Four novel palladium（（Ⅱ）） complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reactio...Four novel palladium（（Ⅱ）） complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reaction of aryl halides with electron-deficient olefins. The coupling reaction of awl halide bearig different functional groups with olefin derivatives took place and the corresponding products were isolated in good to excellent yields under optimal conditions. The procedure exhibits good functional group tolerance and wide substrate scope. This Mizoroki-Heck reaction was further achieved using Pd（OAc）2 and 3,5-di-isopropyl-1H-1,2,4-diazaphospholes as combined catalyst, which provide the convenient and alternative method in organic synthesis展开更多
The noncovalent interaction-assisted transition metal catalysis has attracted intense interest,and emerged as a powerful tool to develop new privileged ligands.Herein,we developed a library of novel mantis-shaped bifu...The noncovalent interaction-assisted transition metal catalysis has attracted intense interest,and emerged as a powerful tool to develop new privileged ligands.Herein,we developed a library of novel mantis-shaped bifunctional chiral monodentate-type phosphine ligands having octahydroindole-imidazolone skeleton as the key stereodirecting monochiral arm and the tertiary amine group as an H-bond acceptor,namely OPI-Phos ligands,which were prepared from the optically pure easily accessible octahydroindole-amides in one step.These ligands are characteristic of easy synthesis,rigid backbone,high tunability and air stability.They were proven to be a class of efficient chiral ligands for Pd-catalyzed asymmetric allylic substitution reactions of rac-allyl acetates with O and C-nucleophiles,achieving high reactivity and enantioselectivity.Single crystal structure of OPI-Phos ligand/palladium complexes revealed a possible monodentate manner-type reaction mechanism.展开更多
Herein,a novel sensor(TPE-UiO-66)was designed via anchoring monodentate tetraphenylethylene(TPE)onto UiO-66 framework.The combination of the distinct aggregation-induced emission(AIE)of TPE and the easy replacement of...Herein,a novel sensor(TPE-UiO-66)was designed via anchoring monodentate tetraphenylethylene(TPE)onto UiO-66 framework.The combination of the distinct aggregation-induced emission(AIE)of TPE and the easy replacement of monodentate linker by vip phosphate,makes TPE-UiO-66 an ideal pltform for sensing HPO_(4)^(2-)。Experimental results indicate that TPE-UiO-66 can selectively sense HPO_(4)^(2-)from other common anions.展开更多
The history for the development of chiral phos- phorus ligands in catalytic asymmetric hydrogenation is briefly highlighted. This review focuses on the recent ad- vances in the synthesis of the monodentate phosphorus ...The history for the development of chiral phos- phorus ligands in catalytic asymmetric hydrogenation is briefly highlighted. This review focuses on the recent ad- vances in the synthesis of the monodentate phosphorus ligands and their applications in catalytic asymmetric hydrogenation. The examples highlighted in this article clearly demonstrated the importance and advantages of monodentate phosphorus ligands, which had been ignored for 30 a and experienced arenaissance at the very beginning of this millennium, particularly in the area of asymmetric hydrogenation.展开更多
La1-x Cax MnO3 （x=0-0.3） perovskite-type oxides were synthesized by citrate sol-gel method. The physical and chemical properties were characterized by X-ray diffraction （XRD）, Brumauer-Emmett-Teller method （BET）...La1-x Cax MnO3 （x=0-0.3） perovskite-type oxides were synthesized by citrate sol-gel method. The physical and chemical properties were characterized by X-ray diffraction （XRD）, Brumauer-Emmett-Teller method （BET）, X-ray photoelectron spectroscopy （XPS）, NO＋O2 -TPD （temperature-programmed desorption）, activated oxygen evaluation and H2 -TPR （temperature-programmed reduction） technologies. The results showed that NO catalytic oxidation activity was significantly improved by Ca substitution, especially for lower temperature activity. The La0.9 Ca0.1 MnO 3 sample showed the maximum conversion of 82% at 300 oC. The monodentate nitrates played a crucial role for the formation of NO2 . The reducibility of Mn 4＋ ions and reactivity of activated oxygen were favorable for the catalytic performances of NO oxidation.展开更多
A series of MnMgA10 samples with different amounts of Ce doping were facilely prepared using coprecipitation method and their catalytic soot combustion activity was evaluated by temperature programmed oxidation reacti...A series of MnMgA10 samples with different amounts of Ce doping were facilely prepared using coprecipitation method and their catalytic soot combustion activity was evaluated by temperature programmed oxidation reaction （TPO）. The methods of X-ray diffraction （XRD）, Brumauer-Emmett-Teller （BET）, H2-TPR, NO-TPO and in situ 1R were used to characterize the physio- chemical properties of these samples. Dopant Ce improved the soot combustion performance of MnMgA10 catalyst due to the en- hanced redox ability. Introduction of NOx led to the further increase of catalytic soot oxidation activity on these samples. Over Ce-containing samples, the catalytic activity was slightly decreased as the amount of dopant Ce increased in 02. Diftbrently, in NO＋O2, a certain amount of dopant Ce was much more favorable and excess amount of Ce resulted in a sharp drop of the catalytic soot combustion activity. Both NO： and nitrates were found to have great contributions to the effects of NOx on the soot combustion activity of Ce-doped catalysts. More NO2 was generated as dopant Ce increased. When appropriate amount of Ce was introduced, the as-formed NO2 was stored as bridging bidentate nitrate on Mn-Ce site, which was confirmed to have higher reactivity with soot than nitrite or monodentate nitrate on Mn and/or Ce sites. Overall, Mno.sMg2.sCeo.lAlo.90 was considered as the most potential catalyst for soot combustion.展开更多
By allowing H_(2)SeO_(4),Cy_(2)NH,CyNH_(2) or Bz2NH to react respectively with SnPh_(3)Cl(in methanol),SnPh_(2)Cl_(2)(in water+methanol)and MgCl_(2)·6H_(2)O(in methanol)in specific ratios,the studied complexes ar...By allowing H_(2)SeO_(4),Cy_(2)NH,CyNH_(2) or Bz2NH to react respectively with SnPh_(3)Cl(in methanol),SnPh_(2)Cl_(2)(in water+methanol)and MgCl_(2)·6H_(2)O(in methanol)in specific ratios,the studied complexes are obtained.The suggested structures are discrete and polymer,the environment of the tin center being trans trigonal bipyramidal(compound 1),tetrahedral(compound 2)and octahedral(compound 3),the anions behaving as a bidentate selenate.展开更多
One new hydrogenosuccinate and two succinate adduct and complex have been synthesized and studied by infrared,UV-Visible and NMR(Nuclear Magnetic Resonance Spectroscopy)^(119)Sn spectroscopies.The suggested structure ...One new hydrogenosuccinate and two succinate adduct and complex have been synthesized and studied by infrared,UV-Visible and NMR(Nuclear Magnetic Resonance Spectroscopy)^(119)Sn spectroscopies.The suggested structure is discrete,the hydrogenosuccinate behaving as a monodentate ligand or only involved in hydrogen bonding,the environment around the magnesium centre being triangular(compound 3).The succiate anion is a monochelating ligand(compound 1 and 2).In all the suggested structures,when extra hydrogen bonds are considered,supramolecular architectures are obtained(compound 2 and 3).展开更多
Three new salicylate complexes and derivatives have been synthesized and studied by infrared, 119Sn NMR and UV-visible spectroscopies. The suggested structures for the two compounds are discrete with NH-O and NH-Cl hy...Three new salicylate complexes and derivatives have been synthesized and studied by infrared, 119Sn NMR and UV-visible spectroscopies. The suggested structures for the two compounds are discrete with NH-O and NH-Cl hydrogen bonds. The salicylate oxyanion is monochelating for the first salicylate compound with an octahedral tin (IV) centre and monodentate for the second salicylate compound, the environments around the tin centre being tetrahedral. For the cooper complex, the salicylate ligand is monochelating and the environments around the copper atom centre are tetrahedral.展开更多
Eight diiron_((I))bis-cyclopentadienyl complexes with a bridging methylthiocarbyne ligand were prepared from the tris-carbonyl precursor[Fe_(2)Cp_(2)(CO)_(2)(μ-CO)(μ-CSMe)]CF_(3)SO_(3)(Cp=η^(5)-C_(5)H_(5))through t...Eight diiron_((I))bis-cyclopentadienyl complexes with a bridging methylthiocarbyne ligand were prepared from the tris-carbonyl precursor[Fe_(2)Cp_(2)(CO)_(2)(μ-CO)(μ-CSMe)]CF_(3)SO_(3)(Cp=η^(5)-C_(5)H_(5))through the substitution of one or two terminal carbonyls with a variety of monodentate ligands including phosphanes/phosphite,alkyl/aryl isocyanides or iodide.All compounds were isolated in 57-84%yield and characterized by IR and multinuclear NMR spectroscopy and by X-ray diffraction in five representative cases.Their bonding,stereochemistry and isomerization processes were investigated by NMR and DFT techniques.The water solubility and octanol-water partition coefficient heavily depend on the different monodentate ligands.All cationic complexes displayed substantial inertness in aqueous and cell culture medium solutions at 37℃over 24-48 h.Their cytotoxicity was assessed on a panel of human cancer cell lines(HCT 116,MCF-7 and A2780).Four compounds showed IC_(50) values down to the nanomolar range in colorectal,breast and ovarian cancer cell lines.The most potent compound,[Fe_(2)Cp_(2)(CO)(PPh_(3))(μ-CO)(μ-CSMe)]CF_(3)SO_(3),revealed enhanced Fe accumulation and significant disruption of cell redox homeostasis in A2780 cells that resulted in caspase-independent apoptotic cell death.The six times higher sensitivity of A2780 cells in comparison to healthy fibroblasts(MRC-5)underlines the potential of this compound to preferably target cancer cells.Overall,the variation of monodentate ligands on a diiron_((I))bis-cyclopentadienylμ-thiocarbyne core represents a simple strategy to obtain robust compounds with tuneable physico-chemical properties and possibly also a remarkable anticancer activity.展开更多
A synthetic route to flapping poly-Lewis acids(PLAs)based on dibenzocyclooctatetraene was developed.The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases(LB)including drugs was...A synthetic route to flapping poly-Lewis acids(PLAs)based on dibenzocyclooctatetraene was developed.The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases(LB)including drugs was investigated in detail.By using different monodentate LBs,the different effective Lewis acidities(eLA)of the respective pairings were determined and compared with each other.The reaction with multidentate LBs yielded a range of adducts,which were analysed in solution by NMR methods,including DOSY NMR spectroscopy,and in the solid state by X-ray diffraction.The adducts include specific oligomers,and coordination polymers constructed via B-P,Al-P and Al-N interactions.The solid-state structures of these coordination polymers have been determined.The results of complexation of bidentate LB by the tetradentate PLA show that LB is preferentially chelated in the binding pockets,which does not impede the flapping movement during chelating complexation.This phenomenon can be attributed to a reduction in entropy when this flapping motion is lost.The aluminium containing PLAs were observed to form a complex with two caffeine molecules,exhibiting remarkable preference for oxygen functions.In contrast,the reaction with theobromine resulted in the degradation of the PLAs due to the presence of acidic protons in theobromine,leading to the formation of a dimeric aluminium containing theobromine derivative.These findings demonstrate the interaction of PLAs with drugs.They provide a foundation for the advancement of PLAs with a tuneable orientation of Lewis acidic functions.展开更多
We report the preparation,spectroscopic characterisation,crystal structure determination and cryomagnetic investigation of three cobalt(II)complexes of formula trans-[Co(bim)_(4)(NCS)_(2)](1),[Co(bim)_(2)(NCO)_(2)](_(...We report the preparation,spectroscopic characterisation,crystal structure determination and cryomagnetic investigation of three cobalt(II)complexes of formula trans-[Co(bim)_(4)(NCS)_(2)](1),[Co(bim)_(2)(NCO)_(2)](_(2))and[Co(bim)_(2)(N_(3))_(2)]_(n)(_(3))(bim=1-benzylimidazole).The structure of 1 is made up of neutral[Co(bim)_(4)(NCS)_(2)]mononuclear units,where the cobalt(II)ion is six-coordinate with four monodentate bim ligands in equatorial positions and two N-thiocyanato groups in the axial sites building a slightly compressed octahedron.展开更多
Structural distortions from the ideal octahedral geometry are known to facilitate the photorelease of kinetically inert groups in Ru_((II))polypyridyl complexes.Building on this principle,here we report,for the first ...Structural distortions from the ideal octahedral geometry are known to facilitate the photorelease of kinetically inert groups in Ru_((II))polypyridyl complexes.Building on this principle,here we report,for the first time,the design of a water-soluble Ru_((II))complex containing a terpyridine-dicarboxylate pentadentate ligand(LH_(2)),formulated as[Ru{ptpy(COO^(-))_(2)}(DMSO)](RuL),engineered for efficient photorelease of the bound monodentate DMSO ligand in aqueous medium.This work presents a novel idea for inducing axial Ru-DMSO bond photolability from the conformational strain originating from a pentadentate ligand in an Ru_((II))complex,triggering photodissociation to create potent cytotoxic species for phototherapeutic application.The molecular identity,and photophysical and electrochemical features with solution speciation of the RuL were examined.The blue-light-triggered photo-substitution was studied to gain insight into potential adduct formation with biological targets relevant to photo-activated chemotherapeutic(PACT)uses.The geometry-optimized structure and the nature of the frontier molecular orbitals have been determined using DFT calculations.The photosubstitution quantum yield(Φ_(PS))in acetonitrile was thirteen times greater than that in water,highlighting the significant influence of solvent on the photochemical efficiency.Notably,the RuL ligand exhibited substantial cytotoxicity under light irradiation,while remaining non-cytotoxic in the dark,underscoring its potential utility in Ru_((II))-based photo-activated chemotherapy.展开更多
Low-coordinate lanthanide(Ln)complexes have attracted considerable attention in the field of molecular magnetism by virtue of their excellent potential in constructing high-performance single-molecule magnets(SMMs).Fr...Low-coordinate lanthanide(Ln)complexes have attracted considerable attention in the field of molecular magnetism by virtue of their excellent potential in constructing high-performance single-molecule magnets(SMMs).From the chemical synthesis point of view,it is challenging to isolate stable Ln(III)complexes with a coordination number(CN)lower than six owing to the large ionic radius,variable coordination pattern and little preference in the bond direction of Ln(III)ions.Herein,a super bulky Schiff-base ligand HL(2-((2,6-dibenzhydryl-4-isopropylphenylimino)methyl)-4,6-di-tert-butylphenol)was used to construct a five-coordinate mononuclear Dy(III)complex,DyL_(2)I(5-Dy-I).Magnetic investigations showed that the strong interaction between Dy(III)and phenolate induces a strong block of magnetization giving the largest anisotropy barrier of 1237 cm-1 and the highest blocking temperature up to 20 K for any reported mononuclear Ln(III)SMMs with CN<6,which greatly motivated researchers to use a bulky monodentate phenolate ligand to synthesize a two-coordinate Dy(III)SMM.展开更多
基金Financial support from Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No. 2015157)Teaching Reform Project of Shanxi Normal University(No. SD2014JGKT-52)Undergraduate Training Programs for Innovation and Entrepreneurship of Modern College of Arts and Sciences, Shanxi Normal University(No. WL2015CXCY-YJ-26)
文摘Four novel palladium（（Ⅱ）） complexes coordinated by phosphorus atoms from both 3,5-disubstituted-1H- 1,2,4-diazaphospholes in monodentate fashion were developed as efficient catalyst for the Mizoroki- Heck reaction of aryl halides with electron-deficient olefins. The coupling reaction of awl halide bearig different functional groups with olefin derivatives took place and the corresponding products were isolated in good to excellent yields under optimal conditions. The procedure exhibits good functional group tolerance and wide substrate scope. This Mizoroki-Heck reaction was further achieved using Pd（OAc）2 and 3,5-di-isopropyl-1H-1,2,4-diazaphospholes as combined catalyst, which provide the convenient and alternative method in organic synthesis
基金Guizhou Provincial Science and Technology Support Program(QKHS[2025]110)Guizhou Provincial Basic Research Program(ZK[2024]374,ZK[2023]404 and ZK[2024]370)the Guiyang City Science and Technology Plan Project([2024]2-37).
文摘The noncovalent interaction-assisted transition metal catalysis has attracted intense interest,and emerged as a powerful tool to develop new privileged ligands.Herein,we developed a library of novel mantis-shaped bifunctional chiral monodentate-type phosphine ligands having octahydroindole-imidazolone skeleton as the key stereodirecting monochiral arm and the tertiary amine group as an H-bond acceptor,namely OPI-Phos ligands,which were prepared from the optically pure easily accessible octahydroindole-amides in one step.These ligands are characteristic of easy synthesis,rigid backbone,high tunability and air stability.They were proven to be a class of efficient chiral ligands for Pd-catalyzed asymmetric allylic substitution reactions of rac-allyl acetates with O and C-nucleophiles,achieving high reactivity and enantioselectivity.Single crystal structure of OPI-Phos ligand/palladium complexes revealed a possible monodentate manner-type reaction mechanism.
基金This work is supported by the Ph.D.Scientific Research Foun-dation of Taiyuan University of Science and Technology(Nos.20182020,20182058)the National Natural Science Foundation of China(No.21978212)+2 种基金the Science and Technology Plans of Tian-jin(No.18PTSYJC00180)the Scientific and Technological Innova-tion Project of University in Shanxi Province(Nos.2019L0657,2019L0628)the Doctoral Award Fund of Shanxi Province(No.20192045).
文摘Herein,a novel sensor(TPE-UiO-66)was designed via anchoring monodentate tetraphenylethylene(TPE)onto UiO-66 framework.The combination of the distinct aggregation-induced emission(AIE)of TPE and the easy replacement of monodentate linker by vip phosphate,makes TPE-UiO-66 an ideal pltform for sensing HPO_(4)^(2-)。Experimental results indicate that TPE-UiO-66 can selectively sense HPO_(4)^(2-)from other common anions.
基金supported by the National Natural Science Foundation of China(Grant Nos.20225204,20121202,20l320l0 and 20372071)the Chinese Academy of Sciences.the Maior Basic Research Development Program of China(Grant No.G2000077506)the Science and Technology Commission of Shang-hai M unicipality
文摘The history for the development of chiral phos- phorus ligands in catalytic asymmetric hydrogenation is briefly highlighted. This review focuses on the recent ad- vances in the synthesis of the monodentate phosphorus ligands and their applications in catalytic asymmetric hydrogenation. The examples highlighted in this article clearly demonstrated the importance and advantages of monodentate phosphorus ligands, which had been ignored for 30 a and experienced arenaissance at the very beginning of this millennium, particularly in the area of asymmetric hydrogenation.
基金Project supported by National High Technology Research and Development Program of China(863Program,2011AA03A405)
文摘La1-x Cax MnO3 （x=0-0.3） perovskite-type oxides were synthesized by citrate sol-gel method. The physical and chemical properties were characterized by X-ray diffraction （XRD）, Brumauer-Emmett-Teller method （BET）, X-ray photoelectron spectroscopy （XPS）, NO＋O2 -TPD （temperature-programmed desorption）, activated oxygen evaluation and H2 -TPR （temperature-programmed reduction） technologies. The results showed that NO catalytic oxidation activity was significantly improved by Ca substitution, especially for lower temperature activity. The La0.9 Ca0.1 MnO 3 sample showed the maximum conversion of 82% at 300 oC. The monodentate nitrates played a crucial role for the formation of NO2 . The reducibility of Mn 4＋ ions and reactivity of activated oxygen were favorable for the catalytic performances of NO oxidation.
基金supported by National Natural Science Foundation of China(21107030,21277060,21077043)the Foundation for Outstanding Young Scientist in Shandong Province(BS2011HZ002)
文摘A series of MnMgA10 samples with different amounts of Ce doping were facilely prepared using coprecipitation method and their catalytic soot combustion activity was evaluated by temperature programmed oxidation reaction （TPO）. The methods of X-ray diffraction （XRD）, Brumauer-Emmett-Teller （BET）, H2-TPR, NO-TPO and in situ 1R were used to characterize the physio- chemical properties of these samples. Dopant Ce improved the soot combustion performance of MnMgA10 catalyst due to the en- hanced redox ability. Introduction of NOx led to the further increase of catalytic soot oxidation activity on these samples. Over Ce-containing samples, the catalytic activity was slightly decreased as the amount of dopant Ce increased in 02. Diftbrently, in NO＋O2, a certain amount of dopant Ce was much more favorable and excess amount of Ce resulted in a sharp drop of the catalytic soot combustion activity. Both NO： and nitrates were found to have great contributions to the effects of NOx on the soot combustion activity of Ce-doped catalysts. More NO2 was generated as dopant Ce increased. When appropriate amount of Ce was introduced, the as-formed NO2 was stored as bridging bidentate nitrate on Mn-Ce site, which was confirmed to have higher reactivity with soot than nitrite or monodentate nitrate on Mn and/or Ce sites. Overall, Mno.sMg2.sCeo.lAlo.90 was considered as the most potential catalyst for soot combustion.
文摘By allowing H_(2)SeO_(4),Cy_(2)NH,CyNH_(2) or Bz2NH to react respectively with SnPh_(3)Cl(in methanol),SnPh_(2)Cl_(2)(in water+methanol)and MgCl_(2)·6H_(2)O(in methanol)in specific ratios,the studied complexes are obtained.The suggested structures are discrete and polymer,the environment of the tin center being trans trigonal bipyramidal(compound 1),tetrahedral(compound 2)and octahedral(compound 3),the anions behaving as a bidentate selenate.
基金Plasseraud,ICMUB UMR CNRS 6302,University of Burgundy,Faculty of Sciences,Dijon,France.
文摘One new hydrogenosuccinate and two succinate adduct and complex have been synthesized and studied by infrared,UV-Visible and NMR(Nuclear Magnetic Resonance Spectroscopy)^(119)Sn spectroscopies.The suggested structure is discrete,the hydrogenosuccinate behaving as a monodentate ligand or only involved in hydrogen bonding,the environment around the magnesium centre being triangular(compound 3).The succiate anion is a monochelating ligand(compound 1 and 2).In all the suggested structures,when extra hydrogen bonds are considered,supramolecular architectures are obtained(compound 2 and 3).
文摘Three new salicylate complexes and derivatives have been synthesized and studied by infrared, 119Sn NMR and UV-visible spectroscopies. The suggested structures for the two compounds are discrete with NH-O and NH-Cl hydrogen bonds. The salicylate oxyanion is monochelating for the first salicylate compound with an octahedral tin (IV) centre and monodentate for the second salicylate compound, the environments around the tin centre being tetrahedral. For the cooper complex, the salicylate ligand is monochelating and the environments around the copper atom centre are tetrahedral.
基金support from the University of Pisa under the“PRA 2022-2023-Progetti di Ricerca di Ateneo”(Institutional Research Grants)-Project no.PRA_2022_12“New challenges of transition metal and lanthanide complexes in the perspective of green chemistry”the Ministry of Science,Technological Development,and Innovation of the Republic of Serbia(No.451-03-136/2025-03/200007)for the financial support.
文摘Eight diiron_((I))bis-cyclopentadienyl complexes with a bridging methylthiocarbyne ligand were prepared from the tris-carbonyl precursor[Fe_(2)Cp_(2)(CO)_(2)(μ-CO)(μ-CSMe)]CF_(3)SO_(3)(Cp=η^(5)-C_(5)H_(5))through the substitution of one or two terminal carbonyls with a variety of monodentate ligands including phosphanes/phosphite,alkyl/aryl isocyanides or iodide.All compounds were isolated in 57-84%yield and characterized by IR and multinuclear NMR spectroscopy and by X-ray diffraction in five representative cases.Their bonding,stereochemistry and isomerization processes were investigated by NMR and DFT techniques.The water solubility and octanol-water partition coefficient heavily depend on the different monodentate ligands.All cationic complexes displayed substantial inertness in aqueous and cell culture medium solutions at 37℃over 24-48 h.Their cytotoxicity was assessed on a panel of human cancer cell lines(HCT 116,MCF-7 and A2780).Four compounds showed IC_(50) values down to the nanomolar range in colorectal,breast and ovarian cancer cell lines.The most potent compound,[Fe_(2)Cp_(2)(CO)(PPh_(3))(μ-CO)(μ-CSMe)]CF_(3)SO_(3),revealed enhanced Fe accumulation and significant disruption of cell redox homeostasis in A2780 cells that resulted in caspase-independent apoptotic cell death.The six times higher sensitivity of A2780 cells in comparison to healthy fibroblasts(MRC-5)underlines the potential of this compound to preferably target cancer cells.Overall,the variation of monodentate ligands on a diiron_((I))bis-cyclopentadienylμ-thiocarbyne core represents a simple strategy to obtain robust compounds with tuneable physico-chemical properties and possibly also a remarkable anticancer activity.
基金funded by the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)grant MI 477/39-1,project no.424957011the Regional Computing Centre of the University of Cologne(RRZK)for providing computing time and support on the DFG-funded(Funding number:INST 216/512/1FUGG)HPC system CHEOPS.
文摘A synthetic route to flapping poly-Lewis acids(PLAs)based on dibenzocyclooctatetraene was developed.The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases(LB)including drugs was investigated in detail.By using different monodentate LBs,the different effective Lewis acidities(eLA)of the respective pairings were determined and compared with each other.The reaction with multidentate LBs yielded a range of adducts,which were analysed in solution by NMR methods,including DOSY NMR spectroscopy,and in the solid state by X-ray diffraction.The adducts include specific oligomers,and coordination polymers constructed via B-P,Al-P and Al-N interactions.The solid-state structures of these coordination polymers have been determined.The results of complexation of bidentate LB by the tetradentate PLA show that LB is preferentially chelated in the binding pockets,which does not impede the flapping movement during chelating complexation.This phenomenon can be attributed to a reduction in entropy when this flapping motion is lost.The aluminium containing PLAs were observed to form a complex with two caffeine molecules,exhibiting remarkable preference for oxygen functions.In contrast,the reaction with theobromine resulted in the degradation of the PLAs due to the presence of acidic protons in theobromine,leading to the formation of a dimeric aluminium containing theobromine derivative.These findings demonstrate the interaction of PLAs with drugs.They provide a foundation for the advancement of PLAs with a tuneable orientation of Lewis acidic functions.
基金supported by the Polish National Agency for Academic Exchange(PPN/BEK/2018/1/00239/U/00001/01)the Ministerio Español de Ciencia e Innovación(Projects CTQ2016-75068P and PID2019-109735GB-I00Unidad de Excelencia María de Maetzu MDM-2015-0538).
文摘We report the preparation,spectroscopic characterisation,crystal structure determination and cryomagnetic investigation of three cobalt(II)complexes of formula trans-[Co(bim)_(4)(NCS)_(2)](1),[Co(bim)_(2)(NCO)_(2)](_(2))and[Co(bim)_(2)(N_(3))_(2)]_(n)(_(3))(bim=1-benzylimidazole).The structure of 1 is made up of neutral[Co(bim)_(4)(NCS)_(2)]mononuclear units,where the cobalt(II)ion is six-coordinate with four monodentate bim ligands in equatorial positions and two N-thiocyanato groups in the axial sites building a slightly compressed octahedron.
基金acknowledge the Indian Council of Medical Research(ICMR)(project no.2020-2677)the Council of Scientific and Industrial Research(CSIR)(project no.01(3048)/21/EMR-II)+1 种基金the Science and Engineering Research Board(SERB)(CRG/2021/000527)for financial supportDepartment of Science and Technology(DST)for a research fellowship.
文摘Structural distortions from the ideal octahedral geometry are known to facilitate the photorelease of kinetically inert groups in Ru_((II))polypyridyl complexes.Building on this principle,here we report,for the first time,the design of a water-soluble Ru_((II))complex containing a terpyridine-dicarboxylate pentadentate ligand(LH_(2)),formulated as[Ru{ptpy(COO^(-))_(2)}(DMSO)](RuL),engineered for efficient photorelease of the bound monodentate DMSO ligand in aqueous medium.This work presents a novel idea for inducing axial Ru-DMSO bond photolability from the conformational strain originating from a pentadentate ligand in an Ru_((II))complex,triggering photodissociation to create potent cytotoxic species for phototherapeutic application.The molecular identity,and photophysical and electrochemical features with solution speciation of the RuL were examined.The blue-light-triggered photo-substitution was studied to gain insight into potential adduct formation with biological targets relevant to photo-activated chemotherapeutic(PACT)uses.The geometry-optimized structure and the nature of the frontier molecular orbitals have been determined using DFT calculations.The photosubstitution quantum yield(Φ_(PS))in acetonitrile was thirteen times greater than that in water,highlighting the significant influence of solvent on the photochemical efficiency.Notably,the RuL ligand exhibited substantial cytotoxicity under light irradiation,while remaining non-cytotoxic in the dark,underscoring its potential utility in Ru_((II))-based photo-activated chemotherapy.
基金National Natural Science Foundation of China(21871247 and 21973046)the Key Research Program of Frontier Sciences,CAS(ZDBS-LY-SLH023)+1 种基金the Key Research Program of the Chinese Academy of Sciences(ZDRW-CN-2021-3-3)the National Science and Technology Major Project(2020YFE0204500)for financial support.
文摘Low-coordinate lanthanide(Ln)complexes have attracted considerable attention in the field of molecular magnetism by virtue of their excellent potential in constructing high-performance single-molecule magnets(SMMs).From the chemical synthesis point of view,it is challenging to isolate stable Ln(III)complexes with a coordination number(CN)lower than six owing to the large ionic radius,variable coordination pattern and little preference in the bond direction of Ln(III)ions.Herein,a super bulky Schiff-base ligand HL(2-((2,6-dibenzhydryl-4-isopropylphenylimino)methyl)-4,6-di-tert-butylphenol)was used to construct a five-coordinate mononuclear Dy(III)complex,DyL_(2)I(5-Dy-I).Magnetic investigations showed that the strong interaction between Dy(III)and phenolate induces a strong block of magnetization giving the largest anisotropy barrier of 1237 cm-1 and the highest blocking temperature up to 20 K for any reported mononuclear Ln(III)SMMs with CN<6,which greatly motivated researchers to use a bulky monodentate phenolate ligand to synthesize a two-coordinate Dy(III)SMM.
