Multi-stimuli responsive materials controlled and coupled by two or more channels have a broad range of applications in the field of switches,memories,and molecular machines.The exploration of the material is currentl...Multi-stimuli responsive materials controlled and coupled by two or more channels have a broad range of applications in the field of switches,memories,and molecular machines.The exploration of the material is currently focused on the pure organic system,which limits the development o such materials greatly.In this work,we present a new chiral organic-inorganic hybrid salt,(R-3hydroxypyrrolidinium)_(2)[Fe(CN)_(5)(NO)](1),which exhibits rare multi-stimuli responsive behaviors in ther mal,mechanical and optical channels.In detail,1 undergoes a C2-P2_(1)22_(1) phase transition deriving from the thermal motion of organic cations with the increase of temperature,but the reverse transition can only be induced by mechanical pressure.Moreover,polycrystalline hybrid salt showed photo-responsive performance,i.e.,the ground-state N-bound nitrosyl ligand adopts two configurations in excited state caused by light in 532 nm irradiation,accompanying with a photo-induced structural transformation o the anionic framework.Namely,the thermal motion characteristics of organic cations,the photoresponse characteristics of anionic inorganic skeleton and the pressure characteristics from hydrogen bonds are si multaneously integrated in 1.This unprecedented coupling mechanism of multi-stimuli responses make1 a potential candidate for future multichannel data storage applications.展开更多
Atomic-scale insight into decompositions in energetic materials(EMs)is essential for harnessing energy release,which remains elusive due to both instrumental and computational limitations.Herein,we developed DeepEMs-2...Atomic-scale insight into decompositions in energetic materials(EMs)is essential for harnessing energy release,which remains elusive due to both instrumental and computational limitations.Herein,we developed DeepEMs-25,a deep-learning potential trained on diverse EMs towards accurate and efficient simulations.Applying DeepEMs‑25 to an isostructural ABX_(3)molecular perovskites series,with A-site organic cations,B-site alkali or ammonium cations,and X-site perchlorate anions,we probe the effect of cation size on reactivity.Arrhenius analysis of 100-ps trajectories reveals that increasing B‑site ionic radius simultaneously decreases X–A collision’s activation energy(enhancing reaction rates)and decreases X–A collision’s pre‑exponential factor(reducing collision frequency),producing opposing kinetic effects.Such“kinetic tug‑of‑war”explains why an intermediate‑sized cation yields maximal thermal stability by optimally balancing reactivity and collision dissipation.A similarly sized reactive cation promotes additional hydrogen-transfer pathways causing accelerating decomposition.Our findings link atomistic kinetics to macroscopic stability,informing nextgeneration EMs design.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22071273 and 21821003)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.23lgzy001)。
文摘Multi-stimuli responsive materials controlled and coupled by two or more channels have a broad range of applications in the field of switches,memories,and molecular machines.The exploration of the material is currently focused on the pure organic system,which limits the development o such materials greatly.In this work,we present a new chiral organic-inorganic hybrid salt,(R-3hydroxypyrrolidinium)_(2)[Fe(CN)_(5)(NO)](1),which exhibits rare multi-stimuli responsive behaviors in ther mal,mechanical and optical channels.In detail,1 undergoes a C2-P2_(1)22_(1) phase transition deriving from the thermal motion of organic cations with the increase of temperature,but the reverse transition can only be induced by mechanical pressure.Moreover,polycrystalline hybrid salt showed photo-responsive performance,i.e.,the ground-state N-bound nitrosyl ligand adopts two configurations in excited state caused by light in 532 nm irradiation,accompanying with a photo-induced structural transformation o the anionic framework.Namely,the thermal motion characteristics of organic cations,the photoresponse characteristics of anionic inorganic skeleton and the pressure characteristics from hydrogen bonds are si multaneously integrated in 1.This unprecedented coupling mechanism of multi-stimuli responses make1 a potential candidate for future multichannel data storage applications.
基金funded by the National Natural Science Foundation of China(U2341287 and 22488101)Guangzhou Science and Technology Program(2024A04J6499)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(23lgzy001).The funder played no role in study design,data collection,analysis,interpretation of data,or the writing of this manuscript.The computational resource was supported by the Bohrium Cloud Platform(https://bohrium.dp.tech/)and the National Supercomputing Center in Guangzhou(NSCC-GZ,Tianhe-2).M.-Y.G.thanks Chengqian Zhang and Duo Zhang for fruitful discussions.Language polishing was assisted by DeepSeek-v3 and finalized by human authors.
文摘Atomic-scale insight into decompositions in energetic materials(EMs)is essential for harnessing energy release,which remains elusive due to both instrumental and computational limitations.Herein,we developed DeepEMs-25,a deep-learning potential trained on diverse EMs towards accurate and efficient simulations.Applying DeepEMs‑25 to an isostructural ABX_(3)molecular perovskites series,with A-site organic cations,B-site alkali or ammonium cations,and X-site perchlorate anions,we probe the effect of cation size on reactivity.Arrhenius analysis of 100-ps trajectories reveals that increasing B‑site ionic radius simultaneously decreases X–A collision’s activation energy(enhancing reaction rates)and decreases X–A collision’s pre‑exponential factor(reducing collision frequency),producing opposing kinetic effects.Such“kinetic tug‑of‑war”explains why an intermediate‑sized cation yields maximal thermal stability by optimally balancing reactivity and collision dissipation.A similarly sized reactive cation promotes additional hydrogen-transfer pathways causing accelerating decomposition.Our findings link atomistic kinetics to macroscopic stability,informing nextgeneration EMs design.
