Transformations of the world unseen in a century are unfolding at a faster pace.Changes of the world,of our times,and of the historical trajectory are taking place in ways like never before.As the new round of technol...Transformations of the world unseen in a century are unfolding at a faster pace.Changes of the world,of our times,and of the historical trajectory are taking place in ways like never before.As the new round of technological revolution and industrial transformation advances,the international power structure and world order are undergoing tectonic realignments and constantly being reshaped.The protracted Ukraine crisis and the escalating Palestinian-Israeli conflict exemplify the intensification of major-power strategic rivalries and geopolitical conflicts.At the same time,non-traditional security issues are getting severe and more deeply intertwined with traditional security.Challenges such as climate change,cybersecurity,energy security,and food security are becoming critical global issues which confront humanity with unprecedented threats and herald a new era of instability and transformation for the world’s development.展开更多
The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migration...The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migrationbarrier are respectively around 10^(−4)S/cm and 0.3 eV.In this Letter,through first-principles calculations we predictthe existence of 1D superionicity as the Li ions in O_(2)LiCoO_(2)are transformed into Zn_(0.5)CoO_(2)or Li_(0.5)CoO_(2)via cation-exchange reaction or deintercalation.The ion migration barriers(0.01-0.02 eV)even lower than roomtemperature∼𝑘B𝑇are reduced by more than an order of magnitude compared with LiCoO_(2),which are facilitatedby facile transition of mobile ions between two coordination configurations.The room-temperature ion conductivityis estimated to be over 50 S/cm,enhanced by 2-3 orders of magnitude compared with the current highestreported value.Such unprecedented superionicity may also exist in other similar layered ion conductors,whichmay lead to technical advances and exotic effects such as ultrafast ion batteries and quantized ferroelectricity.展开更多
To the editor The present problematic outbreak in Africa is the Ebola virus infection among local population in the capital of Guinea.It becomes a great concern since the present outbreak(March to April 2014)is consid...To the editor The present problematic outbreak in Africa is the Ebola virus infection among local population in the capital of Guinea.It becomes a great concern since the present outbreak(March to April 2014)is considered to be the biggest outbreak,the first discovery of this viral infection[1].A high death rate can be seen.Severe diarrhea and bleeding can be seen in almost all cases and death rate is very high(about 75%).Focusing on the present outbreak,there are many considerations on this situation.First,this outbreak occurs in urban area insead of a remote rural area。展开更多
Under the guidance of the approach which integrates molecular networking,MolNetEnhancer and Net-work Annotation Propagation(NAP),daphnaltaicanoids A and B(1 and 2)with unprecedented 9-oxa-tetracyclo[6.6.1.0^(2,6).0^(8...Under the guidance of the approach which integrates molecular networking,MolNetEnhancer and Net-work Annotation Propagation(NAP),daphnaltaicanoids A and B(1 and 2)with unprecedented 9-oxa-tetracyclo[6.6.1.0^(2,6).0^(8,13)]pentadecane and tetracyclo[5.3.0.1^(2,5).2^(4,11)]tridecane central frameworks were iso-lated from Daphne altaica Pall.,representing two types of unparalleled meroterpenoid cores.Their struc-tures were elucidated by extensive spectroscopic analysis,nuclear magnetic resonance(NMR)calcula-tions,DP4+analysis and electronic circular dichroism(ECD)calculations.The plausible biosynthetic path-ways for 1 and 2 were postulated.Biologically,2 exerted potent neuroprotective activities which were su-perior to trolox at 12.5 and 25μmol/L.Moreover,1 and 2 exhibited more noticeable acetylcholinesterase inhibitory activities than donepezil.Molecular docking simulations were performed to explore the inter-molecular interaction of compounds 1 and 2 with acetylcholinesterase.The bioactivity evaluation results highlight the prospects of 1 and 2 as a novel category of neurological agents.展开更多
ZTE Corporation,a leading global provider of telecommunications equipment and network solutions,announced on June 6,2007 that it has signed a strategic cooperation agreement with Polkomtel S.A.,one of the top three mo...ZTE Corporation,a leading global provider of telecommunications equipment and network solutions,announced on June 6,2007 that it has signed a strategic cooperation agreement with Polkomtel S.A.,one of the top three mobile telephony operators in Poland.展开更多
China＇s Xinhua News Agency calls it the ＂biggest government reshuffle in years＂ in what is seen as a dra matic continuation of the previous seven rounds of cabinet restructuring that began in 1982.
The reactions of K_(2)ZnSb(0.234 mol)and Ni(CO)_(2)(PPh_(3))_(2)(x mol)in ethylenediamine(en)solutions of 18-crown-6 at 60℃yielded half-centered[Ni_(0.5)@{Sb_(6)Ni_(6)(CO)_(8)}]_(4)-(x=0.023,1)and fully embedded[Ni@{...The reactions of K_(2)ZnSb(0.234 mol)and Ni(CO)_(2)(PPh_(3))_(2)(x mol)in ethylenediamine(en)solutions of 18-crown-6 at 60℃yielded half-centered[Ni_(0.5)@{Sb_(6)Ni_(6)(CO)_(8)}]_(4)-(x=0.023,1)and fully embedded[Ni@{Sb_(7)Ni_(5)(CO)_(6)}]^(3-)(x=0.047,2),wherein the chair-like Sb_(6)subunit is bicapped by two Ni_(3) triangles to form the single Sb_(6)Ni_(6) icosahedron of 1 and by the triangular Ni_(2)Sb and Ni_(3) to form the single Sb_(7)Ni_(5) icosahedron of 2.Surprisingly,a smaller amount of Ni(CO)_(2)(PPh_(3))_(2)(x=0.016)led to the formation of the unprecedented dimer[(Sb_(8)){Sb_(7)Ni_(5)(CO)_(4)}_(2)]^(6-)(4),wherein the Sb_(7)Ni_(5) icosahedral unit built of boat-like Sb_(6),Ni_(2)Sb and Ni_(3) is linked together by the realgar-like Sb_(8) to form the icosahedral dimer 4,providing a new way of thinking for the preparation of icosahedral oligomers/polymers.A similar hexa-anionic dimer(3)can be solely obtained using PBu^(4+)as the countercation under the same reaction conditions.The structure and bonding of this novel series of icosahedral clusters containing polyantimony were discussed for the first time.展开更多
Although great efforts have been made to explore the exquisite rare-earth(RE)clusters,the design and construction of planar RE clusters with disk-like geometrical features are still scarce.Herein,a novel disklike RE-c...Although great efforts have been made to explore the exquisite rare-earth(RE)clusters,the design and construction of planar RE clusters with disk-like geometrical features are still scarce.Herein,a novel disklike RE-cluster Y_(12)(abbreviated as 1),formulated as[Y_(12)(L)_(10)(CO_(3))_(4)(NO_(3))_(2)(μ_(3)-OH)_(6)](H_(2)L=7,7’-(2-methylmethylene)bis(8-quinolonol))was synthesized successfully under solvothermal conditions.Owing to the template effect and fruitful coordination modes of NO_(3)^(-),a novel Y_(2)⊂Y_(10)type structure with dual-core in the center position of the cluster,which distinguishes it from the traditional brucite-type disk-like REcluster was achieved.Based on the ESI-MS analysis,the possible assembly mechanism of Y_(5)→Y_(8)→Y_(12)is proposed.The luminescence investigation illustrates that this cluster not only shows green emission in solid-state and common organic solvents but also has obvious electroluminescent performance,which can be used as the emitting layer in organic light-emitting diodes(OLEDs).展开更多
A new layered manganese(II)phosphite,|NH_(4)|_(4)[Mn_(4)(PO_(3)H)_(6)](JIS-10),has been synthesised via the ionothermal method by using 1-pentyl-3-methylimidazolium bromide([Pmim]Br)as the solvent.JIS-10 is the first ...A new layered manganese(II)phosphite,|NH_(4)|_(4)[Mn_(4)(PO_(3)H)_(6)](JIS-10),has been synthesised via the ionothermal method by using 1-pentyl-3-methylimidazolium bromide([Pmim]Br)as the solvent.JIS-10 is the first manganese phosphite with a Mn/P ratio of 2/3,whose layered framework is built by the alternate connection of Mn_(2)O_(9)dimers and PO3H pseudo-tetrahedra.JIS-10 represents an antiferromagnetic dimer system with S=5/2 for each Mn^(2+)ion.展开更多
As a contribution to the development of new ruthenium complexes with pharmacologically interesting properties,two new mononuclear ruthenium(II)complexes of the general formula[Ru(H-Nap-sbdtc)Cl-(CO)(EPh_(3))_(2)](1&am...As a contribution to the development of new ruthenium complexes with pharmacologically interesting properties,two new mononuclear ruthenium(II)complexes of the general formula[Ru(H-Nap-sbdtc)Cl-(CO)(EPh_(3))_(2)](1&2)[H-(Nap-sbdtc)=2-hydroxy-1-naphthaldehyde-S-benzyl-dithiocarbazate;E=P or As]were synthesized.The new ruthenium(II)carbonyl complexes are remarkably stable and were obtained in good yields.Their identities have been established by satisfactory elemental analyses and various spectroscopic techniques(IR,UV/visible,(^(1)H,^(13)C,and ^(31)P)NMR,and ESI-MS).For a better definition,the molecular structure of complexes 1 and 2 has been determined by X-ray crystallography,which confirms the coordination mode of the ligand and reveals a distorted octahedral geometry around the ruthenium ion.The molecular structure of complexes 1 and 2 has been optimized by DFT calculations.展开更多
Pressure can shorten the distance between molecules or atoms,which can change the periodicity of elements and provide more unprecedented novel materials.In order to produce substances that can remain stable or metasta...Pressure can shorten the distance between molecules or atoms,which can change the periodicity of elements and provide more unprecedented novel materials.In order to produce substances that can remain stable or metastable under an atmospheric pressure,pressure has become an indispensable and powerful means.Recent research suggests that high-pressure synthesis methods have unlimited potential in different research fields.For example,high T_(c)(transition temperature)superconductors with a transition temperature of up to 250 K and super-hard nano-diamonds(NDs)with a hardness of 1 TPa can be synthesized under high-temperature and high-pressure(HTHP)conditions,and these materials cannot be achieved by other synthetic methods.Many recent research achievements involve the synthesis of some compounds with special structures and properties,such as high-entropy alloys,non-stoichiometric substances,inert element compounds,and heterostructure nanocrystals.This review will introduce the latest developments in inorganic compounds obtained under high pressure.Materials with different application backgrounds are classified,some materials with high performance or high potential are introduced,and possible synthesis mechanisms are discussed.In the Conclusions section,we summarize research directions in which the field of high-pressure synthesis research may have great breakthroughs in the next few years,and look forward to the future development of high-pressure synthesis methods.展开更多
The uncontrolled assembly of Al(III)octahedra makes the synthesis of related two-dimensional(2D)compounds unpredictable,thus limiting their potential applications.In contrast to traditional synthesis methods,we propos...The uncontrolled assembly of Al(III)octahedra makes the synthesis of related two-dimensional(2D)compounds unpredictable,thus limiting their potential applications.In contrast to traditional synthesis methods,we propose a stepwise synthetic approach based on aluminum molecular rings.By fine-tuning the angle of the coordination unit and direction of anchoring modulation,a zero-dimensional(0D)aluminum molecular ring(AlOC-196)can be successfully preserved as a unique building block,allowing for the construction of a targeted 2D configuration(AlOC-197).Notably,the weak interlayer interactions facilitate its further exfoliation process.Moreover,compared to bulk crystals,nanosheets produced through liquidphase exfoliation exhibit enhanced third-order nonlinear optical(NLO)properties.This coordinationdriven self-assembly strategy shows promise in expanding the structural diversity and functionality of layered materials.展开更多
Two Lu_(2)O@C_(80)isomers have been successfully isolated and unambiguously assigned as Lu_(2)O@C_(1)(31876)-C_(80)and Lu_(2)O@C_(2v)(5)-C_(80),respectively,by X-ray crystallography.Interestingly,C1(31876)-C_(80)is an...Two Lu_(2)O@C_(80)isomers have been successfully isolated and unambiguously assigned as Lu_(2)O@C_(1)(31876)-C_(80)and Lu_(2)O@C_(2v)(5)-C_(80),respectively,by X-ray crystallography.Interestingly,C1(31876)-C_(80)is an unprecedented cage with a pair of adjacent pentagons,which can be closely connected with C_(2v)(5)-C_(80)via a two-step Stone–Wales transformation.展开更多
Exploration of ultraviolet phosphates with balanced overall performance is of great significance and difficulty.Herein,the first barium bismuth zincophosphate,Ba_(2)Bi_(2)[Zn(PO_(4))_(4)],was rationally obtained by io...Exploration of ultraviolet phosphates with balanced overall performance is of great significance and difficulty.Herein,the first barium bismuth zincophosphate,Ba_(2)Bi_(2)[Zn(PO_(4))_(4)],was rationally obtained by ion mixing and anionic condensation,while single crystals of Ba_(2)Bi_(2)[Zn(PO_(4))_(4)]were synthesized by a high temperature molten salt method.In the strucutre of Ba_(2)Bi_(2)[Zn(PO_(4))_(4)],unprecedented_(∞)[Zn(PO_(4))_(4)]^(10−)chains,which were made up through the condensation of infrequent[Zn(PO_(4))_(5)]^(13−)groups,were ionically bridged by massive Ba^(2+)and Bi^(3+).Having benefitted from its unique one-dimensional anionic frame and the ultilization of mutiple ions,Ba_(2)Bi_(2)[Zn(PO_(4))_(4)]was characterized by a balanced overall performance over birefrigence,band gap and physicochemical stability.Especially,Ba_(2)Bi_(2)[Zn(PO_(4))_(4)]was verified as a congruently melting crystal with a high melting point of about 965℃,being conducive to practical applications.展开更多
The first example of unique coordination induced intramolecular pancake bonding was achieved through the reduction of two bis(pyrazolyl)-tetrazine ligands,affording[M_(2)^(Ⅲ)(μ-(bpytz)_(2))(THMD)4](M=Dy,Y;bpytz=3,6-...The first example of unique coordination induced intramolecular pancake bonding was achieved through the reduction of two bis(pyrazolyl)-tetrazine ligands,affording[M_(2)^(Ⅲ)(μ-(bpytz)_(2))(THMD)4](M=Dy,Y;bpytz=3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine;TMHD=2,2,6,6-tetramethyl-3,5-heptanedionate).To provide a cohesive magneto-structural correlation,the mono bis(pyrazolyl)-tetrazine bridged congener[Dy_(2)^(Ⅲ)(μ-bpytz)(THMD)6]·4(C6H6)was also isolated.Both metal complexes exhibit single-molecule magnet behaviour under an applied dc field.展开更多
The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas stor...The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas storage/separation,catalysis and so on.In this study,we designed and constructed a highly porous(3,36)-connected txt-type acylamide-functionalized metal–organic framework(HNUST-8)from a pyridine-based acylamide-linking diisophthalate and dicopper(II)-paddlewheel clusters.展开更多
Nickel-based layered double hydroxides(LDHs)are widely recognized as promising substitutes for noble metal catalysts in the oxygen evolution reaction(OER).However,conventional Ni^(2+)sites exhibit a high-spin configur...Nickel-based layered double hydroxides(LDHs)are widely recognized as promising substitutes for noble metal catalysts in the oxygen evolution reaction(OER).However,conventional Ni^(2+)sites exhibit a high-spin configuration(d_(xz)^(2)d_(yz)^(2)d_(xy)^(2)d_(x^(2)-y^(2))^(1)d_(z^(2))^(1))with excessive frontier-orbital occupancy,resulting in weak binding strength toward oxygen intermediates,which dramatically limits their OER performance.Herein,we first report the successful construction of low-spin state Ni^(2+)(d_(xz)^(2)d_(yz)^(2)d_(xy)^(2)d_(x^(2)-y^(2))^(1)d_(z^(2))^(0))in NiCoFe-LDH(LS-NCF)through oxygen defect engineering.LS-NCF exhibits a splendid OER activity with an ultralow overpotential of 241 mV at the current density of 1 A·cm^(−2),which is 79 mV lower than that of the conventional NiCoFe-LDH d_(z^(2)) with high-spin Ni^(2+)(HS-NCF),significantly outperforming previously reported transition metal-based catalysts.Comprehensive studies reveal that LS Ni^(2+)with reduced orbital occupancy effectively enhances oxygen intermediates adsorption through reinforcing the orbital hybridization between Ni 3d and O 2p.Moreover,the d-band center of LS Ni^(2+)is closer to the Fermi level compared to that of HS Ni^(2+),thus accelerating electron transfer.Consequently,the strengthened adsorption of ^(*)O intermediate and accelerated electron transfer in LS-NCF efficiently lower the reaction energy barrier of the rate-determining step(^(*)O→^(*)OOH),thereby greatly boosting its OER performance.This work provides valuable insights into designing high-performance Ni-based electrocatalysts via spintronic-level engineering.展开更多
Multiple diagnoses,from both East and West,converge on the view that we are living through a turbulent juncture reminiscent of the inflection points that preceded major wars,not as a claim of historical symmetry,but a...Multiple diagnoses,from both East and West,converge on the view that we are living through a turbulent juncture reminiscent of the inflection points that preceded major wars,not as a claim of historical symmetry,but as an indication of the depth of the present crisis.What concerns us here is to affirm the essence of that assessment:we are indeed facing an unprecedented crisis that compels a rethinking of the entire existing international order,as U.S.展开更多
Fluorooxoborate has emerged as a promising system for exploring optical materials due to their rich structural chemistry and physicochemical properties,yet so far not fully studied.Herein,we report a new fluorooxobora...Fluorooxoborate has emerged as a promising system for exploring optical materials due to their rich structural chemistry and physicochemical properties,yet so far not fully studied.Herein,we report a new fluorooxoborate,Ba_(2)B_(9)O_(13)F_(4)·BF_(4),which contains the greatest variety of structural basic units,[BO_(3)],[BO_(2)F_(2)],[BO_(3)F],and[BF_(4)],and exhibits unprecedented 1D infinite[B_(18)O_(26)F_(8)]tubes.The unique structure avoids the dangling bonds caused by terminal oxygens,which is beneficial to the large bandgap and deep-ultraviolet cutoff edge.This article expands the crystal structure of fluorooxoborates and contributes to the exploration of deep-ultraviolet optical materials in fluorooxoborate systems.展开更多
文摘Transformations of the world unseen in a century are unfolding at a faster pace.Changes of the world,of our times,and of the historical trajectory are taking place in ways like never before.As the new round of technological revolution and industrial transformation advances,the international power structure and world order are undergoing tectonic realignments and constantly being reshaped.The protracted Ukraine crisis and the escalating Palestinian-Israeli conflict exemplify the intensification of major-power strategic rivalries and geopolitical conflicts.At the same time,non-traditional security issues are getting severe and more deeply intertwined with traditional security.Challenges such as climate change,cybersecurity,energy security,and food security are becoming critical global issues which confront humanity with unprecedented threats and herald a new era of instability and transformation for the world’s development.
基金supported by the National Natural Science Foundation of China(Grant No.22073034)。
文摘The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migrationbarrier are respectively around 10^(−4)S/cm and 0.3 eV.In this Letter,through first-principles calculations we predictthe existence of 1D superionicity as the Li ions in O_(2)LiCoO_(2)are transformed into Zn_(0.5)CoO_(2)or Li_(0.5)CoO_(2)via cation-exchange reaction or deintercalation.The ion migration barriers(0.01-0.02 eV)even lower than roomtemperature∼𝑘B𝑇are reduced by more than an order of magnitude compared with LiCoO_(2),which are facilitatedby facile transition of mobile ions between two coordination configurations.The room-temperature ion conductivityis estimated to be over 50 S/cm,enhanced by 2-3 orders of magnitude compared with the current highestreported value.Such unprecedented superionicity may also exist in other similar layered ion conductors,whichmay lead to technical advances and exotic effects such as ultrafast ion batteries and quantized ferroelectricity.
文摘To the editor The present problematic outbreak in Africa is the Ebola virus infection among local population in the capital of Guinea.It becomes a great concern since the present outbreak(March to April 2014)is considered to be the biggest outbreak,the first discovery of this viral infection[1].A high death rate can be seen.Severe diarrhea and bleeding can be seen in almost all cases and death rate is very high(about 75%).Focusing on the present outbreak,there are many considerations on this situation.First,this outbreak occurs in urban area insead of a remote rural area。
基金supported by the National Natural Science Foundation of China(Nos.82073736,81872766)Science and Technology Planning Project of Liaoning Province(No.2021JH1/10400049)Liaoning revitalization talents program(Nos.XLYC2002066,XLYC2007180).
文摘Under the guidance of the approach which integrates molecular networking,MolNetEnhancer and Net-work Annotation Propagation(NAP),daphnaltaicanoids A and B(1 and 2)with unprecedented 9-oxa-tetracyclo[6.6.1.0^(2,6).0^(8,13)]pentadecane and tetracyclo[5.3.0.1^(2,5).2^(4,11)]tridecane central frameworks were iso-lated from Daphne altaica Pall.,representing two types of unparalleled meroterpenoid cores.Their struc-tures were elucidated by extensive spectroscopic analysis,nuclear magnetic resonance(NMR)calcula-tions,DP4+analysis and electronic circular dichroism(ECD)calculations.The plausible biosynthetic path-ways for 1 and 2 were postulated.Biologically,2 exerted potent neuroprotective activities which were su-perior to trolox at 12.5 and 25μmol/L.Moreover,1 and 2 exhibited more noticeable acetylcholinesterase inhibitory activities than donepezil.Molecular docking simulations were performed to explore the inter-molecular interaction of compounds 1 and 2 with acetylcholinesterase.The bioactivity evaluation results highlight the prospects of 1 and 2 as a novel category of neurological agents.
文摘ZTE Corporation,a leading global provider of telecommunications equipment and network solutions,announced on June 6,2007 that it has signed a strategic cooperation agreement with Polkomtel S.A.,one of the top three mobile telephony operators in Poland.
文摘China＇s Xinhua News Agency calls it the ＂biggest government reshuffle in years＂ in what is seen as a dra matic continuation of the previous seven rounds of cabinet restructuring that began in 1982.
基金supported by the National Natural Science Foundation of China(21873102).
文摘The reactions of K_(2)ZnSb(0.234 mol)and Ni(CO)_(2)(PPh_(3))_(2)(x mol)in ethylenediamine(en)solutions of 18-crown-6 at 60℃yielded half-centered[Ni_(0.5)@{Sb_(6)Ni_(6)(CO)_(8)}]_(4)-(x=0.023,1)and fully embedded[Ni@{Sb_(7)Ni_(5)(CO)_(6)}]^(3-)(x=0.047,2),wherein the chair-like Sb_(6)subunit is bicapped by two Ni_(3) triangles to form the single Sb_(6)Ni_(6) icosahedron of 1 and by the triangular Ni_(2)Sb and Ni_(3) to form the single Sb_(7)Ni_(5) icosahedron of 2.Surprisingly,a smaller amount of Ni(CO)_(2)(PPh_(3))_(2)(x=0.016)led to the formation of the unprecedented dimer[(Sb_(8)){Sb_(7)Ni_(5)(CO)_(4)}_(2)]^(6-)(4),wherein the Sb_(7)Ni_(5) icosahedral unit built of boat-like Sb_(6),Ni_(2)Sb and Ni_(3) is linked together by the realgar-like Sb_(8) to form the icosahedral dimer 4,providing a new way of thinking for the preparation of icosahedral oligomers/polymers.A similar hexa-anionic dimer(3)can be solely obtained using PBu^(4+)as the countercation under the same reaction conditions.The structure and bonding of this novel series of icosahedral clusters containing polyantimony were discussed for the first time.
基金supported by the NSFC of China(22271217,21571139,22035003 and 22001132).
文摘Although great efforts have been made to explore the exquisite rare-earth(RE)clusters,the design and construction of planar RE clusters with disk-like geometrical features are still scarce.Herein,a novel disklike RE-cluster Y_(12)(abbreviated as 1),formulated as[Y_(12)(L)_(10)(CO_(3))_(4)(NO_(3))_(2)(μ_(3)-OH)_(6)](H_(2)L=7,7’-(2-methylmethylene)bis(8-quinolonol))was synthesized successfully under solvothermal conditions.Owing to the template effect and fruitful coordination modes of NO_(3)^(-),a novel Y_(2)⊂Y_(10)type structure with dual-core in the center position of the cluster,which distinguishes it from the traditional brucite-type disk-like REcluster was achieved.Based on the ESI-MS analysis,the possible assembly mechanism of Y_(5)→Y_(8)→Y_(12)is proposed.The luminescence investigation illustrates that this cluster not only shows green emission in solid-state and common organic solvents but also has obvious electroluminescent performance,which can be used as the emitting layer in organic light-emitting diodes(OLEDs).
基金National Natural Science Foundation of China(Grant No:21273098,21473024,and 21501062)the Program for New Century Excellent Talents in University(NCET-13-0246)the Research Project of the Science and Technology of Jilin Province,China(Grant no:201413001)for financial support.
文摘A new layered manganese(II)phosphite,|NH_(4)|_(4)[Mn_(4)(PO_(3)H)_(6)](JIS-10),has been synthesised via the ionothermal method by using 1-pentyl-3-methylimidazolium bromide([Pmim]Br)as the solvent.JIS-10 is the first manganese phosphite with a Mn/P ratio of 2/3,whose layered framework is built by the alternate connection of Mn_(2)O_(9)dimers and PO3H pseudo-tetrahedra.JIS-10 represents an antiferromagnetic dimer system with S=5/2 for each Mn^(2+)ion.
基金The authors Dr P.V.and P.V.gratefully acknowledge UGC[F.No.40-66/2011(SR)]for financial supportThe author(R.N.)is thankful to DST for financial assistance(project no.SR/FT/CS-95/2010).
文摘As a contribution to the development of new ruthenium complexes with pharmacologically interesting properties,two new mononuclear ruthenium(II)complexes of the general formula[Ru(H-Nap-sbdtc)Cl-(CO)(EPh_(3))_(2)](1&2)[H-(Nap-sbdtc)=2-hydroxy-1-naphthaldehyde-S-benzyl-dithiocarbazate;E=P or As]were synthesized.The new ruthenium(II)carbonyl complexes are remarkably stable and were obtained in good yields.Their identities have been established by satisfactory elemental analyses and various spectroscopic techniques(IR,UV/visible,(^(1)H,^(13)C,and ^(31)P)NMR,and ESI-MS).For a better definition,the molecular structure of complexes 1 and 2 has been determined by X-ray crystallography,which confirms the coordination mode of the ligand and reveals a distorted octahedral geometry around the ruthenium ion.The molecular structure of complexes 1 and 2 has been optimized by DFT calculations.
基金supported by the National Natural Science Foundation of China(no.21271082 and 21371068).
文摘Pressure can shorten the distance between molecules or atoms,which can change the periodicity of elements and provide more unprecedented novel materials.In order to produce substances that can remain stable or metastable under an atmospheric pressure,pressure has become an indispensable and powerful means.Recent research suggests that high-pressure synthesis methods have unlimited potential in different research fields.For example,high T_(c)(transition temperature)superconductors with a transition temperature of up to 250 K and super-hard nano-diamonds(NDs)with a hardness of 1 TPa can be synthesized under high-temperature and high-pressure(HTHP)conditions,and these materials cannot be achieved by other synthetic methods.Many recent research achievements involve the synthesis of some compounds with special structures and properties,such as high-entropy alloys,non-stoichiometric substances,inert element compounds,and heterostructure nanocrystals.This review will introduce the latest developments in inorganic compounds obtained under high pressure.Materials with different application backgrounds are classified,some materials with high performance or high potential are introduced,and possible synthesis mechanisms are discussed.In the Conclusions section,we summarize research directions in which the field of high-pressure synthesis research may have great breakthroughs in the next few years,and look forward to the future development of high-pressure synthesis methods.
基金supported by the National Natural Science Foundation of China(22371278,U23A2095)the Natural Science Foundation of Fujian Province(2021J06035)Youth Innovation Promotion Association CAS(Y2021081).
文摘The uncontrolled assembly of Al(III)octahedra makes the synthesis of related two-dimensional(2D)compounds unpredictable,thus limiting their potential applications.In contrast to traditional synthesis methods,we propose a stepwise synthetic approach based on aluminum molecular rings.By fine-tuning the angle of the coordination unit and direction of anchoring modulation,a zero-dimensional(0D)aluminum molecular ring(AlOC-196)can be successfully preserved as a unique building block,allowing for the construction of a targeted 2D configuration(AlOC-197).Notably,the weak interlayer interactions facilitate its further exfoliation process.Moreover,compared to bulk crystals,nanosheets produced through liquidphase exfoliation exhibit enhanced third-order nonlinear optical(NLO)properties.This coordinationdriven self-assembly strategy shows promise in expanding the structural diversity and functionality of layered materials.
基金Financial support from NSFC(No.21925104,21573172,and 21773181)the Hubei Provincial Natural Science Foundation of China(No.2021CFA020)is gratefully acknowl-edged。
文摘Two Lu_(2)O@C_(80)isomers have been successfully isolated and unambiguously assigned as Lu_(2)O@C_(1)(31876)-C_(80)and Lu_(2)O@C_(2v)(5)-C_(80),respectively,by X-ray crystallography.Interestingly,C1(31876)-C_(80)is an unprecedented cage with a pair of adjacent pentagons,which can be closely connected with C_(2v)(5)-C_(80)via a two-step Stone–Wales transformation.
基金supported by the PhD research startup foundation of China West Normal University(No.412923).
文摘Exploration of ultraviolet phosphates with balanced overall performance is of great significance and difficulty.Herein,the first barium bismuth zincophosphate,Ba_(2)Bi_(2)[Zn(PO_(4))_(4)],was rationally obtained by ion mixing and anionic condensation,while single crystals of Ba_(2)Bi_(2)[Zn(PO_(4))_(4)]were synthesized by a high temperature molten salt method.In the strucutre of Ba_(2)Bi_(2)[Zn(PO_(4))_(4)],unprecedented_(∞)[Zn(PO_(4))_(4)]^(10−)chains,which were made up through the condensation of infrequent[Zn(PO_(4))_(5)]^(13−)groups,were ionically bridged by massive Ba^(2+)and Bi^(3+).Having benefitted from its unique one-dimensional anionic frame and the ultilization of mutiple ions,Ba_(2)Bi_(2)[Zn(PO_(4))_(4)]was characterized by a balanced overall performance over birefrigence,band gap and physicochemical stability.Especially,Ba_(2)Bi_(2)[Zn(PO_(4))_(4)]was verified as a congruently melting crystal with a high melting point of about 965℃,being conducive to practical applications.
基金the University of Ottawa,the CFI,the NSERC and the Academy of Finland(projects 315829,320015)for their financial supportConselho Nacional de Desenvolvimento Científico e Tecnológico(CNPQ,201395/2014-6)for a PhD scholarship.
文摘The first example of unique coordination induced intramolecular pancake bonding was achieved through the reduction of two bis(pyrazolyl)-tetrazine ligands,affording[M_(2)^(Ⅲ)(μ-(bpytz)_(2))(THMD)4](M=Dy,Y;bpytz=3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine;TMHD=2,2,6,6-tetramethyl-3,5-heptanedionate).To provide a cohesive magneto-structural correlation,the mono bis(pyrazolyl)-tetrazine bridged congener[Dy_(2)^(Ⅲ)(μ-bpytz)(THMD)6]·4(C6H6)was also isolated.Both metal complexes exhibit single-molecule magnet behaviour under an applied dc field.
基金supported by the National Natural Science Foundation of China(Grant No.21401055,21371150 and 21201062)Hunan Provincial Natural Science Foundation of China(Grant No.2018JJ2113 and 2017JJ2095)State Key Laboratory of Coordination Chemistry(Grant No.SKLCC1417).
文摘The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas storage/separation,catalysis and so on.In this study,we designed and constructed a highly porous(3,36)-connected txt-type acylamide-functionalized metal–organic framework(HNUST-8)from a pyridine-based acylamide-linking diisophthalate and dicopper(II)-paddlewheel clusters.
基金supported by the National Natural Science Foundation of China(Nos.22379023 and 22102007)the China Postdoctoral Science Foundation(No.2023M740555)+3 种基金Heilongjiang Provincial Postdoctoral Science Foundation(No.LBH-Z23001)Heilongjiang Provincial Natural Science Foundation Outstanding Youth Fund Project(No.YQ2024B002)the Foundation of State Key Laboratory of Catalysis(No.N-22-07)the Fundamental Research Funds for the Central Universities(No.2572023CT10).
文摘Nickel-based layered double hydroxides(LDHs)are widely recognized as promising substitutes for noble metal catalysts in the oxygen evolution reaction(OER).However,conventional Ni^(2+)sites exhibit a high-spin configuration(d_(xz)^(2)d_(yz)^(2)d_(xy)^(2)d_(x^(2)-y^(2))^(1)d_(z^(2))^(1))with excessive frontier-orbital occupancy,resulting in weak binding strength toward oxygen intermediates,which dramatically limits their OER performance.Herein,we first report the successful construction of low-spin state Ni^(2+)(d_(xz)^(2)d_(yz)^(2)d_(xy)^(2)d_(x^(2)-y^(2))^(1)d_(z^(2))^(0))in NiCoFe-LDH(LS-NCF)through oxygen defect engineering.LS-NCF exhibits a splendid OER activity with an ultralow overpotential of 241 mV at the current density of 1 A·cm^(−2),which is 79 mV lower than that of the conventional NiCoFe-LDH d_(z^(2)) with high-spin Ni^(2+)(HS-NCF),significantly outperforming previously reported transition metal-based catalysts.Comprehensive studies reveal that LS Ni^(2+)with reduced orbital occupancy effectively enhances oxygen intermediates adsorption through reinforcing the orbital hybridization between Ni 3d and O 2p.Moreover,the d-band center of LS Ni^(2+)is closer to the Fermi level compared to that of HS Ni^(2+),thus accelerating electron transfer.Consequently,the strengthened adsorption of ^(*)O intermediate and accelerated electron transfer in LS-NCF efficiently lower the reaction energy barrier of the rate-determining step(^(*)O→^(*)OOH),thereby greatly boosting its OER performance.This work provides valuable insights into designing high-performance Ni-based electrocatalysts via spintronic-level engineering.
文摘Multiple diagnoses,from both East and West,converge on the view that we are living through a turbulent juncture reminiscent of the inflection points that preceded major wars,not as a claim of historical symmetry,but as an indication of the depth of the present crisis.What concerns us here is to affirm the essence of that assessment:we are indeed facing an unprecedented crisis that compels a rethinking of the entire existing international order,as U.S.
基金supported by the National Key Research Project of China(2022YFE0134500)the National Natural Science Foundation of China(61922084,61835014)+4 种基金the West Light Foundation of Chinese Academy of Sciences(2019-YDYLTD-002)the Instrument Developing Project of Chinese Academy of Sciences(GJJSTD20200007)the Xinjiang Major Science and Technology Project(2021A01001)the International Partnership Program of Chinese Academy of Sciences(1A1365KYSB20200008)the Science and Technology Service Network Initiative of Chinese Academy of Sciences(KFJ-STS-QYZD-130)。
文摘Fluorooxoborate has emerged as a promising system for exploring optical materials due to their rich structural chemistry and physicochemical properties,yet so far not fully studied.Herein,we report a new fluorooxoborate,Ba_(2)B_(9)O_(13)F_(4)·BF_(4),which contains the greatest variety of structural basic units,[BO_(3)],[BO_(2)F_(2)],[BO_(3)F],and[BF_(4)],and exhibits unprecedented 1D infinite[B_(18)O_(26)F_(8)]tubes.The unique structure avoids the dangling bonds caused by terminal oxygens,which is beneficial to the large bandgap and deep-ultraviolet cutoff edge.This article expands the crystal structure of fluorooxoborates and contributes to the exploration of deep-ultraviolet optical materials in fluorooxoborate systems.
