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
The M2 protein from influenza A virus is a tetrameric ion channel. It was reported that the permeation of the ion channel is correlated with the hydrogen bond network among His37 residues and the cation-π interaction...The M2 protein from influenza A virus is a tetrameric ion channel. It was reported that the permeation of the ion channel is correlated with the hydrogen bond network among His37 residues and the cation-π interactions between His37 and Trp41. In the present study,the hydrogen bonding network of 4-methyl-imidazoles was built to mimic the hydrogen bonds between His37 residues,and the cation-π interactions between 4-methyl-imidazolium and indole systems were selected to represent the interac-tions between His37 and Trp41. Then,quantum chemistry calculations at the MP2/6-311G level were carried out to explore the properties of the hydrogen bonds and the cation-π interactions. The calcula-tion results indicate that the binding strength of the N-H···N hydrogen bond between imidazole rings is up to -6.22 kcal·mol-1,and the binding strength of the strongest cation-π interaction is up to -18.8 kcal·mol-1(T-shaped interaction) or -12.3 kcal·mol-1(parallel stacking interaction). Thus,the calcu-lated binding energies indicate that it is possible to control the permeation of the M2 ion channel through the hydrogen bond network and the cation-π interactions by altering the pH values.展开更多
In recent years,significant progress has been witnessed in organic solar cells(OSCs),which is mainly attributed to the new active layer materials design,especially fused ring acceptors.However,the majority of fused-ri...In recent years,significant progress has been witnessed in organic solar cells(OSCs),which is mainly attributed to the new active layer materials design,especially fused ring acceptors.However,the majority of fused-ring acceptors suffer from complicated synthetic procedures and unsatisfactory reaction yields and thus high preparation cost.It is difficult to reconcile with the necessity for OPVs to demonstrate the low cost advantage compared with other photovoltaic technologies such as silicon or perovskite solar cells,thus significantly limiting the future application of OSCs.Therefore,it is necessary to develop high efficiency but low cost acceptor materials,i.e.non-fused ring electron acceptors(NFREAs).In this review,the recent development of NFREAs from the viewpoint of materials design is discussed.In the first and second sections,NFREAs with different central cores are reviewed.Then,the progress of fully non-fused NFREAs is summarized.Finally,an outlook on the remaining challenges to the field is provided.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
Macrocyclic compounds are of great interest for their ability to capture guest molecules into their cavities.In particular,host-guest interaction plays a crucial role in the formation of supramolecular compounds.Herei...Macrocyclic compounds are of great interest for their ability to capture guest molecules into their cavities.In particular,host-guest interaction plays a crucial role in the formation of supramolecular compounds.Herein,two host-guest supramolecular compounds,[Al_(8)(OH)_(8)(L)_(16)]·2HL(HL@AlOC-166,HL=4-Iodobenzoic acid)and[Al_(8)(OH)_(8)(L)_(8)(L1)_(8)]·2DMF(DMF@AlOC-166,HL1=isoamyl alcohol),are acquired by introducing different types of guest components based on the internal pore cavities of the aluminum molecular ring[Al_(8)(OH)_(8)(L)_(16)](AlOC-166).The inclusion of these guests is attributed to the presence of abundant hydrophilic OH serving as the hydrogen bond donors inward the ring cavity.Host-guest compounds usually exhibit superior nonlinear optical(NLO)response due to the existence of guest molecules that could change symmetry,dipole moments,charge distributions,etc.Unexpectedly,the AlOC-166 achieved the best NLO results,although it had no guest molecules inside its molecular ring,which breaks the traditional concept.The reason for this trend can be explained by the difference in intermolecular force rather than intramolecular interaction,mainly related to the amount and strength ofπ···πand C—I···πinteractions in different compounds.This work investigates the effect of host-guest interaction on NLO,representing a new perspective for designing optical limiting materials.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
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 (Grant No. 20572117)the Shanghai Postdoctoral Scientific Program (Grant No. Y200-2-08)
文摘The M2 protein from influenza A virus is a tetrameric ion channel. It was reported that the permeation of the ion channel is correlated with the hydrogen bond network among His37 residues and the cation-π interactions between His37 and Trp41. In the present study,the hydrogen bonding network of 4-methyl-imidazoles was built to mimic the hydrogen bonds between His37 residues,and the cation-π interactions between 4-methyl-imidazolium and indole systems were selected to represent the interac-tions between His37 and Trp41. Then,quantum chemistry calculations at the MP2/6-311G level were carried out to explore the properties of the hydrogen bonds and the cation-π interactions. The calcula-tion results indicate that the binding strength of the N-H···N hydrogen bond between imidazole rings is up to -6.22 kcal·mol-1,and the binding strength of the strongest cation-π interaction is up to -18.8 kcal·mol-1(T-shaped interaction) or -12.3 kcal·mol-1(parallel stacking interaction). Thus,the calcu-lated binding energies indicate that it is possible to control the permeation of the M2 ion channel through the hydrogen bond network and the cation-π interactions by altering the pH values.
基金the financial support from the Hong Kong Scholar Program(XJ2021-038)the Natural Science Foundation Research Project of Shaanxi Province(Programs No.2021JQ-595)+2 种基金the National Natural Science Foundation of China(52025033,21935007)Tianjin City(20JCZDJC00740)the Postgraduate Innovation and Practical Ability Training Program of Xi'an Shiyou University(YCS21212144).
文摘In recent years,significant progress has been witnessed in organic solar cells(OSCs),which is mainly attributed to the new active layer materials design,especially fused ring acceptors.However,the majority of fused-ring acceptors suffer from complicated synthetic procedures and unsatisfactory reaction yields and thus high preparation cost.It is difficult to reconcile with the necessity for OPVs to demonstrate the low cost advantage compared with other photovoltaic technologies such as silicon or perovskite solar cells,thus significantly limiting the future application of OSCs.Therefore,it is necessary to develop high efficiency but low cost acceptor materials,i.e.non-fused ring electron acceptors(NFREAs).In this review,the recent development of NFREAs from the viewpoint of materials design is discussed.In the first and second sections,NFREAs with different central cores are reviewed.Then,the progress of fully non-fused NFREAs is summarized.Finally,an outlook on the remaining challenges to the field is provided.
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supported by the National Natural Science Foundation of China(U23A2095,22371278)Funding of the Fujian Provincial Chemistry Discipline Alliance,Natural Science Foundation of Fujian Province(2021J06035)Youth Innovation Promotion Association of the Chinese Academy of Sciences(Y2018081).
文摘Macrocyclic compounds are of great interest for their ability to capture guest molecules into their cavities.In particular,host-guest interaction plays a crucial role in the formation of supramolecular compounds.Herein,two host-guest supramolecular compounds,[Al_(8)(OH)_(8)(L)_(16)]·2HL(HL@AlOC-166,HL=4-Iodobenzoic acid)and[Al_(8)(OH)_(8)(L)_(8)(L1)_(8)]·2DMF(DMF@AlOC-166,HL1=isoamyl alcohol),are acquired by introducing different types of guest components based on the internal pore cavities of the aluminum molecular ring[Al_(8)(OH)_(8)(L)_(16)](AlOC-166).The inclusion of these guests is attributed to the presence of abundant hydrophilic OH serving as the hydrogen bond donors inward the ring cavity.Host-guest compounds usually exhibit superior nonlinear optical(NLO)response due to the existence of guest molecules that could change symmetry,dipole moments,charge distributions,etc.Unexpectedly,the AlOC-166 achieved the best NLO results,although it had no guest molecules inside its molecular ring,which breaks the traditional concept.The reason for this trend can be explained by the difference in intermolecular force rather than intramolecular interaction,mainly related to the amount and strength ofπ···πand C—I···πinteractions in different compounds.This work investigates the effect of host-guest interaction on NLO,representing a new perspective for designing optical limiting materials.
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.
