of metal ions coordinated.This study sheds light on the crucial role of multiple noncovalent interactions in the construction of BNG and advances the exploration and potential applications of BNG-based functional materials with tunable mechanical and optical properties in such fields as electronics and optics.
基金financially supported by the National Natural Science Foundation of China(grant numbers 22205040,U2001222,and 52273168)the Basic and Applied Basic Research Foundation of Guangdong Province(grant number 2021A1515110417)J.Zhang acknowledges the support from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie actions grant(101105790)。
文摘The unfavorable photochemical processes at the molecular level have become a bar-rier limiting the use of aromatic amides as high-performance luminescent materials.Herein,we propose a reliable strategy for manipulating noncovalent conformational lock(NCL)via side-chain engineering to burst out eye-catching luminescence at the aggregate level.Contrary to the invisible emission in dilute solutions,dyad OO with a three-centered H-bond gave the wondrous crystallization-induced emis-sion with a quantum yield of 66.8%and clusterization-triggered emission,which were much brighter than those of isomers.Theoretical calculations demonstrate that crystallization-induced planarized intramolecular charge transfer(PICT),con-formation rigidification,and through-space conjugation(TSC)are responsible for aggregate-state luminescence.Robust NCL composed of intramolecular N-H⋅⋅⋅Ointeractions could boost molecular rigidity and planarity,thus greatly facilitating PICT and TSC.This study would inspire researchers to design efficient luminescent materials at the aggregate level via rational conformational control.
