The dominant oxidation state for lanthanide ions is+3 due to the loss of 5d and 6s electrons from their shared configuration of[Xe]4f^(0-14)5d^(0-16)s(2).There are however several exceptions because of the completely ...The dominant oxidation state for lanthanide ions is+3 due to the loss of 5d and 6s electrons from their shared configuration of[Xe]4f^(0-14)5d^(0-16)s(2).There are however several exceptions because of the completely empty(Ce(Ⅳ)),half-filled(Eu(Ⅱ)),or fully filled(Yb(Ⅱ))4f subshell.As such,stable complexes are formed primarily with Ln(Ⅲ)ions[1].展开更多
The reaction behaviors of the title complexes have been studied in thesystem of dinitrogen gas by means of in situ IR. It has been found that some activefragments created at some stage of the thermal decomposition pro...The reaction behaviors of the title complexes have been studied in thesystem of dinitrogen gas by means of in situ IR. It has been found that some activefragments created at some stage of the thermal decomposition process of the complexes.enable.the acetic acid both obtained from the ligand of the complexes and introducedfrom outside to convert to acetone by decarboxylation. Their optimum reaction temperatures are of 240~270℃ for [Fe2MnO(O2CCH3),(H2O)3], 290~320 C for [Fe3Q(O2CCH3)6(H2O)3], 300~330℃ for [Fe2CoO(O2CCH3),(H2O)3] and 320~ 350℃for [Fe2NiO(O2CCH3)6(H2O)3], indicating the lowering sequence of the activity of active species. At the same time it has been shown that this activity may come from thejoined contributions of both the coordinating capability of the hetero-metals in the complexes and their structural factors. On the basis of the TGA, DTA and EI-MS data,the composition of the active fragments has been tentatively inferred as [Fe2MnO(O2CCH3)3-2].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
To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(...To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(6)](X_(2)pdt=(SCH_(2))_(2)CX_(2),X=Me,H)with aminodiphosphines(Ph_(2)PCH_(2))_(2)NY(Y=(CH_(2))_(2)OH,(CH_(2))_(3)OH)to obtain two new diiron aminophosphine complexes[Fe_(2)(L1)(μ-Me_(2)pdt)(CO)_(5)](1)and[Fe_(2)(L2)(μ-H_(2)pdt)(CO)_(5)](2),where L1=3-[(diphe-nylphosphaneyl)methyl]oxazolidine,L2=3-[(diphenylphosphaneyl)methyl]-1,3-oxazinane.Moreover,the structures of 1 and 2 have been fully confirmed by elemental analysis,spectroscopic techniques,and single-crystal X-ray diffraction.Using cyclic voltammetry(CV),we investigated the electrochemical redox performance and proton reduc-tion activities of 1 and 2 in acetic acid(HOAc).The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H 2 generation in the presence of HOAc.CCDC:2443967,1;2443969,2.展开更多
We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic ligh...We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.展开更多
Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal s...Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.展开更多
Transition metal possesses a unique d-orbital electronic structure,which imparts a diverse range of physical and chemical properties.These properties render them significant in fields such as chemistry and materials s...Transition metal possesses a unique d-orbital electronic structure,which imparts a diverse range of physical and chemical properties.These properties render them significant in fields such as chemistry and materials science.The distinctive optical,electrical,and magnetic properties of these complexes can be attributed to the variations in the quantity of d-orbital electrons,thereby influencing their spin and orbital characteristics.The d-orbitals facilitate the formation of stable multidirectional bonds with ligands,resulting in a variety of geometric structures and rich coordination chemistry.These interactions result in variations in energy levels,thereby producing diverse electrical properties,including low attenuation coefficients,high rectification ratios,and unique multichannel transmission.Moreover,the unpaired electrons inthe d-orbitals can give rise to diverse magnetic behaviors,leading to magnetic effects such as spin-related interfaces,switches,and magnetoresistance.This paves the way for extensive possibilities in the design and application of single-molecule devices.This review elaborates on singlemolecule physical properties of transition metal complexes,including length attenuation,rectification,multi-channel transmission,thermoelectric effect,and spin regulation,which are vital for the functionalization and regulation of molecular electronics.In addition,this review also explores the correlation between these physical properties and the electronic structure of transition metals,discussing the broad prospects of transition metal complexes in the fields of nanoelectronics,optoelectronics,and quantum technology.展开更多
In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactio...In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactions in the crystal state.Unexpectedly,substituting pyridine with the more extensivelyπ-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands.This alteration disrupts theπ-πinteractions between molecules,resulting in distinct optical properties upon exposure to external stimuli.By integrating these complexes into polymers,we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes.These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials,achieved through the employment of simple chromophores.展开更多
Photochromic materials attract significant attention for their applications in anticounterfeiting devices,optical switches and molecular sensors.However,the influence of solvent molecules,particularly coordinated solv...Photochromic materials attract significant attention for their applications in anticounterfeiting devices,optical switches and molecular sensors.However,the influence of solvent molecules,particularly coordinated solvents,on electron transfer(ET)photochromic systems remains poorly understood.In this study,we synthesized a series of isostructural metal-organic complexes(MOCs),[Mn(ADC)(L)]n(ADC=9,10-anthracenedicarboxylic acid,L=DMF for 1,DMA for 2,MEA for 3,and DMSO for 4)to investigate the solvent-chromic behavior.All these MOCs exhibit typical radical-induced chromism upon illumination with a xenon lamp at room temperature.It is worth noting that coordination solvent molecules significantly modulate the photochromic response rate.Among the compounds studied,compound 1 exhibits the fastest response,while compound 3 shows the slowest.This variation in rate correlates with differences in the optimal ET path length within their structures.Specifically,solvent molecules regulate the C-H…π interaction distance through their steric hindrance and electronic prop-erties.Shorter C-H…π paths facilitate more efficient ET upon photoexcitation,thus leading to faster photo-chromic response rates.Furthermore,illumination actuates magnetic couplings between photogenerated radicals and Mn^(2+)centers,resulting in a significant increase in room-temperature magnetization,demonstrating a photomagnetic response.This study demonstrates that coordinating solvent selection effectively controls photoinduced ET behavior,providing new insights for designing advanced photoactive materials.展开更多
Microstructure topology evolution during severe plastic deformation(SPD)is crucial for understanding and optimising the mechanical properties of metallic materials,though its prediction remains challenging.Herein,we c...Microstructure topology evolution during severe plastic deformation(SPD)is crucial for understanding and optimising the mechanical properties of metallic materials,though its prediction remains challenging.Herein,we combine discrete cell complexes(DCC),a fully discrete algebraic topology model-with finite element analysis(FEA)to simulate and analyse the microstructure topology of pure copper under SPD.Using DCC,we model the evolution of microstructure topology characterised by Betti numbers(β_(0),β_(1),β_(2))and Euler characteristic(χ).This captures key changes in GBNs and topological features within representative volume elements(RVEs)containing several hundred grains during SPD-induced recrystallisation.As SPD cycles increase,high-angle grain boundaries(HAGBs)progressively form.Topological analysis reveals an overall decrease in β_(0)values,indicating fewer isolated HAGB substructures,while β_(2) values show a steady upward trend,highlighting new grain formation.Leveraging DCC-derived RVE topology and FEA-generated plastic strain data,we directly simulate the evolution and spatial distribution of microstructure topology and HAGB fraction in a copper tube undergoing cyclic parallel tube channel angular pressing(PTCAP),a representative SPD technique.Within the tube,the HAGB fraction continuously increases with PTCAP cycles,reflecting the microstructure’s gradual transition from subgrains to fully-formed grains.Analysis of Betti number distribution and evolution reveals the microstructural reconstruction mechanism underpinning this subgrain to grain transition during PTCAP.We further demonstrate the significant influence of spatially non-uniform plastic strain distribution on microstructure reconstruction kinetics.This study demonstrates a feasible approach for simulating microstructure topology evolution of metals processed by cyclic SPD via the integration of DCC and FEA.展开更多
The deep geologic processes between the Xing’an-Mongolian Orogenic Belt and the North China Craton in the Mesozoic are crucial to reveal the magmatic and tectonic evolution and their constraints on mineralization in ...The deep geologic processes between the Xing’an-Mongolian Orogenic Belt and the North China Craton in the Mesozoic are crucial to reveal the magmatic and tectonic evolution and their constraints on mineralization in the Jiapigou-Haigou collage zone.In this paper,We have presented the geochronology,geochemistry and Sr-Nd-Hf isotopic compositions of the Middle Jurassic granitic complexes in the Songjianghe area,Jilin Province.The granitic complexes can be categorized into four groups based on their geologic characteristics,with corresponding zircon U-Pb isotope ages of 177 Ma,172 Ma,169 Ma and 168-167 Ma,respectively.These granitoids exhibit calcalkaline to high-K calc-alkaline,metaluminous to weakly peraluminous Ⅰ-type characteristics,which show relative enrichment in LILEs(Rb,Sr,Ba)and depletion in HFSEs(Nb,Zr).Geochemical analyses reveal high initial^(87)Sr/^(86)Sr ratios of 0.70633-0.70740,coupled with lowεNd(t)values ranging from−10.65 to−13.23.The zircon analyses show similarly negativeεHf(t)values ranging from−16.9 to−3.2.The integrated elemental and Hf-Sr-Nd isotopic signatures demonstrate that the primitive magmas of the four group rocks were primarily derived from partial melting of thickened Archean lower crust,with the exception of the Group Ⅳ rocks,which exhibit significant evidence of crustal contamination.The residual mineral assemblages during the magma-forming process varied from amphibole to eclogite facies.These findings indicate that magmatism in the Songjianghe region likely resulted from the accretion and delamination of the Archean crust in the collage zone during the subduction of the Paleo-Pacific Plate beneath the Eurasian continent.展开更多
Intracellular bacteria(ICB),cloaked by the protective barriers of host cells,pose a formidable challenge to selective and efficient eradication.The employment of activatable photosensitizers based antibacterial photod...Intracellular bacteria(ICB),cloaked by the protective barriers of host cells,pose a formidable challenge to selective and efficient eradication.The employment of activatable photosensitizers based antibacterial photodynamic therapy(a PDT)holds significant potential for selective imaging and photo-inactivation of ICB while minimizing side effects on normal cells.Drawing inspiration from the elevated hypochlorous acid(HClO)levels in ICB infected phagocytes,herein we firstly designed and synthesized a series of HCl Oresponsive dinuclear Ru(Ⅱ)complexes(Ru1-Ru3)to achieve such a goal.Initially,the luminescence,^(1)O_(2)generation and a PDT activity of these Ru(Ⅱ)complexes were suppressed due to the quenching effect of the azo group,but were recovered after reaction with HCl O in solutions or within ICB infected phagocytes.The detailed results revealed that Ru1 and Ru3 could not only selectively visualize ICB,but also demonstrated remarkable a PDT activity against ICB,surpassing vancomycin both in vitro and in vivo.展开更多
Luminescent rare earth complexes based on interconfigurational 5d-4f transition have characteristics of adjustable emission spectra and short excited state lifetimes,showing potential applications in display,lighting ...Luminescent rare earth complexes based on interconfigurational 5d-4f transition have characteristics of adjustable emission spectra and short excited state lifetimes,showing potential applications in display,lighting and other fields.In this work,nine Ce^(3+),Eu^(2+)and Yb^(2+)complexes with spiro-bis(pyrazolyl)borate ligands,where pyrazolyl stands for pyrazolyl,3-methylpyrazolyl,or 3,5-dimethylpyrazolyl,were designed and synthesized.Ce^(3+)complexes show emission colors of blue,with photoluminescence quantum yields(PLQYs)of 94%-100%;Eu^(2+)complexes show emission colors of yellow-green,with PLQYs of 60%-78%;Yb^(2+)complexes show emission colors of orange or red,with PLQYs of 3%-4%.In addition,the crystal structures and theoretical calculation results show C-H…M interactions between bridge-head H atoms of the spirane and central metal ions in these complexes.It is found that the introduction of spirane with large steric hindrance and the existence of C-H…M interactions can improve the stability of the complexes in air atmosphere.展开更多
Two novel lanthanide-based coordination complexes,[LaL(Phen)(NO_(3))_(3)]n(1)and[Pr_(2)L_(2)(Phen)2(NO_(3))_(6)]n(2),were synthesized via a stoichiometric 1∶1∶1 reaction of lanthanide nitrates with tetraisopropyl 1,...Two novel lanthanide-based coordination complexes,[LaL(Phen)(NO_(3))_(3)]n(1)and[Pr_(2)L_(2)(Phen)2(NO_(3))_(6)]n(2),were synthesized via a stoichiometric 1∶1∶1 reaction of lanthanide nitrates with tetraisopropyl 1,2-ethylenediphosphate(L)and 1,10-phenanthroline(Phen)in a mixed ethanol-acetonitrile solvent system at room temperature.Their structures were determined by single-crystal X-ray diffraction(SCXRD)and further confirmed by infrared spectroscopy and elemental analysis.Thermogravimetric analysis(TGA)was used to assess thermal stability.Complexes 1 and 2 are both composed of O atoms provided by L and nitrate ions,formed a 10-coordinate configuration with the central Ln^(3+)(Ln=La,Pr)ion.Complex 1 forms a one-dimensional infinite chain connected by bridging ligands and constructs a complex three-dimensional stacking structure through hydrogen bonding andπ…πweak interactions.Complex 2 is connected by ligand L to form a one-dimensional infinite chain and through weak forces such as hydrogen bonding and C-H…πbonds,a novel three-dimensional stacking structure is formed by transverse and longitudinal crossing.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
Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxyge...Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxygen species(ROS),and aggregation-induced ROS quenching.To address these challenges,we present a molecular self-assembly strategy utilizing aggregation-induced emission(AIE)conjugates for metal complexes.As a proof of concept,we synthesized a mitochondrial-targeting cyclometalated Ir(Ⅲ)photosensitizer Ir-TPE.This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups.Ir-TPE readily self-assembles into nanoaggregates in aqueous solution,leading to a significant production of ROS upon light irradiation.Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria,resulting in mitochondrial DNA damage.This damage can lead to ferroptosis and autophagy,two forms of cell death that are highly cytotoxic to cancer cells.The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS,leading to a more pronounced cytotoxic effect.In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication.This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.展开更多
New solid complexes derived from the reaction of aroyl hydrazones, 2-hydroxy-1-naphthaldehyde benzene sulphonyl hydrazone (HNB), and 2-hydroxy-1-naphthaldehyde p-toluene sulphonyl hydrazone (HNT), with Co<sup>2+...New solid complexes derived from the reaction of aroyl hydrazones, 2-hydroxy-1-naphthaldehyde benzene sulphonyl hydrazone (HNB), and 2-hydroxy-1-naphthaldehyde p-toluene sulphonyl hydrazone (HNT), with Co<sup>2+</sup>, Ni<sup>2+</sup>, and Cu<sup>2+</sup> salts have been isolated and characterized using elemental analyses, spectral (UV-vis., IR), molar conductivity and magnetic measurements. The modes of bonding as well as the stereochemistry of the isolated solid complexes were discussed. The results suggested that both HNB and HNT coordinated with the metal ions in a bidentate manner forming a polymeric chain in the case of HNB while monocular complexes were formed in the case of HNT. The amounts of solvent in the solid complexes were determined by TGA measurements. Also, spectral studies of HNT with Co<sup>2+</sup> and Fe<sup>3+</sup> ions in solution were carried and the ratio of complexes was determined by continuous variation, molar ratio, and slope ratio methods. Moreover, the results suggest the formation of 1:1 (M:L) for Co<sup>2+</sup> ions while three species with ratios of 1:1, 1:2, and 2:1 (M:L) have been observed in the case of Ni<sup>2+</sup> and Cu<sup>2+</sup>. Finally, conductance titration of HNB and HNT with Co<sup>2+</sup> ion elucidates the formation of two species with ratios 1:1 and 1:2 (M:L) in the case of the Co<sup>2+</sup>-HNB while 1:1 (M:L) belongs to the Co<sup>2+</sup>-HNT system.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
To achieve efficient catalytic hydrogenation of CO_(2)to formate,we employed a transmetallation strategy to develop three novel iridium(Ⅰ)complexes,which feature N‑heterocyclic carbene‑nitrogen‑phosphine ligands(CNP)...To achieve efficient catalytic hydrogenation of CO_(2)to formate,we employed a transmetallation strategy to develop three novel iridium(Ⅰ)complexes,which feature N‑heterocyclic carbene‑nitrogen‑phosphine ligands(CNP)and a 1,5‑cyclooctadiene(cod)molecule:[Ir(cod)(κ^(3)‑CN^(im)P)]Cl(1⁃Cl),[Ir(cod)(κ^(3)‑CN^(im)P)]PF6(1⁃PF_(6)),and[Ir(cod)(κ^(3)‑CNHP)]Cl(2).The^(1)H NMR spectra,^(31)P NMR spectra,and high‑resolution mass spectra verify the successful synthesis of these three Ir(Ⅰ)‑CNP complexes.Furthermore,single‑crystal X‑ray diffraction analysis confirms the coordination geometry of 1⁃PF_(6).The strong Ir—C(NHC)bond suggests that the carbene carbon plays an enhanced anchoring role to iridium due to its strongσ‑donating ability,which helps stabilize the active metal species during CO_(2)hydrogenation.As a result,the Ir(Ⅰ)‑CNP complex exhibits remarkable activity and long catalytic lifetime for the hydrogenation of CO_(2)to formate,reaching a turnover number(TON)of 1.16×10^(6)after 150 h at a high temperature of 170℃,which was a relatively high value among all the Ir complexes.CCDC:2384071,1⁃PF_(6).展开更多
基金supported by the National Natural Science Foundation of China(22101116,92261203,21971106)Shenzhen Fundamental Research Program(JCYJ20220530115001002 and JCYJ20220818100417037).
文摘The dominant oxidation state for lanthanide ions is+3 due to the loss of 5d and 6s electrons from their shared configuration of[Xe]4f^(0-14)5d^(0-16)s(2).There are however several exceptions because of the completely empty(Ce(Ⅳ)),half-filled(Eu(Ⅱ)),or fully filled(Yb(Ⅱ))4f subshell.As such,stable complexes are formed primarily with Ln(Ⅲ)ions[1].
文摘The reaction behaviors of the title complexes have been studied in thesystem of dinitrogen gas by means of in situ IR. It has been found that some activefragments created at some stage of the thermal decomposition process of the complexes.enable.the acetic acid both obtained from the ligand of the complexes and introducedfrom outside to convert to acetone by decarboxylation. Their optimum reaction temperatures are of 240~270℃ for [Fe2MnO(O2CCH3),(H2O)3], 290~320 C for [Fe3Q(O2CCH3)6(H2O)3], 300~330℃ for [Fe2CoO(O2CCH3),(H2O)3] and 320~ 350℃for [Fe2NiO(O2CCH3)6(H2O)3], indicating the lowering sequence of the activity of active species. At the same time it has been shown that this activity may come from thejoined contributions of both the coordinating capability of the hetero-metals in the complexes and their structural factors. On the basis of the TGA, DTA and EI-MS data,the composition of the active fragments has been tentatively inferred as [Fe2MnO(O2CCH3)3-2].
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.
文摘To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(6)](X_(2)pdt=(SCH_(2))_(2)CX_(2),X=Me,H)with aminodiphosphines(Ph_(2)PCH_(2))_(2)NY(Y=(CH_(2))_(2)OH,(CH_(2))_(3)OH)to obtain two new diiron aminophosphine complexes[Fe_(2)(L1)(μ-Me_(2)pdt)(CO)_(5)](1)and[Fe_(2)(L2)(μ-H_(2)pdt)(CO)_(5)](2),where L1=3-[(diphe-nylphosphaneyl)methyl]oxazolidine,L2=3-[(diphenylphosphaneyl)methyl]-1,3-oxazinane.Moreover,the structures of 1 and 2 have been fully confirmed by elemental analysis,spectroscopic techniques,and single-crystal X-ray diffraction.Using cyclic voltammetry(CV),we investigated the electrochemical redox performance and proton reduc-tion activities of 1 and 2 in acetic acid(HOAc).The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H 2 generation in the presence of HOAc.CCDC:2443967,1;2443969,2.
文摘We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.
文摘Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.
基金financially supported by the National Key R&D Program of China(Nos.2021YFA1200102,2021YFA1200101,2023YFF1205803,2022YFE0128700)the National Natural Science Foundation of China(Nos.22173050,22150013,21727806,21933001)+1 种基金Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-202407)the Natural Science Foundation of Beijing(No.2222009)
文摘Transition metal possesses a unique d-orbital electronic structure,which imparts a diverse range of physical and chemical properties.These properties render them significant in fields such as chemistry and materials science.The distinctive optical,electrical,and magnetic properties of these complexes can be attributed to the variations in the quantity of d-orbital electrons,thereby influencing their spin and orbital characteristics.The d-orbitals facilitate the formation of stable multidirectional bonds with ligands,resulting in a variety of geometric structures and rich coordination chemistry.These interactions result in variations in energy levels,thereby producing diverse electrical properties,including low attenuation coefficients,high rectification ratios,and unique multichannel transmission.Moreover,the unpaired electrons inthe d-orbitals can give rise to diverse magnetic behaviors,leading to magnetic effects such as spin-related interfaces,switches,and magnetoresistance.This paves the way for extensive possibilities in the design and application of single-molecule devices.This review elaborates on singlemolecule physical properties of transition metal complexes,including length attenuation,rectification,multi-channel transmission,thermoelectric effect,and spin regulation,which are vital for the functionalization and regulation of molecular electronics.In addition,this review also explores the correlation between these physical properties and the electronic structure of transition metals,discussing the broad prospects of transition metal complexes in the fields of nanoelectronics,optoelectronics,and quantum technology.
基金supported by the National Natural Science Foundation of China(Nos.22201057 and 22472044)Zhejiang Provincial Natural Science Foundation of China(Nos.LR22B010001 and LQ23B010001)。
文摘In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactions in the crystal state.Unexpectedly,substituting pyridine with the more extensivelyπ-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands.This alteration disrupts theπ-πinteractions between molecules,resulting in distinct optical properties upon exposure to external stimuli.By integrating these complexes into polymers,we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes.These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials,achieved through the employment of simple chromophores.
基金supported by the National Natural Science Foundation of China(22171155,22571174)Natural Science Foundation of Shandong Province(ZR2022YQ07)+1 种基金Taishan Scholar Program(tsqn202306166)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF 2409).
文摘Photochromic materials attract significant attention for their applications in anticounterfeiting devices,optical switches and molecular sensors.However,the influence of solvent molecules,particularly coordinated solvents,on electron transfer(ET)photochromic systems remains poorly understood.In this study,we synthesized a series of isostructural metal-organic complexes(MOCs),[Mn(ADC)(L)]n(ADC=9,10-anthracenedicarboxylic acid,L=DMF for 1,DMA for 2,MEA for 3,and DMSO for 4)to investigate the solvent-chromic behavior.All these MOCs exhibit typical radical-induced chromism upon illumination with a xenon lamp at room temperature.It is worth noting that coordination solvent molecules significantly modulate the photochromic response rate.Among the compounds studied,compound 1 exhibits the fastest response,while compound 3 shows the slowest.This variation in rate correlates with differences in the optimal ET path length within their structures.Specifically,solvent molecules regulate the C-H…π interaction distance through their steric hindrance and electronic prop-erties.Shorter C-H…π paths facilitate more efficient ET upon photoexcitation,thus leading to faster photo-chromic response rates.Furthermore,illumination actuates magnetic couplings between photogenerated radicals and Mn^(2+)centers,resulting in a significant increase in room-temperature magnetization,demonstrating a photomagnetic response.This study demonstrates that coordinating solvent selection effectively controls photoinduced ET behavior,providing new insights for designing advanced photoactive materials.
基金support from Outstanding Youth Fund of Jiangsu Province(BK20240077)Key Project(Provincial-Municipal Joint)of Jiangsu Province(BK20243044)+2 种基金Fundamental Research Funds for the Central Universities(NE2024001)National Youth Talents Programof Chinaa project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Microstructure topology evolution during severe plastic deformation(SPD)is crucial for understanding and optimising the mechanical properties of metallic materials,though its prediction remains challenging.Herein,we combine discrete cell complexes(DCC),a fully discrete algebraic topology model-with finite element analysis(FEA)to simulate and analyse the microstructure topology of pure copper under SPD.Using DCC,we model the evolution of microstructure topology characterised by Betti numbers(β_(0),β_(1),β_(2))and Euler characteristic(χ).This captures key changes in GBNs and topological features within representative volume elements(RVEs)containing several hundred grains during SPD-induced recrystallisation.As SPD cycles increase,high-angle grain boundaries(HAGBs)progressively form.Topological analysis reveals an overall decrease in β_(0)values,indicating fewer isolated HAGB substructures,while β_(2) values show a steady upward trend,highlighting new grain formation.Leveraging DCC-derived RVE topology and FEA-generated plastic strain data,we directly simulate the evolution and spatial distribution of microstructure topology and HAGB fraction in a copper tube undergoing cyclic parallel tube channel angular pressing(PTCAP),a representative SPD technique.Within the tube,the HAGB fraction continuously increases with PTCAP cycles,reflecting the microstructure’s gradual transition from subgrains to fully-formed grains.Analysis of Betti number distribution and evolution reveals the microstructural reconstruction mechanism underpinning this subgrain to grain transition during PTCAP.We further demonstrate the significant influence of spatially non-uniform plastic strain distribution on microstructure reconstruction kinetics.This study demonstrates a feasible approach for simulating microstructure topology evolution of metals processed by cyclic SPD via the integration of DCC and FEA.
基金supported by the Natural Science Foundation of Jilin Province of China(grant no.20230101075JC)the National Natural Science Foundation of China(grant no.42072085).
文摘The deep geologic processes between the Xing’an-Mongolian Orogenic Belt and the North China Craton in the Mesozoic are crucial to reveal the magmatic and tectonic evolution and their constraints on mineralization in the Jiapigou-Haigou collage zone.In this paper,We have presented the geochronology,geochemistry and Sr-Nd-Hf isotopic compositions of the Middle Jurassic granitic complexes in the Songjianghe area,Jilin Province.The granitic complexes can be categorized into four groups based on their geologic characteristics,with corresponding zircon U-Pb isotope ages of 177 Ma,172 Ma,169 Ma and 168-167 Ma,respectively.These granitoids exhibit calcalkaline to high-K calc-alkaline,metaluminous to weakly peraluminous Ⅰ-type characteristics,which show relative enrichment in LILEs(Rb,Sr,Ba)and depletion in HFSEs(Nb,Zr).Geochemical analyses reveal high initial^(87)Sr/^(86)Sr ratios of 0.70633-0.70740,coupled with lowεNd(t)values ranging from−10.65 to−13.23.The zircon analyses show similarly negativeεHf(t)values ranging from−16.9 to−3.2.The integrated elemental and Hf-Sr-Nd isotopic signatures demonstrate that the primitive magmas of the four group rocks were primarily derived from partial melting of thickened Archean lower crust,with the exception of the Group Ⅳ rocks,which exhibit significant evidence of crustal contamination.The residual mineral assemblages during the magma-forming process varied from amphibole to eclogite facies.These findings indicate that magmatism in the Songjianghe region likely resulted from the accretion and delamination of the Archean crust in the collage zone during the subduction of the Paleo-Pacific Plate beneath the Eurasian continent.
基金supported by National Natural Science Foundation of China(No.22371289)。
文摘Intracellular bacteria(ICB),cloaked by the protective barriers of host cells,pose a formidable challenge to selective and efficient eradication.The employment of activatable photosensitizers based antibacterial photodynamic therapy(a PDT)holds significant potential for selective imaging and photo-inactivation of ICB while minimizing side effects on normal cells.Drawing inspiration from the elevated hypochlorous acid(HClO)levels in ICB infected phagocytes,herein we firstly designed and synthesized a series of HCl Oresponsive dinuclear Ru(Ⅱ)complexes(Ru1-Ru3)to achieve such a goal.Initially,the luminescence,^(1)O_(2)generation and a PDT activity of these Ru(Ⅱ)complexes were suppressed due to the quenching effect of the azo group,but were recovered after reaction with HCl O in solutions or within ICB infected phagocytes.The detailed results revealed that Ru1 and Ru3 could not only selectively visualize ICB,but also demonstrated remarkable a PDT activity against ICB,surpassing vancomycin both in vitro and in vivo.
基金Project supported by the National Key R&D Program of China(2021YFB3500400,2021YFB3501800,2022YFB3503700,2023YFB3506901)the National Natural Science Foundation of China(22071003,92156016,62104013)。
文摘Luminescent rare earth complexes based on interconfigurational 5d-4f transition have characteristics of adjustable emission spectra and short excited state lifetimes,showing potential applications in display,lighting and other fields.In this work,nine Ce^(3+),Eu^(2+)and Yb^(2+)complexes with spiro-bis(pyrazolyl)borate ligands,where pyrazolyl stands for pyrazolyl,3-methylpyrazolyl,or 3,5-dimethylpyrazolyl,were designed and synthesized.Ce^(3+)complexes show emission colors of blue,with photoluminescence quantum yields(PLQYs)of 94%-100%;Eu^(2+)complexes show emission colors of yellow-green,with PLQYs of 60%-78%;Yb^(2+)complexes show emission colors of orange or red,with PLQYs of 3%-4%.In addition,the crystal structures and theoretical calculation results show C-H…M interactions between bridge-head H atoms of the spirane and central metal ions in these complexes.It is found that the introduction of spirane with large steric hindrance and the existence of C-H…M interactions can improve the stability of the complexes in air atmosphere.
基金Supported by the National Natural Sciene Foundation of China(21171119,11574408,81573822,21376008)the Beijing Natural Science Foundation(2172017,2172012)+2 种基金the Beijing Municipal Education Commission(KM201510028006)the Scientific Research Base Development Program of the Beijing Municipal Commission of Educationthe Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University)。
文摘Two novel lanthanide-based coordination complexes,[LaL(Phen)(NO_(3))_(3)]n(1)and[Pr_(2)L_(2)(Phen)2(NO_(3))_(6)]n(2),were synthesized via a stoichiometric 1∶1∶1 reaction of lanthanide nitrates with tetraisopropyl 1,2-ethylenediphosphate(L)and 1,10-phenanthroline(Phen)in a mixed ethanol-acetonitrile solvent system at room temperature.Their structures were determined by single-crystal X-ray diffraction(SCXRD)and further confirmed by infrared spectroscopy and elemental analysis.Thermogravimetric analysis(TGA)was used to assess thermal stability.Complexes 1 and 2 are both composed of O atoms provided by L and nitrate ions,formed a 10-coordinate configuration with the central Ln^(3+)(Ln=La,Pr)ion.Complex 1 forms a one-dimensional infinite chain connected by bridging ligands and constructs a complex three-dimensional stacking structure through hydrogen bonding andπ…πweak interactions.Complex 2 is connected by ligand L to form a one-dimensional infinite chain and through weak forces such as hydrogen bonding and C-H…πbonds,a novel three-dimensional stacking structure is formed by transverse and longitudinal crossing.
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.
基金support from the National Natural Science Foundation of China(Nos.22277056,21977052)the Distinguished Young Scholars of Jiangsu Province(No.BK20230006)+2 种基金the Natural Science Foundation of Jiangsu Province(Nos.BK20230977,BK20231090)the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.23KJB150020)the Jiangsu Excellent Postdoctoral Program(No.2022ZB758)。
文摘Metal complexes hold significant promise in tumor diagnosis and treatment.However,their potential applications in photodynamic therapy(PDT)are hindered by issues such as poor photostability,low yield of reactive oxygen species(ROS),and aggregation-induced ROS quenching.To address these challenges,we present a molecular self-assembly strategy utilizing aggregation-induced emission(AIE)conjugates for metal complexes.As a proof of concept,we synthesized a mitochondrial-targeting cyclometalated Ir(Ⅲ)photosensitizer Ir-TPE.This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups.Ir-TPE readily self-assembles into nanoaggregates in aqueous solution,leading to a significant production of ROS upon light irradiation.Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria,resulting in mitochondrial DNA damage.This damage can lead to ferroptosis and autophagy,two forms of cell death that are highly cytotoxic to cancer cells.The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS,leading to a more pronounced cytotoxic effect.In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication.This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.
文摘New solid complexes derived from the reaction of aroyl hydrazones, 2-hydroxy-1-naphthaldehyde benzene sulphonyl hydrazone (HNB), and 2-hydroxy-1-naphthaldehyde p-toluene sulphonyl hydrazone (HNT), with Co<sup>2+</sup>, Ni<sup>2+</sup>, and Cu<sup>2+</sup> salts have been isolated and characterized using elemental analyses, spectral (UV-vis., IR), molar conductivity and magnetic measurements. The modes of bonding as well as the stereochemistry of the isolated solid complexes were discussed. The results suggested that both HNB and HNT coordinated with the metal ions in a bidentate manner forming a polymeric chain in the case of HNB while monocular complexes were formed in the case of HNT. The amounts of solvent in the solid complexes were determined by TGA measurements. Also, spectral studies of HNT with Co<sup>2+</sup> and Fe<sup>3+</sup> ions in solution were carried and the ratio of complexes was determined by continuous variation, molar ratio, and slope ratio methods. Moreover, the results suggest the formation of 1:1 (M:L) for Co<sup>2+</sup> ions while three species with ratios of 1:1, 1:2, and 2:1 (M:L) have been observed in the case of Ni<sup>2+</sup> and Cu<sup>2+</sup>. Finally, conductance titration of HNB and HNT with Co<sup>2+</sup> ion elucidates the formation of two species with ratios 1:1 and 1:2 (M:L) in the case of the Co<sup>2+</sup>-HNB while 1:1 (M:L) belongs to the Co<sup>2+</sup>-HNT system.
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To achieve efficient catalytic hydrogenation of CO_(2)to formate,we employed a transmetallation strategy to develop three novel iridium(Ⅰ)complexes,which feature N‑heterocyclic carbene‑nitrogen‑phosphine ligands(CNP)and a 1,5‑cyclooctadiene(cod)molecule:[Ir(cod)(κ^(3)‑CN^(im)P)]Cl(1⁃Cl),[Ir(cod)(κ^(3)‑CN^(im)P)]PF6(1⁃PF_(6)),and[Ir(cod)(κ^(3)‑CNHP)]Cl(2).The^(1)H NMR spectra,^(31)P NMR spectra,and high‑resolution mass spectra verify the successful synthesis of these three Ir(Ⅰ)‑CNP complexes.Furthermore,single‑crystal X‑ray diffraction analysis confirms the coordination geometry of 1⁃PF_(6).The strong Ir—C(NHC)bond suggests that the carbene carbon plays an enhanced anchoring role to iridium due to its strongσ‑donating ability,which helps stabilize the active metal species during CO_(2)hydrogenation.As a result,the Ir(Ⅰ)‑CNP complex exhibits remarkable activity and long catalytic lifetime for the hydrogenation of CO_(2)to formate,reaching a turnover number(TON)of 1.16×10^(6)after 150 h at a high temperature of 170℃,which was a relatively high value among all the Ir complexes.CCDC:2384071,1⁃PF_(6).
