Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(...Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.展开更多
Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'...Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.展开更多
Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been construc...Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been constructed hydrothermally at 160℃ using H_(3)tpta([1,1':3',1″-terphenyl]-4,4',5'-tricarboxylic acid),py(pyridine),H_(2)biim(2,2'-biimidazole),dpe(1,2-di(4-pyridyl)ethylene),and zinc,nickel and cadmium chlorides,resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy,element analysis,thermogravimetric analysis,as well as structural analyses conducted via single-crystal X-ray diffraction.The findings from these single-crystal Xray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P2_(1)/c space group(1)or triclinic system P1 space group(2 and 3),and possess 1D,0D,and 3D structures,respectively.Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions.In addition,complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.CCDC:2449810,1;2449811,2;2449812,3.展开更多
The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when th...The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when the cations are the same and the anions are different,in complex 1,Na^(+)closes one port of CyB5Q[5]through Na—O seven coordination bonds to form a molecular bowl;in complex 3,Na^(+)completely closes the two ports of CyB5Q[5]to form a molecular capsule with six Na—O coordination bonds;in complexes 2 and 4,the two ports of CyB5Q[5]are completely closed to form K—O coordinated molecular capsules,but the K^(+)of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated.and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.CCDC:2457122,1;2457121,2;2457400,3;2457120,4.展开更多
We present zircon ages and geochemical data for the Hongshishan Carboniferous Alaskan-type mafic–ultramafic complex exposed in the Beishan area along the Sino–Mongolian boundary, southern margin of the Central Asian...We present zircon ages and geochemical data for the Hongshishan Carboniferous Alaskan-type mafic–ultramafic complex exposed in the Beishan area along the Sino–Mongolian boundary, southern margin of the Central Asian Orogenic Belt. This complex mainly consists of dunite,harzburgite, lherzolite, wehrlite, and gabbro, which intrudes Early Carboniferous volcanic rocks and reveals a zoned structure. Zircons of a gabbro sample yielded a 206Pb/238 U age of 357 ± 4 Ma, reflecting the time of Early Carboniferous magmatism. Zircon ages were also obtained for an andesite(322 ± 3 Ma) and a basaltic andesite(304 ± 2 Ma).High initial Nd isotope whole-rock values suggest that the Hongshishan gabbro [e_(Nd(t))= +9.6-+10.2] and basalt[eNd(t)= +10.0-+10.8] were derived from a depleted mantle source. Slightly lower eNd(t)values for the ultramafic rocks [eNd(t)= +8.5-+8.7] suggest some interaction of the parental magma with the continental crust. In contrast, the Late Carboniferous Quershan samples in this area represent subduction-related arc volcanic rocks with Adakite-like compositions. The early Carboniferous Hongshishan Alaskan-type complex was interpreted to represent the remnants of a magma chamber that crystallized at the base of a mature island arc, whereas the Quershan island arc volcanic rockssuggest the resurrection of the subduction process after arccontinent collision and uplift of the roots of the arc.展开更多
Mikbi intrusion(MI) is a part of the Neoproterozoic Nubian Shield located along the NE-SW trending major fracture zones prevailing southern Eastern Desert of Egypt. In this study, we present for the first time detaile...Mikbi intrusion(MI) is a part of the Neoproterozoic Nubian Shield located along the NE-SW trending major fracture zones prevailing southern Eastern Desert of Egypt. In this study, we present for the first time detailed mineralogical and bulk-rock geochemical data to infer some constraints on the parental magma genesis and to understand the tectonic processes contributed to MI formation. Lithologically, it is composed of fresh peridotite, clinopyroxenite, hornblendite, anorthosite, gabbronorite, pyroxene amphibole gabbro, amphibole gabbro and diorite. All rocks have low Th/La ratios(mostly <0.2) and lack positive Zr and Th anomalies excluding significant crustal contamination. They show very low concentrations of Nb, Ta, Zr and Hf together with sub-chondritic ratios of Nb/Ta(2-15) and Zr/Hf(19-35),suggesting that their mantle source was depleted by earlier melting extraction event. The oxygen fugacity(logfO_2) estimated from diorite biotite is around the nickel-nickel oxide buffer(NNO) indicating crystallization from a relatively oxidized magma. Amphiboles in the studied mafic-ultramafic rocks indicate relative oxygen fugacity(i.e. ΔNNO; nickel-nickel oxide) of 0.28-3 and were in equilibrium mostly with 3.77-8.24 wt.% H_2 O_(melt)(i.e. water content in the melt), consistent with the typical values of subduction-related magmas. Moreover, pressure estimates(0.53-6.79 kbar) indicate polybaric crystallization and suggest that the magma chamber(s) was located at relatively shallow crustal levels. The enrichment in LILE(e.g., Cs, Ba, K and Sr) and the depletion in HFSE(e.g., Th and Nb) relative to primitive mantle are consistent with island arc signature. The olivine, pyroxene and amphibole compositions also reflect arc affinity. These inferences suggest that their primary magma was derived from partial melting of a mantle source that formerly metasomatized in a subduction zone setting. Clinopyroxene and bulkrock data are consistent with orogenic tholeiitic affinity. Consequently, the mineral and bulk-rock chemistry strongly indicate crystallization from hydrous tholeiitic magma. Moreover, their trace element patterns are subparallel indicating that the various rock types possibly result from differentiation of the same primary magma. These petrological, mineralogical and geochemical characteristics show that the MI is a typical Alaskan-type complex.展开更多
Orogenic peridotite is an important component of orogenic belts and retains crucial information on mantle magmatic activity,slab subduction,and melt or fluid metasomatism.To determine the source of the mantle-derived ...Orogenic peridotite is an important component of orogenic belts and retains crucial information on mantle magmatic activity,slab subduction,and melt or fluid metasomatism.To determine the source of the mantle-derived parental magma of the peridotite and to investigate the metasomatism that it experienced,we undertook an integrated study of the petrography,whole-rock major-and trace-element compositions,in situ zircon U-Pb geochronology,and mineral majorand trace-element compositions of an early Paleozoic ultramafic complex in the North Wulan area of North Qaidam.The Halihatu ultramafic-mafic complex is composed of dunite,pyroxene peridotite,and gabbro,which are characteristic of Alaskan-type complexes.The dunite yields a weighted mean^(206)Pb/^(238)U age of 479±5 Ma(MSWD=0.7),which reflects the age of the metasomatism rather than the crystallization age of the ultramafic magma.The peridotites have high Mg^(#)(89.8-91.8)and Cr contents(2419-5190 ppm),low Al_(2)O_(3)(0.20-1.68 wt%)and Ni(289-1012 ppm)contents,and high olivine Fo contents(87-91),suggesting a large degree(~15%-22%)of partial melting of lithospheric ultramafic rocks followed by variable degrees of fractional crystallization of olivine and pyroxene.This is consistent with estimates of 15%-22.3%partial melting calculated using the Cr#of spinel crystals and with the low Yb(0.04-0.33 ppm)and Y(0.72-1.29 ppm)contents of clinopyroxene crystals.Whole-rock trace-element patterns show enrichment in large ion lithophile elements and depletion in high field strength elements,along with high Al_(2)O_(3)(2.10-6.47 wt%)and low TiO_(2)(0.01-0.21 wt%)contents of clinopyroxene crystals,suggesting an arc magma cumulate trend.These features,along with the high olivine Fo contents(87-91 ppm),imply that the Halihatu peridotite is an Alaskan-type crustal cumulates derived from Mgrich hydrous basaltic melts.The high estimated f O_(2)(FMQ+1.97 to FMQ+3.81)further supports the idea that they formed in an arc setting.The Ni/Co and Ni/Mn ratios and cumulate textures of the olivine,quenched boundaries between mafic and felsic melts,and the occurrence of tremolite and phlogopite reflect interactions between the Halihatu peridotite and injected silicate and carbonatitic melts in the lower crust.Therefore,we propose a new cumulate-infiltration model for the petrogenesis of Alaskan-type ultramafic complexes,which improves our understanding of the nature of Alaskan-type continental arc root.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
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 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
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
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
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
Sensitization of metal-centered forbidden transitions is of great significance.Solid MnII-based phosphors with d-d forbidden transition sensitized by CeIIIwith d-f allowed transition are promising light conversion mat...Sensitization of metal-centered forbidden transitions is of great significance.Solid MnII-based phosphors with d-d forbidden transition sensitized by CeIIIwith d-f allowed transition are promising light conversion materials,but the energy transfer mechanism in CeIII-MnIIis still in dispute for the uncertainty of distances between metal centers.Herein,for the first time,we explored the energy transfer mechanism in two well-designed luminescent heteronuclear complexes with clear crystal structures,i.e.,Ce-N8-Mn and Ce-N2O6-Mn(N8=1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane;N2O6=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane).Short distances between metal centers facilitate efficient energy transfer from CeIIIto MnIIin both complexes,resulting in high photoluminescence quantum yield up to unity.After systematic study of the two heteronuclear complexes as well as two reference complexes Ce(N8)Br3and Ce(N2O6)Br3,we concluded that dipole-quadrupole interaction is the dominant energy transfer mechanism in the heteronuclear complexes.展开更多
Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron...Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.展开更多
New complexes of europium,gadolinium and terbium trinitrates with N,N,N’,N’-tetraalkyl substituted phenanthroline diamides were synthesized.The europium complexes were found to be highly efficient in terms of lumine...New complexes of europium,gadolinium and terbium trinitrates with N,N,N’,N’-tetraalkyl substituted phenanthroline diamides were synthesized.The europium complexes were found to be highly efficient in terms of luminescence properties(max quantum yield=67%).The significant influence of the structure of the ligands on the photophysical characteristics of their complexes was demonstrated.Thus,the incorporation of various substituents(Cl,F,O,OH)into the phenanthroline core causes significant changes in the luminescent behavior of the obtained coordination compounds.We observed significant differences in the energy gap between the excited states S_(1)and T_(1),especially in the L2H.Eu(NO_(3))_(3)and L2FOH.Eu(NO_(3))_(3)complexes,which both demonstrated high overall quantum yields(66%and 67%,respectively).Study of the diffuse reflection spectra of terbium complexes suggested the phenomenon of charge transfer,potentially ligand-to-ligand(LLCT)or intra-ligand(ILCT),rather than ligand-to-metal charge transfer(LMCT).These results highlight the complicated relationship between ligand structure,energy transfer mechanisms and quantum yield in rare earth element complexes,shedding light on ways to optimize their luminescent properties.展开更多
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
Pure near-infrared(NIR)phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine.We have designed and synthesized two new B-embedde...Pure near-infrared(NIR)phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine.We have designed and synthesized two new B-embedded pure near-infrared(NIR)-emitting iridium complexes(Ir(Bpiq)2acac and Ir(Bpiq)2dpm)with peaks greater than 720 nm.More importantly,they exhibit very narrow phosphorescent emission with full width at half maximum(FWHM)of only about 50 nm(0.12 e V),resulting in a high NIR content(>90%)in their spectrum.In view of better optical property and solubility,the complex Ir(Bpiq)_(2)dpm was used as the emitting layer of a solution-processed OLED device,and achieved good maximum external quantum efficiency(EQE)(2.8%)peaking at 728 nm.This research provides an important strategy for the design of narrowband NIR-emitting phosphorescent iridium complexes and their optoelectronic applications.展开更多
文摘Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.
文摘Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.
文摘Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been constructed hydrothermally at 160℃ using H_(3)tpta([1,1':3',1″-terphenyl]-4,4',5'-tricarboxylic acid),py(pyridine),H_(2)biim(2,2'-biimidazole),dpe(1,2-di(4-pyridyl)ethylene),and zinc,nickel and cadmium chlorides,resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy,element analysis,thermogravimetric analysis,as well as structural analyses conducted via single-crystal X-ray diffraction.The findings from these single-crystal Xray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P2_(1)/c space group(1)or triclinic system P1 space group(2 and 3),and possess 1D,0D,and 3D structures,respectively.Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions.In addition,complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.CCDC:2449810,1;2449811,2;2449812,3.
文摘The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when the cations are the same and the anions are different,in complex 1,Na^(+)closes one port of CyB5Q[5]through Na—O seven coordination bonds to form a molecular bowl;in complex 3,Na^(+)completely closes the two ports of CyB5Q[5]to form a molecular capsule with six Na—O coordination bonds;in complexes 2 and 4,the two ports of CyB5Q[5]are completely closed to form K—O coordinated molecular capsules,but the K^(+)of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated.and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.CCDC:2457122,1;2457121,2;2457400,3;2457120,4.
基金financially supported by the National Natural Science Foundation of China (Grant Nos.40703012,41030314)Geological Survey of China (Grant Nos.1212011120332,DD20160123-05)Chinese Ministry of Science and Technology (Grant 2012FY120100)
文摘We present zircon ages and geochemical data for the Hongshishan Carboniferous Alaskan-type mafic–ultramafic complex exposed in the Beishan area along the Sino–Mongolian boundary, southern margin of the Central Asian Orogenic Belt. This complex mainly consists of dunite,harzburgite, lherzolite, wehrlite, and gabbro, which intrudes Early Carboniferous volcanic rocks and reveals a zoned structure. Zircons of a gabbro sample yielded a 206Pb/238 U age of 357 ± 4 Ma, reflecting the time of Early Carboniferous magmatism. Zircon ages were also obtained for an andesite(322 ± 3 Ma) and a basaltic andesite(304 ± 2 Ma).High initial Nd isotope whole-rock values suggest that the Hongshishan gabbro [e_(Nd(t))= +9.6-+10.2] and basalt[eNd(t)= +10.0-+10.8] were derived from a depleted mantle source. Slightly lower eNd(t)values for the ultramafic rocks [eNd(t)= +8.5-+8.7] suggest some interaction of the parental magma with the continental crust. In contrast, the Late Carboniferous Quershan samples in this area represent subduction-related arc volcanic rocks with Adakite-like compositions. The early Carboniferous Hongshishan Alaskan-type complex was interpreted to represent the remnants of a magma chamber that crystallized at the base of a mature island arc, whereas the Quershan island arc volcanic rockssuggest the resurrection of the subduction process after arccontinent collision and uplift of the roots of the arc.
文摘Mikbi intrusion(MI) is a part of the Neoproterozoic Nubian Shield located along the NE-SW trending major fracture zones prevailing southern Eastern Desert of Egypt. In this study, we present for the first time detailed mineralogical and bulk-rock geochemical data to infer some constraints on the parental magma genesis and to understand the tectonic processes contributed to MI formation. Lithologically, it is composed of fresh peridotite, clinopyroxenite, hornblendite, anorthosite, gabbronorite, pyroxene amphibole gabbro, amphibole gabbro and diorite. All rocks have low Th/La ratios(mostly <0.2) and lack positive Zr and Th anomalies excluding significant crustal contamination. They show very low concentrations of Nb, Ta, Zr and Hf together with sub-chondritic ratios of Nb/Ta(2-15) and Zr/Hf(19-35),suggesting that their mantle source was depleted by earlier melting extraction event. The oxygen fugacity(logfO_2) estimated from diorite biotite is around the nickel-nickel oxide buffer(NNO) indicating crystallization from a relatively oxidized magma. Amphiboles in the studied mafic-ultramafic rocks indicate relative oxygen fugacity(i.e. ΔNNO; nickel-nickel oxide) of 0.28-3 and were in equilibrium mostly with 3.77-8.24 wt.% H_2 O_(melt)(i.e. water content in the melt), consistent with the typical values of subduction-related magmas. Moreover, pressure estimates(0.53-6.79 kbar) indicate polybaric crystallization and suggest that the magma chamber(s) was located at relatively shallow crustal levels. The enrichment in LILE(e.g., Cs, Ba, K and Sr) and the depletion in HFSE(e.g., Th and Nb) relative to primitive mantle are consistent with island arc signature. The olivine, pyroxene and amphibole compositions also reflect arc affinity. These inferences suggest that their primary magma was derived from partial melting of a mantle source that formerly metasomatized in a subduction zone setting. Clinopyroxene and bulkrock data are consistent with orogenic tholeiitic affinity. Consequently, the mineral and bulk-rock chemistry strongly indicate crystallization from hydrous tholeiitic magma. Moreover, their trace element patterns are subparallel indicating that the various rock types possibly result from differentiation of the same primary magma. These petrological, mineralogical and geochemical characteristics show that the MI is a typical Alaskan-type complex.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.42272246,41272221,41902235)。
文摘Orogenic peridotite is an important component of orogenic belts and retains crucial information on mantle magmatic activity,slab subduction,and melt or fluid metasomatism.To determine the source of the mantle-derived parental magma of the peridotite and to investigate the metasomatism that it experienced,we undertook an integrated study of the petrography,whole-rock major-and trace-element compositions,in situ zircon U-Pb geochronology,and mineral majorand trace-element compositions of an early Paleozoic ultramafic complex in the North Wulan area of North Qaidam.The Halihatu ultramafic-mafic complex is composed of dunite,pyroxene peridotite,and gabbro,which are characteristic of Alaskan-type complexes.The dunite yields a weighted mean^(206)Pb/^(238)U age of 479±5 Ma(MSWD=0.7),which reflects the age of the metasomatism rather than the crystallization age of the ultramafic magma.The peridotites have high Mg^(#)(89.8-91.8)and Cr contents(2419-5190 ppm),low Al_(2)O_(3)(0.20-1.68 wt%)and Ni(289-1012 ppm)contents,and high olivine Fo contents(87-91),suggesting a large degree(~15%-22%)of partial melting of lithospheric ultramafic rocks followed by variable degrees of fractional crystallization of olivine and pyroxene.This is consistent with estimates of 15%-22.3%partial melting calculated using the Cr#of spinel crystals and with the low Yb(0.04-0.33 ppm)and Y(0.72-1.29 ppm)contents of clinopyroxene crystals.Whole-rock trace-element patterns show enrichment in large ion lithophile elements and depletion in high field strength elements,along with high Al_(2)O_(3)(2.10-6.47 wt%)and low TiO_(2)(0.01-0.21 wt%)contents of clinopyroxene crystals,suggesting an arc magma cumulate trend.These features,along with the high olivine Fo contents(87-91 ppm),imply that the Halihatu peridotite is an Alaskan-type crustal cumulates derived from Mgrich hydrous basaltic melts.The high estimated f O_(2)(FMQ+1.97 to FMQ+3.81)further supports the idea that they formed in an arc setting.The Ni/Co and Ni/Mn ratios and cumulate textures of the olivine,quenched boundaries between mafic and felsic melts,and the occurrence of tremolite and phlogopite reflect interactions between the Halihatu peridotite and injected silicate and carbonatitic melts in the lower crust.Therefore,we propose a new cumulate-infiltration model for the petrogenesis of Alaskan-type ultramafic complexes,which improves our understanding of the nature of Alaskan-type continental arc root.
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 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).
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financial support from the National Key R&D Program of China(Nos.2022YFB3503702,2023YFB3506901,2021YFB3501800)the National Natural Science Foundation of China(Nos.92156016,62104013,22071003)。
文摘Sensitization of metal-centered forbidden transitions is of great significance.Solid MnII-based phosphors with d-d forbidden transition sensitized by CeIIIwith d-f allowed transition are promising light conversion materials,but the energy transfer mechanism in CeIII-MnIIis still in dispute for the uncertainty of distances between metal centers.Herein,for the first time,we explored the energy transfer mechanism in two well-designed luminescent heteronuclear complexes with clear crystal structures,i.e.,Ce-N8-Mn and Ce-N2O6-Mn(N8=1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane;N2O6=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane).Short distances between metal centers facilitate efficient energy transfer from CeIIIto MnIIin both complexes,resulting in high photoluminescence quantum yield up to unity.After systematic study of the two heteronuclear complexes as well as two reference complexes Ce(N8)Br3and Ce(N2O6)Br3,we concluded that dipole-quadrupole interaction is the dominant energy transfer mechanism in the heteronuclear complexes.
文摘Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.
基金support from M.V.Lomonosov Moscow State University Program of Development。
文摘New complexes of europium,gadolinium and terbium trinitrates with N,N,N’,N’-tetraalkyl substituted phenanthroline diamides were synthesized.The europium complexes were found to be highly efficient in terms of luminescence properties(max quantum yield=67%).The significant influence of the structure of the ligands on the photophysical characteristics of their complexes was demonstrated.Thus,the incorporation of various substituents(Cl,F,O,OH)into the phenanthroline core causes significant changes in the luminescent behavior of the obtained coordination compounds.We observed significant differences in the energy gap between the excited states S_(1)and T_(1),especially in the L2H.Eu(NO_(3))_(3)and L2FOH.Eu(NO_(3))_(3)complexes,which both demonstrated high overall quantum yields(66%and 67%,respectively).Study of the diffuse reflection spectra of terbium complexes suggested the phenomenon of charge transfer,potentially ligand-to-ligand(LLCT)or intra-ligand(ILCT),rather than ligand-to-metal charge transfer(LMCT).These results highlight the complicated relationship between ligand structure,energy transfer mechanisms and quantum yield in rare earth element complexes,shedding light on ways to optimize their luminescent properties.
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].
基金support from the National Natural Science Foundation of China(Nos.22171109,52373195 and 22001097)Natural Science Foundation of Jiangsu Province of China(No.BK20201003)+1 种基金the Postdoctoral Research Foundation of China(No.2021M701657)the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,Jianghan University(No.JDGD-202301)。
文摘Pure near-infrared(NIR)phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine.We have designed and synthesized two new B-embedded pure near-infrared(NIR)-emitting iridium complexes(Ir(Bpiq)2acac and Ir(Bpiq)2dpm)with peaks greater than 720 nm.More importantly,they exhibit very narrow phosphorescent emission with full width at half maximum(FWHM)of only about 50 nm(0.12 e V),resulting in a high NIR content(>90%)in their spectrum.In view of better optical property and solubility,the complex Ir(Bpiq)_(2)dpm was used as the emitting layer of a solution-processed OLED device,and achieved good maximum external quantum efficiency(EQE)(2.8%)peaking at 728 nm.This research provides an important strategy for the design of narrowband NIR-emitting phosphorescent iridium complexes and their optoelectronic applications.
