Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions an...Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.展开更多
The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic...The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic study on isostructural 2D coordination polymers(CPs)based on 1,10-ferrocenediyl-bis(H-phosphinic)acid,with cobalt,manganese,and cadmium metals as electrocatalysts for OER.These polymers were synthesized via a facile solution reaction,yielding crystalline materials with excellent structural integrity.The electrocatalytic performance of CPs composites,prepared with carbon and phosphonium ionic liquid,was evaluated in 0.1 M KOH using a three-electrode system.Notably,the Co-and Cd-based CPs demonstrated exceptional OER activity,achieving an overpotential as low as 236–255 mV at 10 mA cm^(-2),surpassing those of many previously reported CP-based OER catalysts.Furthermore,these materials exhibited high stability over prolonged electrolysis,maintaining their activity without significant degradation.This work not only introduces a new class of ferrocenyl phosphinatebased CPs as highly active and durable OER catalysts but also provides valuable insights into their structureactivity relationships,paving the way for future advancements in electrocatalysis.展开更多
The magnetization dynamics of lanthanide coordination compounds are fundamentals governing their potential applications such as information storage or molecular switches.Herein,two two-dimensional coordination polymer...The magnetization dynamics of lanthanide coordination compounds are fundamentals governing their potential applications such as information storage or molecular switches.Herein,two two-dimensional coordination polymers[Er(CA)_(1.5)(bpy)(DMF)]_(n)(1)and[Er(CA)_(1.5)(phen)(DMF)]_(n)(2)(H_(2)CA=2,5-dichloro-3,6-dihydroxy-p-quinone,bpy=2,2'-bipyridine,phen=1,10-phenanthroline)were synthesized and fully characterized.By the irradiation of ultraviolet light,1 and 2 were converted to la and 2a which contain light-generated radicals,inducing an increase ofχ_(MT)at room temperature.A detailed study of the dynamic magnetic property shows that the magnetization dynamics observed for 1 and la are dominated by Raman process,but Orbach and Raman processes are observed in 2 and 2a.The structural factors influencing the magnetic properties of this photomagnetic system are discussed.展开更多
This study presents the microwave-assisted synthesis and characterization of a series of heterometal lic coordination polymers(HMCPs)with a 4-methyl-2,6-di[(1H-1,2,4-triazol-1-yl)]phenoxo ligand with varying Eu^(Ⅲ)/T...This study presents the microwave-assisted synthesis and characterization of a series of heterometal lic coordination polymers(HMCPs)with a 4-methyl-2,6-di[(1H-1,2,4-triazol-1-yl)]phenoxo ligand with varying Eu^(Ⅲ)/Tb^(Ⅲ)ratios.Single crystal X-ray diffraction reveals a double-chain structure bridged by triazolyl groups.Powder X-ray diffraction confirms the isostructural nature of the synthesized HMCPs.The photophysical properties depend on lanthanide ion concentration and excitation wavelength,leading to a color shift from green to blue as the proportion of Tb^(Ⅲ)decreases and Eu^(Ⅲ)increases.White light generation is achieved in the 8/2 Eu^(Ⅲ)/Tb^(Ⅲ)HMCP(CIE:0.293,0.326)under 335 nm excitation.The study suggests energy transfer from Tb^(Ⅲ)to Eu^(Ⅲ),but both experimental and theoretical calculations indicate that this transfer is orders of magnitude lower than the sensitization through ligand states.展开更多
Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1....Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.展开更多
We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),campho...We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.展开更多
Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfull...Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.展开更多
Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(...Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.展开更多
Chemodynamic therapy(CDT)relying on the transformation of endogenous hydrogen peroxide(H_(2)O_(2))into cytotoxic hydroxyl radicals(·OH)based on the catalysis of Fenton/Fenton-type reactions exhibits great potenti...Chemodynamic therapy(CDT)relying on the transformation of endogenous hydrogen peroxide(H_(2)O_(2))into cytotoxic hydroxyl radicals(·OH)based on the catalysis of Fenton/Fenton-type reactions exhibits great potentiality for cancer treatment.However,the inadequate H_(2)O_(2)supply and intricate redox homeostasis in tumor microenvironment(TME)severely impair the efficacy of CDT.Herein,we design selfassembled 1,2-distearoyl-sn-glycero-3-phosphoethanolamine conjugated polyethylene glycol(DSPE-PEG)-modified Fe(Ⅲ)-juglone nanoscale coordination polymers(FJP NCPs)as redox homeostasis disruptors for juglone-enhanced CDT.Responding to glutathione(GSH)-rich and acidic TME,the Fe^(2+)/Fe^(3+)-guided CDT and GSH consumption by Fe^(3+)are activated,resulting in·OH downstream and up-regulation of lipid peroxidation(LPO).In addition,the released juglone not only depletes GSH through Michael addition,but also elevates intracellular H_(2)O_(2)level for achieving·OH further bursting.With the impressive efficiency of GSH exhaustion and reactive oxygen species(ROS)storm generation,ferroptosis and apoptosis are significantly enhanced by FJP NCPs in vivo.In brief,this facile and efficient design for versatile nanoscale coordination polymers presents a novel paradigm for effectively elevating CDT efficiency and tumor synergistic therapy.展开更多
Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,...Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.展开更多
Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed...Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.展开更多
Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been construc...Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.展开更多
Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmeth...Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.展开更多
Two coordination polymers were synthesized by hydrothermal reaction,namely,[Cd(H_(3)cpbda)(2,2′‑bipy)(H_(2)O)]_(n)(1)and[Mn(H_(3)cpbda)(phen)(H_(2)O)]_(n)(2),where H_(5)cpbda=5,5′‑[(5‑carboxy‑1,3‑phenyl)bis(oxy)]tri...Two coordination polymers were synthesized by hydrothermal reaction,namely,[Cd(H_(3)cpbda)(2,2′‑bipy)(H_(2)O)]_(n)(1)and[Mn(H_(3)cpbda)(phen)(H_(2)O)]_(n)(2),where H_(5)cpbda=5,5′‑[(5‑carboxy‑1,3‑phenyl)bis(oxy)]triisophthalic acid,2,2′‑bipy=2,2′‑bipyridine,phen=1,10‑phenanthroline.The two complexes were characterized by single‑crystal X‑ray diffraction,powder diffraction,infrared spectroscopy,and thermogravimetric analysis.Complexes 1 and 2 are“V”‑shaped 1D chains,and the molecules form 2D(1)and 3D framework(2)structures through weakπ…πstacking.Furthermore,complex 1 was dispersed in an aqueous solution and its fluorescence intensity demonstrated excellent stability.Complex 1 can specifically detect ciprofloxacin in urine with a detection limit of 1.91×10^(-8)mol·L^(-1).CCDC:2359498,1;2359499,2.展开更多
In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxyme...In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.展开更多
Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La_(2)(L)_(3)(DMF)(H_(2)O)_(3)]·H_(2)O}_n(1),{[Eu_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·(H_(2)O)}_n(2){Tb_(2)(L)_(3)(DMF)_(2)(H_(2)O)]...Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La_(2)(L)_(3)(DMF)(H_(2)O)_(3)]·H_(2)O}_n(1),{[Eu_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·(H_(2)O)}_n(2){Tb_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·H_(2)O}n(3) were successfully synthesized from H_(2)L(N,N'-bis(4-carbozylbenzyl)aniline).Remarkably,compound 3 has extremely high sensitivity to 4-nitrophenol.When the concentration of 4-nitrophenol reaches 5.98 × 10^(-3) mmol/L,the fluorescence intensity of compound 3 is quenched by 59%.The calculated K_(SV) is 7.56 × 10~4 and limit of detection(LOD) is 4.73 μg/L.3 exhibits a highly sensitive detection towards Fe^(3+) and compound 2 shows outstanding antibacterial effects on Staphylococcus aureus,re spectively.The white light emission was also investigated by changing the mixing ratio of LaNO_(3),EuNO_(3) and TbNO_(3) during the preparation of coordination polymers.展开更多
Two new coordination polymers,named {[Co3（pfca）6（phen）2]·2H2O}n（1） and[Cu（pfca）2（4,4＇-bpy）（H2O）]n（2）（Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine）,were hydrothermally synthesized an...Two new coordination polymers,named {[Co3（pfca）6（phen）2]·2H2O}n（1） and[Cu（pfca）2（4,4＇-bpy）（H2O）]n（2）（Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine）,were hydrothermally synthesized and characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 crystallizes in the triclinic crystal system,space group P1 with a = 10.939（3）,b = 12.430（4）,c = 13.815（4） A,α=78.436（3）,β= 70.261（3）,γ= 80.268（3）°,V= 1721.8（9） A^3,Dc = 1.508 g/cm^3,Mr= 1564.06,Z = 1,F（000） = 799,μ= 0.802 mm^（-1）,the final R = 0.0432 and wR = 0.1015 for 13250 observed reflections with I 2σ（I）.Complex 2 is of monoclinic system,space group P2／lc with a =15.4985（14）,b = 15.8424（14）,c = 10.9528（10） A,β= 107.1600（10）°,V= 2569.6（4） A^3,Dc = 1.468g/cm^3,Mr = 568.02,Z = 4,F（000） = 1164,μ= 0.906 mm^（-1）,the final R = 0.0371 and wR = 0.0842 for 18183 observed reflections with I〉 2σ（I）.Complex 1 features linear Co（Ⅱ）-trinuclear units,which are assembled into a final 3D supramolecular structure through π…π stacking interactions and F-H weak interactions.Complex 2 consists of 1D polymeric Cu（Ⅱ）-chains that are further cohered together by extensive H-bonds.展开更多
The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges,...The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits： （1） nanoporous spin crossover materials with single metal nodes; （2） metal-radical approach with rigid organic radical ligands and single metal nodes; （C） PCPs with rigid organic ligands and metal oligomer nodes; （D） PCPs with metal complex linkers and polymetal cluster nodes; （E） PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious： the pore benefits from the big cluster according to ＂Scale Chemistry＂, and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.展开更多
Three lanthanide coordination polymers [Ln（bcpb）0.5（NO3）（DEF）2] （Ln = Y （1）, Tb （2）, Eu （3）, H4bcpb = 2,5-bis（2,4-dicarboxyphenyl） pyridine and DEF = N,N-diethylformamide）） have been solvothermally sy...Three lanthanide coordination polymers [Ln（bcpb）0.5（NO3）（DEF）2] （Ln = Y （1）, Tb （2）, Eu （3）, H4bcpb = 2,5-bis（2,4-dicarboxyphenyl） pyridine and DEF = N,N-diethylformamide）） have been solvothermally synthesized under hydrothermal conditions with a novel Hnbcpb ligand and trivalent lanthanide nitrates. Single-crystal X-ray diffraction analysis reveals that compounds 1-3 are isostructural and crystallize in the monoclinic system, space group P21/n. Crystal data for 1： C20H26N409Y, Mr = 555.36, a = 13.022（9）, b = 17.778（12）, c = 10.861（8） A, β= 100.208（3）°, V = 2475（3） A3, Z = 4; Crystal data for 2： C20H26N4OgTb, Mr = 625.37, a = 13.0476（4）, b = 17.8037（7）, c = 10.9398（3） A, β = 100.008（4）°, V = 2496.4（12） A3, Z = 4; Crystal data for 3： C20H26N409Eu, Mr = 618.41, a = 13.055（4）, b = 17.833（5）, c = 10.893（3）A, β = 100.133（4）°, V= 2496.4（12） A3, Z = 4. The compounds were characterized by thermogravimetric analysis （TGA）, IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1-3 all feature 2D networks with -ABAB- fashions. The luminescent properties of compounds 1-3 and free H4bcpb ligand were investigated at room temperature. The results show that the H4bcpb ligand can efficiently transfer energy to the Tb（III） ions, while the energy is not fully transferred from the H4bcpb ligand to the Eu（III） ions.展开更多
The assembly reactions of o- （or m-, or p-） tetrafluorobenzenedicarboxylic acid （denoted as o-H2L, m-H2L and p-HzL, respectively）, benzonitrile and Ag＋ ion led to three compounds： [Ag2（PhCN）2（o-HL）2]n （1）,...The assembly reactions of o- （or m-, or p-） tetrafluorobenzenedicarboxylic acid （denoted as o-H2L, m-H2L and p-HzL, respectively）, benzonitrile and Ag＋ ion led to three compounds： [Ag2（PhCN）2（o-HL）2]n （1）, [Ag2（PhCN）2（m-HL）2]n （2） and [Ag2（PhCN）2（p-L）], （3）. 1 and 2 feature a 1D coordination chain, while 3 bears a 2D net structure. A variety of weak interactions are observed in the compounds. Strong nwrinteractions connect the 1D chains into a 3D supramolecular network in 1. Hydrogen bonds connect the chains into layers in 2. Three types of interesting π-π interactions also assemble the 2D layers into a 3D overall structure in 3.展开更多
文摘Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.
文摘The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic study on isostructural 2D coordination polymers(CPs)based on 1,10-ferrocenediyl-bis(H-phosphinic)acid,with cobalt,manganese,and cadmium metals as electrocatalysts for OER.These polymers were synthesized via a facile solution reaction,yielding crystalline materials with excellent structural integrity.The electrocatalytic performance of CPs composites,prepared with carbon and phosphonium ionic liquid,was evaluated in 0.1 M KOH using a three-electrode system.Notably,the Co-and Cd-based CPs demonstrated exceptional OER activity,achieving an overpotential as low as 236–255 mV at 10 mA cm^(-2),surpassing those of many previously reported CP-based OER catalysts.Furthermore,these materials exhibited high stability over prolonged electrolysis,maintaining their activity without significant degradation.This work not only introduces a new class of ferrocenyl phosphinatebased CPs as highly active and durable OER catalysts but also provides valuable insights into their structureactivity relationships,paving the way for future advancements in electrocatalysis.
基金Project supported by the National Natural Science Foundation of China(21971123,21931004,92156002)。
文摘The magnetization dynamics of lanthanide coordination compounds are fundamentals governing their potential applications such as information storage or molecular switches.Herein,two two-dimensional coordination polymers[Er(CA)_(1.5)(bpy)(DMF)]_(n)(1)and[Er(CA)_(1.5)(phen)(DMF)]_(n)(2)(H_(2)CA=2,5-dichloro-3,6-dihydroxy-p-quinone,bpy=2,2'-bipyridine,phen=1,10-phenanthroline)were synthesized and fully characterized.By the irradiation of ultraviolet light,1 and 2 were converted to la and 2a which contain light-generated radicals,inducing an increase ofχ_(MT)at room temperature.A detailed study of the dynamic magnetic property shows that the magnetization dynamics observed for 1 and la are dominated by Raman process,but Orbach and Raman processes are observed in 2 and 2a.The structural factors influencing the magnetic properties of this photomagnetic system are discussed.
基金Project supported by Fondo Nacional de Desarrollo Científico y Tecnologico,FONDECYT(1200033)the National Doctoral Scholarship(21192195)+2 种基金Chile,Conselho Nacional de Desenvolvimento Científico e Tecnologico(CNPq,427164/2018-4 and 310307/2021-0)Funda?āo de AmparoàPesquisa do Estado de Goiás(FAPEG),Brazil,developed within the scope of the project CICECO-Aveiro Institute of Materials(UIDB/50011/2020,UIDP/50011/2020,LA/P/0006/2020)LogicALL(PTDC/CTMCTM/0340/2021)financed through the FCT-Foundation for Science and Technology/Ministry of Education(PIDDAC-Central Government Investment and Development Expenditure Program),Portugal。
文摘This study presents the microwave-assisted synthesis and characterization of a series of heterometal lic coordination polymers(HMCPs)with a 4-methyl-2,6-di[(1H-1,2,4-triazol-1-yl)]phenoxo ligand with varying Eu^(Ⅲ)/Tb^(Ⅲ)ratios.Single crystal X-ray diffraction reveals a double-chain structure bridged by triazolyl groups.Powder X-ray diffraction confirms the isostructural nature of the synthesized HMCPs.The photophysical properties depend on lanthanide ion concentration and excitation wavelength,leading to a color shift from green to blue as the proportion of Tb^(Ⅲ)decreases and Eu^(Ⅲ)increases.White light generation is achieved in the 8/2 Eu^(Ⅲ)/Tb^(Ⅲ)HMCP(CIE:0.293,0.326)under 335 nm excitation.The study suggests energy transfer from Tb^(Ⅲ)to Eu^(Ⅲ),but both experimental and theoretical calculations indicate that this transfer is orders of magnitude lower than the sensitization through ligand states.
文摘Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.
文摘We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
文摘Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.
基金financially supported by the National Key Research and Development Program of China(No.2022YFB3503700)the National Natural Science Foundation of China(NSFC,Nos.51929201,52102354,and 52202353)the projects for science and technology development plan of Jilin province(Nos.20220101070JC,20210402046GH,and 20220508089RC)。
文摘Chemodynamic therapy(CDT)relying on the transformation of endogenous hydrogen peroxide(H_(2)O_(2))into cytotoxic hydroxyl radicals(·OH)based on the catalysis of Fenton/Fenton-type reactions exhibits great potentiality for cancer treatment.However,the inadequate H_(2)O_(2)supply and intricate redox homeostasis in tumor microenvironment(TME)severely impair the efficacy of CDT.Herein,we design selfassembled 1,2-distearoyl-sn-glycero-3-phosphoethanolamine conjugated polyethylene glycol(DSPE-PEG)-modified Fe(Ⅲ)-juglone nanoscale coordination polymers(FJP NCPs)as redox homeostasis disruptors for juglone-enhanced CDT.Responding to glutathione(GSH)-rich and acidic TME,the Fe^(2+)/Fe^(3+)-guided CDT and GSH consumption by Fe^(3+)are activated,resulting in·OH downstream and up-regulation of lipid peroxidation(LPO).In addition,the released juglone not only depletes GSH through Michael addition,but also elevates intracellular H_(2)O_(2)level for achieving·OH further bursting.With the impressive efficiency of GSH exhaustion and reactive oxygen species(ROS)storm generation,ferroptosis and apoptosis are significantly enhanced by FJP NCPs in vivo.In brief,this facile and efficient design for versatile nanoscale coordination polymers presents a novel paradigm for effectively elevating CDT efficiency and tumor synergistic therapy.
文摘Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.
文摘Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.
文摘Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.
文摘Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.
文摘Two coordination polymers were synthesized by hydrothermal reaction,namely,[Cd(H_(3)cpbda)(2,2′‑bipy)(H_(2)O)]_(n)(1)and[Mn(H_(3)cpbda)(phen)(H_(2)O)]_(n)(2),where H_(5)cpbda=5,5′‑[(5‑carboxy‑1,3‑phenyl)bis(oxy)]triisophthalic acid,2,2′‑bipy=2,2′‑bipyridine,phen=1,10‑phenanthroline.The two complexes were characterized by single‑crystal X‑ray diffraction,powder diffraction,infrared spectroscopy,and thermogravimetric analysis.Complexes 1 and 2 are“V”‑shaped 1D chains,and the molecules form 2D(1)and 3D framework(2)structures through weakπ…πstacking.Furthermore,complex 1 was dispersed in an aqueous solution and its fluorescence intensity demonstrated excellent stability.Complex 1 can specifically detect ciprofloxacin in urine with a detection limit of 1.91×10^(-8)mol·L^(-1).CCDC:2359498,1;2359499,2.
基金financially supported by the Natural Science Foundation of China(no.21576059)the Key Technologies R&D Program(no.2011BAE06B02)+1 种基金the International Science&Technology Cooperation Program of China(2010DFB60840)the Science and Technology Project of Guizhou Province(nos.[2012]6012 and[2011]3016)
文摘In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.
基金supported by the Science and Technology Development Planning of Jilin Province,China (20210101129JC)。
文摘Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La_(2)(L)_(3)(DMF)(H_(2)O)_(3)]·H_(2)O}_n(1),{[Eu_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·(H_(2)O)}_n(2){Tb_(2)(L)_(3)(DMF)_(2)(H_(2)O)]·H_(2)O}n(3) were successfully synthesized from H_(2)L(N,N'-bis(4-carbozylbenzyl)aniline).Remarkably,compound 3 has extremely high sensitivity to 4-nitrophenol.When the concentration of 4-nitrophenol reaches 5.98 × 10^(-3) mmol/L,the fluorescence intensity of compound 3 is quenched by 59%.The calculated K_(SV) is 7.56 × 10~4 and limit of detection(LOD) is 4.73 μg/L.3 exhibits a highly sensitive detection towards Fe^(3+) and compound 2 shows outstanding antibacterial effects on Staphylococcus aureus,re spectively.The white light emission was also investigated by changing the mixing ratio of LaNO_(3),EuNO_(3) and TbNO_(3) during the preparation of coordination polymers.
基金Supported by the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.14HASTIT017)the Program for Innovative Research Team(in Science and Technology)in University of Henan Province(No.14IRTSTHN008)+1 种基金the Foundation of Education Committee of Henan Province(No.142300410301)the National Natural Science Foundation of China(No.21571093)
文摘Two new coordination polymers,named {[Co3（pfca）6（phen）2]·2H2O}n（1） and[Cu（pfca）2（4,4＇-bpy）（H2O）]n（2）（Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine）,were hydrothermally synthesized and characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 crystallizes in the triclinic crystal system,space group P1 with a = 10.939（3）,b = 12.430（4）,c = 13.815（4） A,α=78.436（3）,β= 70.261（3）,γ= 80.268（3）°,V= 1721.8（9） A^3,Dc = 1.508 g/cm^3,Mr= 1564.06,Z = 1,F（000） = 799,μ= 0.802 mm^（-1）,the final R = 0.0432 and wR = 0.1015 for 13250 observed reflections with I 2σ（I）.Complex 2 is of monoclinic system,space group P2／lc with a =15.4985（14）,b = 15.8424（14）,c = 10.9528（10） A,β= 107.1600（10）°,V= 2569.6（4） A^3,Dc = 1.468g/cm^3,Mr = 568.02,Z = 4,F（000） = 1164,μ= 0.906 mm^（-1）,the final R = 0.0371 and wR = 0.0842 for 18183 observed reflections with I〉 2σ（I）.Complex 1 features linear Co（Ⅱ）-trinuclear units,which are assembled into a final 3D supramolecular structure through π…π stacking interactions and F-H weak interactions.Complex 2 consists of 1D polymeric Cu（Ⅱ）-chains that are further cohered together by extensive H-bonds.
基金supported by the State Key Laboratory of Structural Chemistry, NNSFC (20733003)Chinese Academy of Sciences (KJCX2-YW-M05)+1 种基金973 Program (2007CB815301, 2006CB932900)the NSF of Fujian Province (2006L2005, 2006J0014)
文摘The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits： （1） nanoporous spin crossover materials with single metal nodes; （2） metal-radical approach with rigid organic radical ligands and single metal nodes; （C） PCPs with rigid organic ligands and metal oligomer nodes; （D） PCPs with metal complex linkers and polymetal cluster nodes; （E） PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious： the pore benefits from the big cluster according to ＂Scale Chemistry＂, and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.
基金supported by the Fundamental Research Funds for the Central Universities(JB-ZR1119)the Research Foundation for Talented Scholars(09BS518,13B0095)+1 种基金the NSF of Fujian Province(Nos.2013J01237)the Educational Office of Fujian Province(JA12010)
文摘Three lanthanide coordination polymers [Ln（bcpb）0.5（NO3）（DEF）2] （Ln = Y （1）, Tb （2）, Eu （3）, H4bcpb = 2,5-bis（2,4-dicarboxyphenyl） pyridine and DEF = N,N-diethylformamide）） have been solvothermally synthesized under hydrothermal conditions with a novel Hnbcpb ligand and trivalent lanthanide nitrates. Single-crystal X-ray diffraction analysis reveals that compounds 1-3 are isostructural and crystallize in the monoclinic system, space group P21/n. Crystal data for 1： C20H26N409Y, Mr = 555.36, a = 13.022（9）, b = 17.778（12）, c = 10.861（8） A, β= 100.208（3）°, V = 2475（3） A3, Z = 4; Crystal data for 2： C20H26N4OgTb, Mr = 625.37, a = 13.0476（4）, b = 17.8037（7）, c = 10.9398（3） A, β = 100.008（4）°, V = 2496.4（12） A3, Z = 4; Crystal data for 3： C20H26N409Eu, Mr = 618.41, a = 13.055（4）, b = 17.833（5）, c = 10.893（3）A, β = 100.133（4）°, V= 2496.4（12） A3, Z = 4. The compounds were characterized by thermogravimetric analysis （TGA）, IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1-3 all feature 2D networks with -ABAB- fashions. The luminescent properties of compounds 1-3 and free H4bcpb ligand were investigated at room temperature. The results show that the H4bcpb ligand can efficiently transfer energy to the Tb（III） ions, while the energy is not fully transferred from the H4bcpb ligand to the Eu（III） ions.
基金Supported by the NNSFC (21071025,91122031, 21107008)Doctoral Fund of Ministry of Education of China (20100041120021)the Fundamental Research Funds for the Central Universities (DUT12YQ04)
文摘The assembly reactions of o- （or m-, or p-） tetrafluorobenzenedicarboxylic acid （denoted as o-H2L, m-H2L and p-HzL, respectively）, benzonitrile and Ag＋ ion led to three compounds： [Ag2（PhCN）2（o-HL）2]n （1）, [Ag2（PhCN）2（m-HL）2]n （2） and [Ag2（PhCN）2（p-L）], （3）. 1 and 2 feature a 1D coordination chain, while 3 bears a 2D net structure. A variety of weak interactions are observed in the compounds. Strong nwrinteractions connect the 1D chains into a 3D supramolecular network in 1. Hydrogen bonds connect the chains into layers in 2. Three types of interesting π-π interactions also assemble the 2D layers into a 3D overall structure in 3.
