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
Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have be...Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have been developed with A-π_A-π_D-D-π_D-π_A-A non-fused structures. It is revealed that the introduction of electron deficient π-bridge(π_A) and multiple intramolecular noncovalent interactions effectively retained the structural planarity and intramolecular charge transfer of NFRAs, extending strong NIR photon absorption up to 950 nm. Further, the chlorinated acceptor, with the enlarged π-surface compared to the fluorinated counterpart, promoted not only molecular stacking in solid, but also the desirable photochemical stability in ambient, which are helpful to thereby improve the exciton and charge dynamics for the corresponding OPVs. Overall, this work provides valuable insights into the design of NIR organic semiconductors.展开更多
Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT gen...Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT generally exhibits low charge mobility mostly due to poor solution processability attributed to dense arrangement of hexylthio side chain in polymer, which led to strong noncovalent interactions among sulfur atoms. To balance the nonvalent interaction and aggregation for P3HTT, herein, we systematically study the effect of hexylthio side chain content in polymer backbone on the structure and properties. A series of regioregular P3HTT-based homopolymers(P3HTT, P3HTT-50,P3HTT-33 and P3HTT-25) were prepared via Kumada catalyst transfer polycondensation method from a set of mono-, bi-, ter-and quarterthiophenes containing different contents of hexylthio side chain. The DFT calculation shows the planarity of polymers backbone could be improved through reducing the density of hexylthio side chain in polymer mainchain. And significant changes in their crystallinity, aggregation and optical properties were observed with the content of hexylthio side chain reducing. The P3HTT-33 displayed the highest field-effect transistor hole mobility of 2.83×10^(-2) cm^(2)·V^(-1)·s^(-1) resulting from a balance between the crystallinity and planarity. This study demonstrates modulating the content of hexylthio side chain in P3HTT is an effective strategy to optimize the opto-electronic properties of polymer obtaining excellent semiconductor device performance.展开更多
Organic low-dimensional crystals have garnered escalating interests in the realms of miniaturized optoelectronics and integrated photonics.The continual expansion of molecular systems and improvement in experimental c...Organic low-dimensional crystals have garnered escalating interests in the realms of miniaturized optoelectronics and integrated photonics.The continual expansion of molecular systems and improvement in experimental conditions have given rise to unconventional organic low-dimensional crystals,which showcase a variety of appealing structure-dependent properties in the realm of organic semiconductors,owing to their adaptable physicochemical characteristics and exceptional optoelectronics performance.Simultaneously,the development of unconventional low-dimensional crystals is filled with abundant possibilities due to their diverse application prospects.Herein,we present a comprehensive overview of advancements in research on representative cases of unconventional low-dimensional organic crystals,using a systematic and rational structural classification.Finally,we have also discussed the existing challenges and future directions,aspiring to deepen understanding and encourage further research exploration in this field.展开更多
Developing fluorescent sensors for small-molecule phosphates offers opportunities in optically detecting biorelevant reactions and events.However,it remains elusive how to identify phosphates from other anions,such as...Developing fluorescent sensors for small-molecule phosphates offers opportunities in optically detecting biorelevant reactions and events.However,it remains elusive how to identify phosphates from other anions,such as carboxylates and sulfates,because current synthetic phosphate receptors lack selectivity.Here we report the construction of a multicolor fluorescent sensor that can identify phosphates from other analogous anions.The key design principle is to take advantage of the highly sensitive conformation-dependent emissive wavelength of diphenyl-9,14-dihydrodibenzo[a,c]phenazine fluorophores to sense the minor structural differences between phosphates and other anions,for example,sulfates and carboxylates.The effect of structural factors such as spacer length and urea versus thiourea has been investigated by comparing the optical properties and binding affinities with the phosphate receptors.This strategy provides a simple and robust fluorescent sensing solution to optically analyze small-molecule phosphates with antiinterference performance.展开更多
Synthetic molecules that form functional noncovalent assemblies in water have received much attention for their potential applications as biomaterials.In this work,we introduce a novel water-compatible monomer based o...Synthetic molecules that form functional noncovalent assemblies in water have received much attention for their potential applications as biomaterials.In this work,we introduce a novel water-compatible monomer based on the phthalhydrazide moiety that assembles into hydrogen-bonded trimeric discs.In bulk,the material exhibits a cylindrical nanostructure in the liquid-crystalline phase at elevated temperatures,morphologically distinct from the crystalline lamellar phase.In water,these molecules effectively form cylinders in a one-dimensional fashion,yielding fibrous structures.The formation of these supramolecular polymers follows a cooperative mechanism,as evidenced by denaturation studies.The trimerized pattern represents a new category of aqueous su pramolecular polymers with future prospects for functional complex molecular systems.展开更多
Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen...Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.展开更多
Two novel acid-base adducts,[H2L1^2＋]（Hpbda）2（1,L1 = 1,4-di（lH-imidazol-4-yl）benzene,H2pbda = 1,4-benzenedicarboxylic acid） and[H2L2^2＋]（NO3）2（2,L2 = l,4-di（l-carboxymethyl-imidazol-4-yl）benzene）,have be...Two novel acid-base adducts,[H2L1^2＋]（Hpbda）2（1,L1 = 1,4-di（lH-imidazol-4-yl）benzene,H2pbda = 1,4-benzenedicarboxylic acid） and[H2L2^2＋]（NO3）2（2,L2 = l,4-di（l-carboxymethyl-imidazol-4-yl）benzene）,have been prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy and elemental analysis.Compound 1 crystallizes in monoclinic,space group P21/n with a = 5.3525（11）,b = 9.1471（19）,c = 19.314（4） ？,β = 92.342（3）°,V= 944.8（3） A°3,Z = 2,C16H16N6O（10）,Mr = 452.35,Dc = 1.590 g/cm^3,μ = 0.135 mm^-1,S = 1.058,F（000） = 468,the final R = 0.0661 and wR = 0.1887 for 2298 observed reflections（I〉 2σ（I））.Compound 2 crystallizes in monoclinic,space group P21/c with a = 9.6923（10）,b = 17.2950（17）,c = 7.1880（7） ？,β =94.801（2）°,V= 1200.7（2）A°3,Z = 2,C（28）H（22）N4O8,Mr = 542.50,Dc = 1.501 g/cm^3,μ = 0.112 mm^-1,S= 1.060,F（000） = 564,the final R = 0.0394 and wR = 0.1017 for 2768 observed reflections（I 〉2σ（I））.In the title compounds,both of L1 and L2 ligands act as weak base to accept protons to exhibit diprotonated H2L1^2＋ and H2L2^2＋ form,which can effectively employ as hydrogen bonding donors to combine anion moieties to form binary adducts respectively.In the crystal packing diagram of two polymers,there exist extensive noncovalent interactions including charge-transfer interactions,C（N）-H…π and N-H…O,C-H…O,O-H…O hydrogen bonding interactions between co-crystal moieties which consolidate the structures of supramolecular polymers,thus generating three-dimensional（3D） frameworks.展开更多
Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement come...Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement comes from fused ring electron acceptors(FREAs)with complex structures,leading to high cost.Hence,it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells.Recently,great progress has been made in fully non-fused ring electron acceptors(NFREAs)with only single-aromatic ring in the electron-donating core,which might achieve a fine balance between the efficiency and cost,thus accelerating the commercial application of organic solar cells.Therefore,this article summarizes the recent advances of fully NFREAs with efficiency over 10%,which may provide a guidance for developing the cost-effective solar cells.展开更多
Comprehensive Summary,The development of novel building blocks with sp3-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors(NFAs),but this remains a challenge ...Comprehensive Summary,The development of novel building blocks with sp3-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors(NFAs),but this remains a challenge due to the lack of strategies to effectively modulate the aggregation behavior of resulting NFAs.Herein,two novel nitrogen-bridged octacyclic ladder-type heteroarenes end-capped with thiophene rings(BTPS)or selenophene rings(BTPSe)are designed and synthesized as the donor cores for constructing NFAs(MQX-2 and MQX-4).It is found that replacing the sulfur atoms(MQX-2)at the outer positions of the heteroarene core with selenium atoms(MQX-4)can effectively modulate the molecular packing mode of the NFAs.The incorporation of selenium atoms induces stronger O···Se noncovalent interaction than O···S,thus promoting the formation of mixed H/J-type aggregates in MQX-4.Benefiting from more electron hopping channels,MQX-4 exhibits higher electron transport(more than 1-fold enhancement)and photovoltaic properties compared to MQX-2,which forms only H-type aggregates.展开更多
TBAJ-876, developed by TB Alliance, a novel anti-tuberculosis-specific drug, has entered Phase II clinical trials. Herein, the first asymmetric synthesis of TBAJ-876 has been realized using synergistic Li/Li catalysis...TBAJ-876, developed by TB Alliance, a novel anti-tuberculosis-specific drug, has entered Phase II clinical trials. Herein, the first asymmetric synthesis of TBAJ-876 has been realized using synergistic Li/Li catalysis with excellent yield of 95% and 88 : 12 er (99.6 : 0.4 er, 10 : 1 dr after simple recrystallization). Furthermore, DFT calculations and 7Li-NMR analysis illustrated the mechanism of the synergistic reaction: a chiral Li-complex activates the nucleophile to control the stereoselectivity, while the other achiral Li-complex activates the electrophile to catalyze the carbonyl addition reaction. Additionally, this protocol has been successfully carried out at 5 gram-scale, showing its industrial potential.展开更多
The precise control of multicomponent complex topological configurations integrating more than one compound or one crystal phase with high spatial and angular precision is extremely challenging due to anisotropic nonc...The precise control of multicomponent complex topological configurations integrating more than one compound or one crystal phase with high spatial and angular precision is extremely challenging due to anisotropic noncovalent interaction and undesirable phase separation.Herein,we present a superstacking self-assembly approach via noncovalent interaction strength(|EBGP-TCNB(−3.14 kcal mol−1)|>|EBGP-TFP(−2.84 kcal mol−1)|>|EBGP-OFN(−2.15 kcal mol−1)|>|EBGP(−1.33 kcal mol−1)|)adjustment for the fine synthesis of molecular heterostructures with various photophysical properties and lowdimensional morphologies,as well as phase heterostructures with multifunctional optoelectrical characteristics and multidimensional morphologies.Notably,the anisotropic noncovalent interaction and lattice matching principle facilitate the sequential crystallization and horizontal/longitudinal growth in the crystal-puzzle process,respectively.This super-stacking self-assembly approach is amenable to precise design and fine synthesis of desirable organic multicomponent complex topological configurations for integrated optoelectronics.展开更多
In this article,morpholine,a non-conjugated heterocycle,is embedded intoπsystem to construct single-component organic room temperature phosphorescence(RTP)luminogens.The effect of morpholine on intermolecular interac...In this article,morpholine,a non-conjugated heterocycle,is embedded intoπsystem to construct single-component organic room temperature phosphorescence(RTP)luminogens.The effect of morpholine on intermolecular interaction,crystal packing modes,and RTP performance is investigated systematically.The experimental and theoretical calculation results illustrate the versatility of morpholine in promoting the n-π*transition and intensifying the intermolecular interactions,which not only enhances the generation of triplet excitons,but also suppresses the nonradiative decay of triplet excitons.Impressively,TMPh containing three morpholine units shows an ultralong lifetime of 1.03 s and a visible afterglow up to 10 s.The unique dual delayed emission and long afterglow property allow potential application of morpholine derivatives in data encryption,and the time-dependent color change of afterglow emission is realized after removing the excitation source,providing a high-level data security.This article provides a new perspective for the design of purely organic RTP system without utilization of metal,or even any heavy atoms.展开更多
Organic luminescent materials play an integral role in the optoelectronic applications of displays and solid-state lighting.Nevertheless, high-performance organic luminescent materials require the efficient combinatio...Organic luminescent materials play an integral role in the optoelectronic applications of displays and solid-state lighting.Nevertheless, high-performance organic luminescent materials require the efficient combination of two or more kinds of materials, which is extremely difficult owing to the completely different self-assembly behaviors of multicomponent molecules.Herein, based on a broad scale from the molecular, micro-/nano-scale, and macroscopic levels, we successfully demonstrate the multiscale construction of organic luminescent microwires of cocrystals, solid solutions, and core-shell microstructures. Through the wide selection of electron donor/acceptor pairs, a series of color-tunable charge-transfer(CT) cocrystals are formed via the intermolecular cooperative self-assembly process. On this basis, the high structural compatibility and perfect lattice mismatching(~1.1%) of cocrystals are critical factors that facilitate the combination of dissimilar materials to form solid solutions and core/shell microwires. Significantly, because of the full-spectrum light transport from 400 to 800 nm, the nano-micro-scaled solid solution microwires act as microscale white-light sources [CIE(0.32, 0.36)]. Meanwhile, the macroscopic-scale core/shell organic-microwires demonstrate tunable white-light emission with a high color-rendering index(CRI) of 83, whose CIE coordinates span from(0.37, 0.39) to(0.40, 0.31). Therefore, our work provides a feasible approach to the multiscale synthesis of novel luminescent organic semiconductor materials, which could lay a solid foundation for organic optoelectronics.展开更多
Cytochrome P450（CYP） 2El is a dual function monoxygenase with a crucial role in the metabolism of 6% of drugs on the market at present. The enzyme is of tremendous interest for its association with alcohol consumpti...Cytochrome P450（CYP） 2El is a dual function monoxygenase with a crucial role in the metabolism of 6% of drugs on the market at present. The enzyme is of tremendous interest for its association with alcohol consumption, diabetes, obesity and fasting. Despite the abundant experimental mutagenesis data, the molecular origin and the structural motifs for the enzymatic activity deficiencies have not been rationalized at the atomic level. In this regard, we have investigated the effects of mutation on the structural and energetic characteristics upon single point mutations in CYP2E1, N219D and $366C. The molecular dynamics（MD） simulation combined with quantum mechanics/molecular mechanics（QM/MM） and noncovalent interaction（NCI） analysis was carried out on CYP2EI and its two mutants. The results highlight the critical role of Phe207, which is responsible for both structural flexibility and energetic variation, shortening the gap between the theory and the experimentally observed results of enzymatic activity decrease, The underlying molecular mechanism of the enzymatic activity deficiencies for mutants may be attributed to the changes of spatial position of Phe207 in the two mutants. This work provides particular explanations to how mutations affect ligand-receptor interactions based on combined MD and QM/MM calculations. Furthermore, the mutational effects on the activity of CYP2E1 obtained in the present study are beneficial to both the experimental and the computational works of CYPs and may allow researchers to achieve desirable changes in enzymatic activity.展开更多
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funded by National Natural Science Foundation of China (No.22125901)the National Key Research and Development Program of China (No.2019YFA0705900)the Fundamental Research Funds for the Central Universities (No.226–2023–00113)。
文摘Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have been developed with A-π_A-π_D-D-π_D-π_A-A non-fused structures. It is revealed that the introduction of electron deficient π-bridge(π_A) and multiple intramolecular noncovalent interactions effectively retained the structural planarity and intramolecular charge transfer of NFRAs, extending strong NIR photon absorption up to 950 nm. Further, the chlorinated acceptor, with the enlarged π-surface compared to the fluorinated counterpart, promoted not only molecular stacking in solid, but also the desirable photochemical stability in ambient, which are helpful to thereby improve the exciton and charge dynamics for the corresponding OPVs. Overall, this work provides valuable insights into the design of NIR organic semiconductors.
基金financially supported by the Science and Technology Commission of Shanghai Municipality (No.20JC1414900)the National Natural Science Foundation of China (No.52203005)the Science and Technology Commission of Shanghai Municipality (No.21ZR1401400)。
文摘Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT generally exhibits low charge mobility mostly due to poor solution processability attributed to dense arrangement of hexylthio side chain in polymer, which led to strong noncovalent interactions among sulfur atoms. To balance the nonvalent interaction and aggregation for P3HTT, herein, we systematically study the effect of hexylthio side chain content in polymer backbone on the structure and properties. A series of regioregular P3HTT-based homopolymers(P3HTT, P3HTT-50,P3HTT-33 and P3HTT-25) were prepared via Kumada catalyst transfer polycondensation method from a set of mono-, bi-, ter-and quarterthiophenes containing different contents of hexylthio side chain. The DFT calculation shows the planarity of polymers backbone could be improved through reducing the density of hexylthio side chain in polymer mainchain. And significant changes in their crystallinity, aggregation and optical properties were observed with the content of hexylthio side chain reducing. The P3HTT-33 displayed the highest field-effect transistor hole mobility of 2.83×10^(-2) cm^(2)·V^(-1)·s^(-1) resulting from a balance between the crystallinity and planarity. This study demonstrates modulating the content of hexylthio side chain in P3HTT is an effective strategy to optimize the opto-electronic properties of polymer obtaining excellent semiconductor device performance.
基金financial support from the National Natural Science Foundation of China (grant nos.52173177,21703148,and 21971185)the Natural Science Foundation of Jiangsu Province (grant no.BK20230010)+1 种基金the Natural Science Foundation of Shandong Province (grant no.ZR2020MB054)the Collaborative Innovation Center of Suzhou Nano Science&Technology.
文摘Organic low-dimensional crystals have garnered escalating interests in the realms of miniaturized optoelectronics and integrated photonics.The continual expansion of molecular systems and improvement in experimental conditions have given rise to unconventional organic low-dimensional crystals,which showcase a variety of appealing structure-dependent properties in the realm of organic semiconductors,owing to their adaptable physicochemical characteristics and exceptional optoelectronics performance.Simultaneously,the development of unconventional low-dimensional crystals is filled with abundant possibilities due to their diverse application prospects.Herein,we present a comprehensive overview of advancements in research on representative cases of unconventional low-dimensional organic crystals,using a systematic and rational structural classification.Finally,we have also discussed the existing challenges and future directions,aspiring to deepen understanding and encourage further research exploration in this field.
基金financially supported by the National Natural Science Foundation of China(22173008)Beijing Key Laboratory for Chemical Power Source and Green Catalysis(2013CX02031)。
基金supported by the National Natural Science Foundation of China(grant nos.22220102004 and 22025503)Shanghai Municipal Science and Technology Major Project(grant no.2018SHZDZX03)+3 种基金the Innovation Program of Shanghai Municipal Education Commission(grant no.2023ZKZD40)the Fundamental Research Funds for the Central Universities,the Programme of Introducing Talents of Discipline to Universities(grant no.B16017)Science and Technology Commission of Shanghai Municipality(grant no.21JC1401700)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(grant no.SN-ZJUSIAS-006).
文摘Developing fluorescent sensors for small-molecule phosphates offers opportunities in optically detecting biorelevant reactions and events.However,it remains elusive how to identify phosphates from other anions,such as carboxylates and sulfates,because current synthetic phosphate receptors lack selectivity.Here we report the construction of a multicolor fluorescent sensor that can identify phosphates from other analogous anions.The key design principle is to take advantage of the highly sensitive conformation-dependent emissive wavelength of diphenyl-9,14-dihydrodibenzo[a,c]phenazine fluorophores to sense the minor structural differences between phosphates and other anions,for example,sulfates and carboxylates.The effect of structural factors such as spacer length and urea versus thiourea has been investigated by comparing the optical properties and binding affinities with the phosphate receptors.This strategy provides a simple and robust fluorescent sensing solution to optically analyze small-molecule phosphates with antiinterference performance.
基金funding from the European Research Council(H2020-EU.1.1.,SYNMAT project,ID 788618)the Dutch Ministry of Education,Culture and Science(Gravitation Program 024.001.035).
文摘Synthetic molecules that form functional noncovalent assemblies in water have received much attention for their potential applications as biomaterials.In this work,we introduce a novel water-compatible monomer based on the phthalhydrazide moiety that assembles into hydrogen-bonded trimeric discs.In bulk,the material exhibits a cylindrical nanostructure in the liquid-crystalline phase at elevated temperatures,morphologically distinct from the crystalline lamellar phase.In water,these molecules effectively form cylinders in a one-dimensional fashion,yielding fibrous structures.The formation of these supramolecular polymers follows a cooperative mechanism,as evidenced by denaturation studies.The trimerized pattern represents a new category of aqueous su pramolecular polymers with future prospects for functional complex molecular systems.
基金Supported by the National Natural Science Foundation of China (Grant No. 20572117)the Shanghai Postdoctoral Scientific Program (Grant No. Y200-2-08)
文摘Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.
基金supported by the National Natural Science Foundation of China(No.21171040 and 21302019)the disguished organic project(2013JCJS01)
文摘Two novel acid-base adducts,[H2L1^2＋]（Hpbda）2（1,L1 = 1,4-di（lH-imidazol-4-yl）benzene,H2pbda = 1,4-benzenedicarboxylic acid） and[H2L2^2＋]（NO3）2（2,L2 = l,4-di（l-carboxymethyl-imidazol-4-yl）benzene）,have been prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy and elemental analysis.Compound 1 crystallizes in monoclinic,space group P21/n with a = 5.3525（11）,b = 9.1471（19）,c = 19.314（4） ？,β = 92.342（3）°,V= 944.8（3） A°3,Z = 2,C16H16N6O（10）,Mr = 452.35,Dc = 1.590 g/cm^3,μ = 0.135 mm^-1,S = 1.058,F（000） = 468,the final R = 0.0661 and wR = 0.1887 for 2298 observed reflections（I〉 2σ（I））.Compound 2 crystallizes in monoclinic,space group P21/c with a = 9.6923（10）,b = 17.2950（17）,c = 7.1880（7） ？,β =94.801（2）°,V= 1200.7（2）A°3,Z = 2,C（28）H（22）N4O8,Mr = 542.50,Dc = 1.501 g/cm^3,μ = 0.112 mm^-1,S= 1.060,F（000） = 564,the final R = 0.0394 and wR = 0.1017 for 2768 observed reflections（I 〉2σ（I））.In the title compounds,both of L1 and L2 ligands act as weak base to accept protons to exhibit diprotonated H2L1^2＋ and H2L2^2＋ form,which can effectively employ as hydrogen bonding donors to combine anion moieties to form binary adducts respectively.In the crystal packing diagram of two polymers,there exist extensive noncovalent interactions including charge-transfer interactions,C（N）-H…π and N-H…O,C-H…O,O-H…O hydrogen bonding interactions between co-crystal moieties which consolidate the structures of supramolecular polymers,thus generating three-dimensional（3D） frameworks.
基金The authors gratefully acknowledge the financial support from National Natural Science Foundation of China(NSFC,Nos.51973169 and 52003209)the Open Project Program of Wuhan National Laboratory for Optoelectronics(No.2020WNLOKF015)the Science Foundation of Wuhan Institute of Technology(Nos.K202023 and K202025).
文摘Benefitting from the development of non-fullerene acceptors(NFAs),remarkable advances have been achieved with the power conversion efficiency(PCE)exceeding 19%over the last few years.However,the major achievement comes from fused ring electron acceptors(FREAs)with complex structures,leading to high cost.Hence,it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells.Recently,great progress has been made in fully non-fused ring electron acceptors(NFREAs)with only single-aromatic ring in the electron-donating core,which might achieve a fine balance between the efficiency and cost,thus accelerating the commercial application of organic solar cells.Therefore,this article summarizes the recent advances of fully NFREAs with efficiency over 10%,which may provide a guidance for developing the cost-effective solar cells.
基金supported by the National Natural Science Foundation of China(Nos.52130306,22075287)the Program of Youth Innovation Promotion Association CAs(No.2021299).
文摘Comprehensive Summary,The development of novel building blocks with sp3-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors(NFAs),but this remains a challenge due to the lack of strategies to effectively modulate the aggregation behavior of resulting NFAs.Herein,two novel nitrogen-bridged octacyclic ladder-type heteroarenes end-capped with thiophene rings(BTPS)or selenophene rings(BTPSe)are designed and synthesized as the donor cores for constructing NFAs(MQX-2 and MQX-4).It is found that replacing the sulfur atoms(MQX-2)at the outer positions of the heteroarene core with selenium atoms(MQX-4)can effectively modulate the molecular packing mode of the NFAs.The incorporation of selenium atoms induces stronger O···Se noncovalent interaction than O···S,thus promoting the formation of mixed H/J-type aggregates in MQX-4.Benefiting from more electron hopping channels,MQX-4 exhibits higher electron transport(more than 1-fold enhancement)and photovoltaic properties compared to MQX-2,which forms only H-type aggregates.
基金funding support of this work by the Bill and Melinda Gates Foundation(No.INV-008413)the National Natural Science Foundation of China(No.21831005)and Shanghai Jiao Tong University.
文摘TBAJ-876, developed by TB Alliance, a novel anti-tuberculosis-specific drug, has entered Phase II clinical trials. Herein, the first asymmetric synthesis of TBAJ-876 has been realized using synergistic Li/Li catalysis with excellent yield of 95% and 88 : 12 er (99.6 : 0.4 er, 10 : 1 dr after simple recrystallization). Furthermore, DFT calculations and 7Li-NMR analysis illustrated the mechanism of the synergistic reaction: a chiral Li-complex activates the nucleophile to control the stereoselectivity, while the other achiral Li-complex activates the electrophile to catalyze the carbonyl addition reaction. Additionally, this protocol has been successfully carried out at 5 gram-scale, showing its industrial potential.
基金support from the National Natural Science Foundation of China(nos.21703148 and 21971185)the Natural Science Foundation of Jiangsu Province(BK20170330)+3 种基金the National Postdoctoral Program for Innovative Talents(no.BX20190228)this project is also funded by the Collaborative Innovation Center of Suzhou Nano Science and Technology(CIC-Nano)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)by the“111”Project of The State Administration of Foreign Experts Affairs of China.
文摘The precise control of multicomponent complex topological configurations integrating more than one compound or one crystal phase with high spatial and angular precision is extremely challenging due to anisotropic noncovalent interaction and undesirable phase separation.Herein,we present a superstacking self-assembly approach via noncovalent interaction strength(|EBGP-TCNB(−3.14 kcal mol−1)|>|EBGP-TFP(−2.84 kcal mol−1)|>|EBGP-OFN(−2.15 kcal mol−1)|>|EBGP(−1.33 kcal mol−1)|)adjustment for the fine synthesis of molecular heterostructures with various photophysical properties and lowdimensional morphologies,as well as phase heterostructures with multifunctional optoelectrical characteristics and multidimensional morphologies.Notably,the anisotropic noncovalent interaction and lattice matching principle facilitate the sequential crystallization and horizontal/longitudinal growth in the crystal-puzzle process,respectively.This super-stacking self-assembly approach is amenable to precise design and fine synthesis of desirable organic multicomponent complex topological configurations for integrated optoelectronics.
基金supported by the National Natural Science Foundation of China(22075100)the Jilin Provincial Science and Technology Department(20220201082GX)the Open Fund of the State Key Laboratory of Luminescent Materials and Devices(South China University of Technology,2021-skllmd)。
文摘In this article,morpholine,a non-conjugated heterocycle,is embedded intoπsystem to construct single-component organic room temperature phosphorescence(RTP)luminogens.The effect of morpholine on intermolecular interaction,crystal packing modes,and RTP performance is investigated systematically.The experimental and theoretical calculation results illustrate the versatility of morpholine in promoting the n-π*transition and intensifying the intermolecular interactions,which not only enhances the generation of triplet excitons,but also suppresses the nonradiative decay of triplet excitons.Impressively,TMPh containing three morpholine units shows an ultralong lifetime of 1.03 s and a visible afterglow up to 10 s.The unique dual delayed emission and long afterglow property allow potential application of morpholine derivatives in data encryption,and the time-dependent color change of afterglow emission is realized after removing the excitation source,providing a high-level data security.This article provides a new perspective for the design of purely organic RTP system without utilization of metal,or even any heavy atoms.
基金supported by the National Natural Science Foundation of China(21971185,51821002)funded by the Collaborative Innovation Center of Suzhou Nano Science and Technology(CIC-Nano)the“111”Project of the State Administration of Foreign Experts Affairs of China。
文摘Organic luminescent materials play an integral role in the optoelectronic applications of displays and solid-state lighting.Nevertheless, high-performance organic luminescent materials require the efficient combination of two or more kinds of materials, which is extremely difficult owing to the completely different self-assembly behaviors of multicomponent molecules.Herein, based on a broad scale from the molecular, micro-/nano-scale, and macroscopic levels, we successfully demonstrate the multiscale construction of organic luminescent microwires of cocrystals, solid solutions, and core-shell microstructures. Through the wide selection of electron donor/acceptor pairs, a series of color-tunable charge-transfer(CT) cocrystals are formed via the intermolecular cooperative self-assembly process. On this basis, the high structural compatibility and perfect lattice mismatching(~1.1%) of cocrystals are critical factors that facilitate the combination of dissimilar materials to form solid solutions and core/shell microwires. Significantly, because of the full-spectrum light transport from 400 to 800 nm, the nano-micro-scaled solid solution microwires act as microscale white-light sources [CIE(0.32, 0.36)]. Meanwhile, the macroscopic-scale core/shell organic-microwires demonstrate tunable white-light emission with a high color-rendering index(CRI) of 83, whose CIE coordinates span from(0.37, 0.39) to(0.40, 0.31). Therefore, our work provides a feasible approach to the multiscale synthesis of novel luminescent organic semiconductor materials, which could lay a solid foundation for organic optoelectronics.
基金Supported by the National Natural Science Foundation of China（No.21273095）.
文摘Cytochrome P450（CYP） 2El is a dual function monoxygenase with a crucial role in the metabolism of 6% of drugs on the market at present. The enzyme is of tremendous interest for its association with alcohol consumption, diabetes, obesity and fasting. Despite the abundant experimental mutagenesis data, the molecular origin and the structural motifs for the enzymatic activity deficiencies have not been rationalized at the atomic level. In this regard, we have investigated the effects of mutation on the structural and energetic characteristics upon single point mutations in CYP2E1, N219D and $366C. The molecular dynamics（MD） simulation combined with quantum mechanics/molecular mechanics（QM/MM） and noncovalent interaction（NCI） analysis was carried out on CYP2EI and its two mutants. The results highlight the critical role of Phe207, which is responsible for both structural flexibility and energetic variation, shortening the gap between the theory and the experimentally observed results of enzymatic activity decrease, The underlying molecular mechanism of the enzymatic activity deficiencies for mutants may be attributed to the changes of spatial position of Phe207 in the two mutants. This work provides particular explanations to how mutations affect ligand-receptor interactions based on combined MD and QM/MM calculations. Furthermore, the mutational effects on the activity of CYP2E1 obtained in the present study are beneficial to both the experimental and the computational works of CYPs and may allow researchers to achieve desirable changes in enzymatic activity.
