Ferroelastic rare earth tantalates(RETaO_(4))are widely researched as the next-generation thermal barrier coatings(TBCs),and RETaO_(4)powders are hugely significant for synthesizing their coatings.The current research...Ferroelastic rare earth tantalates(RETaO_(4))are widely researched as the next-generation thermal barrier coatings(TBCs),and RETaO_(4)powders are hugely significant for synthesizing their coatings.The current research used chemical co-precipitation within an automated experimental device to synthesize RETaO_(4)(RE=Nd,Sm,Gd,Ho,Er)powders.The device automatically monitored and controlled the solutions'pH,improving the chemical co-precipitation efficiency.The crystal structure and microstructure of the RETaO_(4)powders can be controlled by changing the annealing temperature,and the materials undergo an m'-m phase transition.The m'-RETaO_(4)powders exhibit nano-size grains,while m-RETaO_(4)powders evince micron-size grains,altered by the annealing temperatures.A simultaneous thermal analysis es-timates the reversive ferroelastic tetragonal-monoclinic phase transition temperatures.Overall,this research focuses on the synthesis,crystal structures,microstructures,and phase transition of the fabricated RETaO_(4)powders.展开更多
The reaction of Mg^(2+)and 5-{1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid(H_(2)L)leads to two metal-organic frameworks,[Mg(L)(DMF)_(2)(H_(2)O)_(2)]_(2)·5DMF·2H_(2)O(1)with a 1D structure and...The reaction of Mg^(2+)and 5-{1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid(H_(2)L)leads to two metal-organic frameworks,[Mg(L)(DMF)_(2)(H_(2)O)_(2)]_(2)·5DMF·2H_(2)O(1)with a 1D structure and[Mg_(2)(L)_(2)(DMSO)_(3)(H_(2)O)](2)with a 2D(4,4)-net structure.Interestingly,the two compounds exhibit distinct luminescent responses to external mechanical stimuli.1 exhibited exceptional resistance mechanical chromic luminescence(RMCL),which can be attributed to the predominant hydrogen bonds and the presence of high-boiling-point solvent molecules within its structure.2 had a reversible MCL property,which can be attributed to the dominantπ-πweak interactions,coupled with the reversible destruction/restoration of its crystallinity under grinding/fumigation.CCDC:2410963,1;2410964,2.展开更多
Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfull...Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.展开更多
All-inorganic perovskites based on cesium-lead-bromine(Cs-Pb-Br)have been a prominent research focus in optoelectronics in recent years.The optimisation and tunability of their macroscopic properties exploit the confo...All-inorganic perovskites based on cesium-lead-bromine(Cs-Pb-Br)have been a prominent research focus in optoelectronics in recent years.The optimisation and tunability of their macroscopic properties exploit the conformational flexibility,resulting in various crystal structures.Varying synthesis parameters can yield distinct crystal structures from Cs,Pb,and Br precursors,and manually exploring the relationship between these synthesis parameters and the resulting crystal structure is both labour-intensive and time-consuming.Machine learning(ML)can rapidly uncover insights and drive discoveries in chemical synthesis with the support of data,significantly reducing both the cost and development cycle of materials.Here,we gathered synthesis parameters from published literature(220 synthesis runs)and implemented eight distinct ML models,including eXtreme Gradient Boosting(XGB),Decision Tree(DT),Support Vector Machine(SVM),Random Forest(RF),Naïve Bayes(NB),Logistic Regression(LR),Gradient Boosting(GB),and K-Nearest(KN)to classify and predict Cs-Pb-Br crystal structures from given synthesis parameters.Validation accuracy,precision,F1 score,recall,and average area under the curve(AUC)are employed to evaluate these ML models.The XGB model exhibited the best performance,achieving a validation accuracy of 0.841.The trained XGB model was subsequently utilised to predict the structure from 10 experimental runs using a randomised set of parameters,achieving a testing accuracy of 0.8.The results indicate that the Cs/Pb molar ratio,reaction time,and the concentration of organic compounds(ligands)play crucial roles in synthesising various crystal structures of Cs-Pb-Br.This study demonstrates a significant decrease in effort required for experimental procedures and builds a foundational basis for predicting crystal structures from synthesis parameters.展开更多
In this study,a comprehensive analysis of microstructural features,morphology,crystal structures,and interface structures of long-period stacking ordered(LPSO)structures in a non-equilibrium Mg_(97)Zn_(1)Y_(16)Ca_(0.4...In this study,a comprehensive analysis of microstructural features,morphology,crystal structures,and interface structures of long-period stacking ordered(LPSO)structures in a non-equilibrium Mg_(97)Zn_(1)Y_(16)Ca_(0.4)alloy cast in a steel mold was carried out.The addition of Ca element plays an important role in the refinement of LPSO structure.The result reveals new poly-types including 20H F2F2F4,60R(F2F3F3)_(3),and 66H F2F3F3F2(F6)_(4)featuring a 6-Mg structure,alongside the prevalent 18R and 14H LPSO structures.The incoherent interface between 20H and the Mg matrix is split into two dislocation arrays,leading to the formation of a segment of 60R_(1).Moreover,the superstructure 116L,designated as(F2)_(18)F4,is formed through the ordered distribution of F4 stacking faults in 18R.展开更多
Novel ordered intermetallic compounds have stimulated much interest.Ru–Al alloys are a prominent class of hightemperature structural materials,but the experimentally reported crystal structure of the intermetallic Ru...Novel ordered intermetallic compounds have stimulated much interest.Ru–Al alloys are a prominent class of hightemperature structural materials,but the experimentally reported crystal structure of the intermetallic Ru_(2)Al_(5) phase remains elusive and debatable.To resolve this controversy,we extensively explored the crystal structures of Ru_(2)Al_(5) using first-principles calculations combined with crystal structure prediction technique.Among the calculated x-ray diffraction patterns and lattice parameters of five candidate Ru2Al5structures,those of the orthorhombic Pmmn structure best aligned with recent experimental results.The structural stabilities of the five Ru_(2)Al_(5)structures were confirmed through formation energy,elastic constants,and phonon spectrum calculations.We also comprehensively analyzed the mechanical and electronic properties of the five candidates.This work can guide the exploration of novel ordered intermetallic compounds in Ru–Al alloys.展开更多
Two new binary cocrystals formulated as POM·NBA 1 and POM·DNSA 2 （POM = 3-methyl-4-nitro-pyridine-N-oxide, NBA = o-nitrobenzoic acid, DNSA = 3,5-dinitrosalicylic acid） have been successfully synthesized an...Two new binary cocrystals formulated as POM·NBA 1 and POM·DNSA 2 （POM = 3-methyl-4-nitro-pyridine-N-oxide, NBA = o-nitrobenzoic acid, DNSA = 3,5-dinitrosalicylic acid） have been successfully synthesized and characterized by elemental analysis, IR and X-ray single- crystal diffraction analysis. The crystal of 1 crystallizes in triclinic, space group P1, with a = 7.621（4）, b = 7.816（4）, c = 11.702（5） , α = 87.957（10）, β = 83.642（10）, γ = 81.535（10）o, C13H11N3O7, Z = 2, Mr = 321.25, V = 685.1（6） 3, Dc = 1.557 g/cm3, F（000） = 332, μ = 0.129 mm-1, the final R = 0.0632 and wR = 0.0831. The crystal of 2 crystallizes in monoclinic, space group P21/c with a = 14.910（9）, b = 5.904（3）, c =19.321（12） , β = 110.583（10）o, C13H10N4O10, Z = 4, Mr = 382.25, V = 1592.1（16） 3, Dc = 1.595 g/cm3, F（000） = 784, μ = 0.140 mm-1, the final R = 0.0598 and wR = 0.1589. Further structure analysis reveals that the POM with NBA and DNSA molecules in 1 and 2 are linked into 3D structures by the combination of strong O-H…O and weak C-H…O hydrogen bonds, π…π stackings and diverse short contacts, in which different C-H…O weak hydrogen bonds may play a key role in constructing the network structures.展开更多
Subtle microstructure design and an appropriate multicomponent strategy are essential for advanced electromagnetic absorbing(EMA)materials with a wide effective absorption bandwidth(EAB)and intense absorption.However,...Subtle microstructure design and an appropriate multicomponent strategy are essential for advanced electromagnetic absorbing(EMA)materials with a wide effective absorption bandwidth(EAB)and intense absorption.However,sophisticated environments restrict the range of applications for EMA materials.Herein,three hollow spherical bifunctional CoSx/MnS/C nanocomposites with different crystal structures were constructed via cation exchange and subsequent vulcanization.The manganese sulfide and carbon generated during vulcanization exhibit a narrow band gap and enhanced conductivity,thereby facilitating conductive loss.The presence of cobalt sulfide facilitates the improvement of magnetic loss.More importantly,there is a potential difference between different phases at the heterogeneous interface,resulting in a region of space charge,which is conducive to interfacial polarization.The 3D hollow structure and heterogeneous dielectric/magnetic interfaces benefit the predominant EMA performance by forming perfect impedance matching,interface polarization,conduction loss,and magnetic loss effects.Specifically,an optimal reflection loss(RL)of-51.31 dB at 10.72 GHz and an effective EAB of 5.92 GHz at 2.1 mm can be achieved for Co_(1-x) S/MnS/C nanocomposite.Moreover,the nanocomposites maintained promising self-anticorrosion properties in simulated seawater environments.Transition metal sulfides with superior self-anticorrosion properties provide a pathway to efficient wave-absorbing materials in complicated environments.展开更多
Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmeth...Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.展开更多
Dynamic covalent imine reactions between 2,3-dimethoxy-[1,1:4,1-terphenyl]-3,3,5,5-tetracarbaldehyde(DMTT)and cyclohexanediamine,p-phenylenediamine,and benzidine,respectively,generate a porous organic cage(DMPOC)and t...Dynamic covalent imine reactions between 2,3-dimethoxy-[1,1:4,1-terphenyl]-3,3,5,5-tetracarbaldehyde(DMTT)and cyclohexanediamine,p-phenylenediamine,and benzidine,respectively,generate a porous organic cage(DMPOC)and two covalent organic frameworks(COFs),USTB-29,and USTB-30.DMPOC shows a[3+6]topological cage-like structure according to single crystal X-ray diffraction result.In contrast,both microcrystalline USTB-29 and USTB-30 exhibit two-dimensional monoporous structures in an eclipsed AA stacking style based on powder X-ray diffraction and theoretical simulations.In addition,DMPOC is capable of efficiently absorbing the iodine vapor with an outstanding uptake of 5.10 g/g,much higher than that of USTB-29(3.07 g/g)and USTB-30(3.16 g/g).Cage to COFs transformations have been realized from DMPOC to USTB-29 and USTB-30 via the imine bond exchange with slightly increased iodine vapor uptake.Mechanism investigations uncover that both nitrogen and oxygen atoms of POC and COFs contribute to iodine vapor capture due to the formation of charge transfer matter,and loose interaction introducing adaptive expanding voids of DMPOC is suggested to capture more iodine vapor than that of COFs with strongπ-πinteractions.展开更多
A novel compound(H_(2)L)SCN(5⁃methyl⁃3⁃phenyl⁃2H⁃pyrazol⁃1⁃ium thiocyanate)has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol.Two zinccomplexes[Zn(HL)_(2)(NCS)(CH_(3)COO)](1)and[Zn_(...A novel compound(H_(2)L)SCN(5⁃methyl⁃3⁃phenyl⁃2H⁃pyrazol⁃1⁃ium thiocyanate)has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol.Two zinccomplexes[Zn(HL)_(2)(NCS)(CH_(3)COO)](1)and[Zn_(2)(L)_(2)(HL)_(2)(NCS)_(2)]_(2)·2CH_(3)OH(2)have been synthesized by the coordination reactions of Zn(OAc)_(2)·2H_(2)O or ZnCl_(2)with(H_(2)L)SCN under reflux conditions.Elemental analyses and single⁃crystal X⁃ray diffraction have con⁃firmed the structures of the synthesized compounds.The(H_(2)L)SCN ligand and complex 1 pertain to the triclinic sys⁃tem with space group P1,while complex 2 belongs to the monoclinic system with space group P2_(1)/n.Additionally,the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bac⁃terial strains(Candida albicans,Staphylococcus aureus,and Escherichia coli).The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria,and the complexes possessed stronger antibac⁃terial activities against the same bacteria than the free ligand.CCDC:2190252,(H2L)SCN;2190253,1;2190256,2.展开更多
Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,...Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.展开更多
In the traditional process, m-phenylenediamine reacts with fuming sulfuric acid at high temperature to get intermediates, and then after dehydration occurs intramolecular rearrangement to get 2,4-diaminobenzenesulfoni...In the traditional process, m-phenylenediamine reacts with fuming sulfuric acid at high temperature to get intermediates, and then after dehydration occurs intramolecular rearrangement to get 2,4-diaminobenzenesulfonic acid. Traditional methods need to consume a lot of fuming sulfuric acid or concentrated sulfuric acid, resulting in high industrial large-scale production cost, more waste, and posing a serious environmental pollution risk. In this thesis, three different sulfonation reagents were used for the sulfonation reaction of m-phenylenediamine, and the reaction mechanisms and crystal structures of the three pathways were investigated. The three routes are: 1) one-step synthesis of monosulfonated compound 1 from raw material and sulfur trioxide (SO<sub>3</sub>);2) rapid reaction of raw material and chlorosulfonic acid to synthesize bisulfonated compound 2;3) direct eutectic crystallization of raw material and ordinary sulfuric acid to obtain compound 3. The crystal structure of the compounds synthesized by three paths was analyzed by X-ray single crystal diffraction, and compound 1 was characterized by NMR, Fourier infrared spectra, UV-visible spectrum and Mass spectrometry. The one-step synthesis of SO<sub>3</sub> as a sulfonation reagent has the advantages of mild reaction conditions, simple operation and low cost.展开更多
To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bisp...To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.展开更多
A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal st...A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.展开更多
Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene...Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide,H_(2)L_(2)=(E)-N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide,Hdbm=dibenzoylmethane,have been constructed by adopting the solvothermal method.Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd^(3+)ions,two dbm-ions,two CH_(3)OH molecules,and two polydentate Schiff-base ligands(HL_(1)^(2-)or L_(2)^(2-)).In addition,complex 1 contains four free methanol molecules,whereas complex 2 harbors two free methanol molecules.By investigating the interactions between complexes 1 and 2 and four types of bacteria(Bacillus subtilis,Escherichia coli,Staphylococcus aureus,Candida albicans),it was found that both complexes 1 and 2 exhibited potent antibacte-rial activities.The interaction mechanisms between the ligands H_(3)L_(1),H_(2)L_(2),complexes 1 and 2,and calf thymus DNA(CT-DNA)were studied using ultraviolet-visible spectroscopy,fluorescence titration,and cyclic voltammetry.The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules,thereby inhibiting bacterial proliferation to achieve the antibacterial effects.CCDC:2401116,1;2401117,2.展开更多
Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions an...Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.展开更多
Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-d...Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-dpe)·7H_(2)O(3),(1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH_(2))2(H_(2)O)_(2)](4),and[Cd(1,4-ndpaH_(2))(H_(2)O)]·H_(2)O(5),have been synthesized from the selfassembly reactions of 1,4-naphthalenediphosphonic acid(1,4-ndpaH4)with Cd(NO3)2·4H_(2)O by introducing auxiliary ligands with variation of rigidity,such as 4,4'-bipyridine(4,4'-bpy),1,4-bis(1-imidazolyl)benzene(1,4-bib),1,2-di(4-pyridyl)ethylene(1,2-dpe),1,3-di(4-pyridyl)propane(1,3-dpp),and bis(imidazol-1-ylmethyl)benzene(1,2-bix),respectively.Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework,in which the{Cd3(PO2)2}trimers made up of corner-sharing two{CdO4N2}and one{CdO6}octahedra are connected by phosphonate groups,forming a ribbon,which are cross-linked by 4,4'-bipy ligands,forming a 2D layer.Compound 2 shows a 3D open-framework structure,where chains of corner-sharing{CdO4N}trigonal bipyramids and{PO3C}tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups.A 1D ladder-like chain structure is found in compound 3,where the ladder-like chains made up of corner-sharing{CdO5N}octahedra and{PO3C}tetra hedra are connected by 1,4-ndpaH_(2)^(2-).Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure,which is formed by ligand crosslinking double metal chains.Interestingly,In 4,flexible 1,2-bix was singly protonated,as vip molecules,filled between layer and layer,while flexible ligand 1,3-dpp is absent in 5.Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.展开更多
A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]py...A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.展开更多
Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6...Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.展开更多
基金the Rare and Precious Metals Material Genetic Engineering Project of Yunnan Province(202102AB080019-1)National Key Research and Development Program of China(2022YFB3708600)the National Natural Science Foundation of China(91960103).
文摘Ferroelastic rare earth tantalates(RETaO_(4))are widely researched as the next-generation thermal barrier coatings(TBCs),and RETaO_(4)powders are hugely significant for synthesizing their coatings.The current research used chemical co-precipitation within an automated experimental device to synthesize RETaO_(4)(RE=Nd,Sm,Gd,Ho,Er)powders.The device automatically monitored and controlled the solutions'pH,improving the chemical co-precipitation efficiency.The crystal structure and microstructure of the RETaO_(4)powders can be controlled by changing the annealing temperature,and the materials undergo an m'-m phase transition.The m'-RETaO_(4)powders exhibit nano-size grains,while m-RETaO_(4)powders evince micron-size grains,altered by the annealing temperatures.A simultaneous thermal analysis es-timates the reversive ferroelastic tetragonal-monoclinic phase transition temperatures.Overall,this research focuses on the synthesis,crystal structures,microstructures,and phase transition of the fabricated RETaO_(4)powders.
文摘The reaction of Mg^(2+)and 5-{1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid(H_(2)L)leads to two metal-organic frameworks,[Mg(L)(DMF)_(2)(H_(2)O)_(2)]_(2)·5DMF·2H_(2)O(1)with a 1D structure and[Mg_(2)(L)_(2)(DMSO)_(3)(H_(2)O)](2)with a 2D(4,4)-net structure.Interestingly,the two compounds exhibit distinct luminescent responses to external mechanical stimuli.1 exhibited exceptional resistance mechanical chromic luminescence(RMCL),which can be attributed to the predominant hydrogen bonds and the presence of high-boiling-point solvent molecules within its structure.2 had a reversible MCL property,which can be attributed to the dominantπ-πweak interactions,coupled with the reversible destruction/restoration of its crystallinity under grinding/fumigation.CCDC:2410963,1;2410964,2.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
基金the Italian Space Agency(Agenzia Spaziale Italiana,ASI)in the framework of the Research Day“Giornate della Ricerca Spaziale”initiative through the contract ASI N.2023-4-U.0.
文摘All-inorganic perovskites based on cesium-lead-bromine(Cs-Pb-Br)have been a prominent research focus in optoelectronics in recent years.The optimisation and tunability of their macroscopic properties exploit the conformational flexibility,resulting in various crystal structures.Varying synthesis parameters can yield distinct crystal structures from Cs,Pb,and Br precursors,and manually exploring the relationship between these synthesis parameters and the resulting crystal structure is both labour-intensive and time-consuming.Machine learning(ML)can rapidly uncover insights and drive discoveries in chemical synthesis with the support of data,significantly reducing both the cost and development cycle of materials.Here,we gathered synthesis parameters from published literature(220 synthesis runs)and implemented eight distinct ML models,including eXtreme Gradient Boosting(XGB),Decision Tree(DT),Support Vector Machine(SVM),Random Forest(RF),Naïve Bayes(NB),Logistic Regression(LR),Gradient Boosting(GB),and K-Nearest(KN)to classify and predict Cs-Pb-Br crystal structures from given synthesis parameters.Validation accuracy,precision,F1 score,recall,and average area under the curve(AUC)are employed to evaluate these ML models.The XGB model exhibited the best performance,achieving a validation accuracy of 0.841.The trained XGB model was subsequently utilised to predict the structure from 10 experimental runs using a randomised set of parameters,achieving a testing accuracy of 0.8.The results indicate that the Cs/Pb molar ratio,reaction time,and the concentration of organic compounds(ligands)play crucial roles in synthesising various crystal structures of Cs-Pb-Br.This study demonstrates a significant decrease in effort required for experimental procedures and builds a foundational basis for predicting crystal structures from synthesis parameters.
基金supported by the open research fund of Songshan Lake Materials Laboratory(No.2022SLABFN08)Guangxi Science and Technology Base and Talents Special Project(Nos.Guike AD20297034 and AD21220053)+2 种基金the National Natural Science Foundation of China(No.51801214 and 52171021)the Research Start-up Funding from Guangxi University of Science and Technology(No.03200150)the Middle-aged and Young Teachers’Basic Ability Promotion Project of Guangxi(No.2022KY0329)。
文摘In this study,a comprehensive analysis of microstructural features,morphology,crystal structures,and interface structures of long-period stacking ordered(LPSO)structures in a non-equilibrium Mg_(97)Zn_(1)Y_(16)Ca_(0.4)alloy cast in a steel mold was carried out.The addition of Ca element plays an important role in the refinement of LPSO structure.The result reveals new poly-types including 20H F2F2F4,60R(F2F3F3)_(3),and 66H F2F3F3F2(F6)_(4)featuring a 6-Mg structure,alongside the prevalent 18R and 14H LPSO structures.The incoherent interface between 20H and the Mg matrix is split into two dislocation arrays,leading to the formation of a segment of 60R_(1).Moreover,the superstructure 116L,designated as(F2)_(18)F4,is formed through the ordered distribution of F4 stacking faults in 18R.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11965005 and 11964026)the Natural Science Basic Research Plan in Shaanxi Province,China(Grant Nos.2023-JC-YB-021 and 2022JM-035)+1 种基金the Fundamental Research Funds for the Central Universitiesthe 111 Project(Grant No.B17035)。
文摘Novel ordered intermetallic compounds have stimulated much interest.Ru–Al alloys are a prominent class of hightemperature structural materials,but the experimentally reported crystal structure of the intermetallic Ru_(2)Al_(5) phase remains elusive and debatable.To resolve this controversy,we extensively explored the crystal structures of Ru_(2)Al_(5) using first-principles calculations combined with crystal structure prediction technique.Among the calculated x-ray diffraction patterns and lattice parameters of five candidate Ru2Al5structures,those of the orthorhombic Pmmn structure best aligned with recent experimental results.The structural stabilities of the five Ru_(2)Al_(5)structures were confirmed through formation energy,elastic constants,and phonon spectrum calculations.We also comprehensively analyzed the mechanical and electronic properties of the five candidates.This work can guide the exploration of novel ordered intermetallic compounds in Ru–Al alloys.
基金supported by the National Natural Science Foundation of China (No. 50872057)
文摘Two new binary cocrystals formulated as POM·NBA 1 and POM·DNSA 2 （POM = 3-methyl-4-nitro-pyridine-N-oxide, NBA = o-nitrobenzoic acid, DNSA = 3,5-dinitrosalicylic acid） have been successfully synthesized and characterized by elemental analysis, IR and X-ray single- crystal diffraction analysis. The crystal of 1 crystallizes in triclinic, space group P1, with a = 7.621（4）, b = 7.816（4）, c = 11.702（5） , α = 87.957（10）, β = 83.642（10）, γ = 81.535（10）o, C13H11N3O7, Z = 2, Mr = 321.25, V = 685.1（6） 3, Dc = 1.557 g/cm3, F（000） = 332, μ = 0.129 mm-1, the final R = 0.0632 and wR = 0.0831. The crystal of 2 crystallizes in monoclinic, space group P21/c with a = 14.910（9）, b = 5.904（3）, c =19.321（12） , β = 110.583（10）o, C13H10N4O10, Z = 4, Mr = 382.25, V = 1592.1（16） 3, Dc = 1.595 g/cm3, F（000） = 784, μ = 0.140 mm-1, the final R = 0.0598 and wR = 0.1589. Further structure analysis reveals that the POM with NBA and DNSA molecules in 1 and 2 are linked into 3D structures by the combination of strong O-H…O and weak C-H…O hydrogen bonds, π…π stackings and diverse short contacts, in which different C-H…O weak hydrogen bonds may play a key role in constructing the network structures.
基金financially supported by the National Natu-ral Science Foundation of China(Nos.52377026 and 52301192)the Natural Science Foundation of Shandong Province(No.ZR2019YQ24)+3 种基金the Taishan Scholars and Young Experts Program of Shandong Province(No.tsqn202103057)the Qingchuang Talents Induction Program of Shandong Higher Education Institution(Re-search and Innovation Team of Structural-Functional Polymer Com-posites)the Special Financial of Shandong Province(Structural De-sign of High-efficiency Electromagnetic Wave-absorbing Composite Materials and Construction of Shandong Provincial Talent Teams)the“Sanqin Scholars”Innovation Teams Project of Shaanxi Province(Clean Energy Materials and High-Performance Devices Innovation Team of Shaanxi Dongling Smelting Co.,Ltd.).
文摘Subtle microstructure design and an appropriate multicomponent strategy are essential for advanced electromagnetic absorbing(EMA)materials with a wide effective absorption bandwidth(EAB)and intense absorption.However,sophisticated environments restrict the range of applications for EMA materials.Herein,three hollow spherical bifunctional CoSx/MnS/C nanocomposites with different crystal structures were constructed via cation exchange and subsequent vulcanization.The manganese sulfide and carbon generated during vulcanization exhibit a narrow band gap and enhanced conductivity,thereby facilitating conductive loss.The presence of cobalt sulfide facilitates the improvement of magnetic loss.More importantly,there is a potential difference between different phases at the heterogeneous interface,resulting in a region of space charge,which is conducive to interfacial polarization.The 3D hollow structure and heterogeneous dielectric/magnetic interfaces benefit the predominant EMA performance by forming perfect impedance matching,interface polarization,conduction loss,and magnetic loss effects.Specifically,an optimal reflection loss(RL)of-51.31 dB at 10.72 GHz and an effective EAB of 5.92 GHz at 2.1 mm can be achieved for Co_(1-x) S/MnS/C nanocomposite.Moreover,the nanocomposites maintained promising self-anticorrosion properties in simulated seawater environments.Transition metal sulfides with superior self-anticorrosion properties provide a pathway to efficient wave-absorbing materials in complicated environments.
文摘Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.
基金financially supported by the Natural Science Foundation of China(Nos.22235001,22175020,22131005,and 22261132512)Xiaomi Young Scholar Program+1 种基金the Fundamental Research Funds for the Central UniversitiesUniversity of Science and Technology Beijing。
文摘Dynamic covalent imine reactions between 2,3-dimethoxy-[1,1:4,1-terphenyl]-3,3,5,5-tetracarbaldehyde(DMTT)and cyclohexanediamine,p-phenylenediamine,and benzidine,respectively,generate a porous organic cage(DMPOC)and two covalent organic frameworks(COFs),USTB-29,and USTB-30.DMPOC shows a[3+6]topological cage-like structure according to single crystal X-ray diffraction result.In contrast,both microcrystalline USTB-29 and USTB-30 exhibit two-dimensional monoporous structures in an eclipsed AA stacking style based on powder X-ray diffraction and theoretical simulations.In addition,DMPOC is capable of efficiently absorbing the iodine vapor with an outstanding uptake of 5.10 g/g,much higher than that of USTB-29(3.07 g/g)and USTB-30(3.16 g/g).Cage to COFs transformations have been realized from DMPOC to USTB-29 and USTB-30 via the imine bond exchange with slightly increased iodine vapor uptake.Mechanism investigations uncover that both nitrogen and oxygen atoms of POC and COFs contribute to iodine vapor capture due to the formation of charge transfer matter,and loose interaction introducing adaptive expanding voids of DMPOC is suggested to capture more iodine vapor than that of COFs with strongπ-πinteractions.
文摘A novel compound(H_(2)L)SCN(5⁃methyl⁃3⁃phenyl⁃2H⁃pyrazol⁃1⁃ium thiocyanate)has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol.Two zinccomplexes[Zn(HL)_(2)(NCS)(CH_(3)COO)](1)and[Zn_(2)(L)_(2)(HL)_(2)(NCS)_(2)]_(2)·2CH_(3)OH(2)have been synthesized by the coordination reactions of Zn(OAc)_(2)·2H_(2)O or ZnCl_(2)with(H_(2)L)SCN under reflux conditions.Elemental analyses and single⁃crystal X⁃ray diffraction have con⁃firmed the structures of the synthesized compounds.The(H_(2)L)SCN ligand and complex 1 pertain to the triclinic sys⁃tem with space group P1,while complex 2 belongs to the monoclinic system with space group P2_(1)/n.Additionally,the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bac⁃terial strains(Candida albicans,Staphylococcus aureus,and Escherichia coli).The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria,and the complexes possessed stronger antibac⁃terial activities against the same bacteria than the free ligand.CCDC:2190252,(H2L)SCN;2190253,1;2190256,2.
文摘Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.
文摘In the traditional process, m-phenylenediamine reacts with fuming sulfuric acid at high temperature to get intermediates, and then after dehydration occurs intramolecular rearrangement to get 2,4-diaminobenzenesulfonic acid. Traditional methods need to consume a lot of fuming sulfuric acid or concentrated sulfuric acid, resulting in high industrial large-scale production cost, more waste, and posing a serious environmental pollution risk. In this thesis, three different sulfonation reagents were used for the sulfonation reaction of m-phenylenediamine, and the reaction mechanisms and crystal structures of the three pathways were investigated. The three routes are: 1) one-step synthesis of monosulfonated compound 1 from raw material and sulfur trioxide (SO<sub>3</sub>);2) rapid reaction of raw material and chlorosulfonic acid to synthesize bisulfonated compound 2;3) direct eutectic crystallization of raw material and ordinary sulfuric acid to obtain compound 3. The crystal structure of the compounds synthesized by three paths was analyzed by X-ray single crystal diffraction, and compound 1 was characterized by NMR, Fourier infrared spectra, UV-visible spectrum and Mass spectrometry. The one-step synthesis of SO<sub>3</sub> as a sulfonation reagent has the advantages of mild reaction conditions, simple operation and low cost.
文摘To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.
文摘A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.
文摘Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide,H_(2)L_(2)=(E)-N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide,Hdbm=dibenzoylmethane,have been constructed by adopting the solvothermal method.Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd^(3+)ions,two dbm-ions,two CH_(3)OH molecules,and two polydentate Schiff-base ligands(HL_(1)^(2-)or L_(2)^(2-)).In addition,complex 1 contains four free methanol molecules,whereas complex 2 harbors two free methanol molecules.By investigating the interactions between complexes 1 and 2 and four types of bacteria(Bacillus subtilis,Escherichia coli,Staphylococcus aureus,Candida albicans),it was found that both complexes 1 and 2 exhibited potent antibacte-rial activities.The interaction mechanisms between the ligands H_(3)L_(1),H_(2)L_(2),complexes 1 and 2,and calf thymus DNA(CT-DNA)were studied using ultraviolet-visible spectroscopy,fluorescence titration,and cyclic voltammetry.The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules,thereby inhibiting bacterial proliferation to achieve the antibacterial effects.CCDC:2401116,1;2401117,2.
文摘Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.
文摘Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-dpe)·7H_(2)O(3),(1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH_(2))2(H_(2)O)_(2)](4),and[Cd(1,4-ndpaH_(2))(H_(2)O)]·H_(2)O(5),have been synthesized from the selfassembly reactions of 1,4-naphthalenediphosphonic acid(1,4-ndpaH4)with Cd(NO3)2·4H_(2)O by introducing auxiliary ligands with variation of rigidity,such as 4,4'-bipyridine(4,4'-bpy),1,4-bis(1-imidazolyl)benzene(1,4-bib),1,2-di(4-pyridyl)ethylene(1,2-dpe),1,3-di(4-pyridyl)propane(1,3-dpp),and bis(imidazol-1-ylmethyl)benzene(1,2-bix),respectively.Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework,in which the{Cd3(PO2)2}trimers made up of corner-sharing two{CdO4N2}and one{CdO6}octahedra are connected by phosphonate groups,forming a ribbon,which are cross-linked by 4,4'-bipy ligands,forming a 2D layer.Compound 2 shows a 3D open-framework structure,where chains of corner-sharing{CdO4N}trigonal bipyramids and{PO3C}tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups.A 1D ladder-like chain structure is found in compound 3,where the ladder-like chains made up of corner-sharing{CdO5N}octahedra and{PO3C}tetra hedra are connected by 1,4-ndpaH_(2)^(2-).Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure,which is formed by ligand crosslinking double metal chains.Interestingly,In 4,flexible 1,2-bix was singly protonated,as vip molecules,filled between layer and layer,while flexible ligand 1,3-dpp is absent in 5.Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.
文摘A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.
文摘Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.
