Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex...Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.展开更多
Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature ...Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature is challenging but highly desired.In this work,two novel 2D cobalt metal-organic complexes,namely[Co(L)(5-HIP)]·2H_(2)O(Co-MOC-1)and[Co(L)(BTEC)_(0.5)]·H_(2)O(Co-MOC-2)(L=(E)-4,4-(ethene-1,2-diyl))bis(N-(pyridin-3-yl)benzamide;5-H_(2)HIP=5-hydroxyisophthalic acid;H4BTEC=pyromellitic acid)were designed and synthesized through hydrothermal method,which exhibited different metal coordination modes(4-coordinate and 5-coordinate,respectively)and 2D layer structures directed by different carboxylates co-ligands.Two Co-MOCs can serve as heterogeneous catalysts for the selective oxidation of olefins to epoxides at room temperature using O_(2)as oxidant.Furthermore,a higher catalysis activity of Co-MOC-1 than Co-MOC-2(96.7%vs.90.2%yield of 1,2-epoxycyclooctane)was observed,which may be attributed to the coordination unsaturated Co centers,the less coordination number and larger interlayer spacing of Co-MOC-1.展开更多
Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins.However,the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mon...Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins.However,the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mononuclear complex due to the difference of their electronegativities,and coordination capabilities.Herein,we report a novel sulfur-phosphine co-coordinated heterogeneous Rh mononuclear complex catalyst(Rh_(1)/POPs-PPh_(3)&S),which exhibits an unexpected 1.5–2.0 times catalytic activity for hydroformylation of olefins(C_(3)=,C_(5)=–C_(8)=),in comparison with the solely phosphine-coordinated Rh mononuclear complex catalyst(Rh_(1)/POPs-PPh_(3)).In contrast,sulfur coordination alone leads to severe sulfur poisoning with significantly inhibited catalytic performance.Experimental and theoretical analyses reveal that phosphine coordination promotes catalytic activity via its strong electron-donating ability,while sulfur occupies a coordination site and reduces the electronic density of Rh ions.The synergistical coordination of sulfur and phosphine optimizes the electronic density of active Rh ions and decreases the energy barrier of the rate-determining step of olefin insertion,thus enhancing the hydroformylation activity,regioselectivity and stability of Rh_(1)/POPs-PPh_(3)&S.展开更多
With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion...With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion of commonly used polyolefin separators at high temperatures,as well as narrow usable temperature range and high flammability of conventionally commercialized liquid electrolytes.In this work,we report a multifunctional separator mainly consisting of Zn^(2+)-phytate coordination complex nanoparticles and bacterial cellulose nanofibers,named the BZP separator,which possesses high porosity,excellent thermotolerance,good flame retardancy,abilities of anion binding and Ni^(2+)capturing.Through cooperating with the fluoride-free wide-temperature-range electrolyte,Li//LiFePO_(4) cells not only deliver discharge capacities of 110.39 mA h g^(-1)and 113.25 mA h g^(-1)after 2200 cycles (2 C) and1600 cycles (5 C) at 25℃,with capacity retentions of 76.59%and 86.09%,respectively,but also exhibit excellent cycling performance at 80℃ and-40℃.Significantly,the Li//NCM811 cell with a loading of7.8 mg cm^(-2)delivers a discharge capacity of 146.64 mA h g^(-1)after 200 cycles at 0.5 C,with a capacity retention of 89.03%.In addition,pouch cells can work at 120℃ and have low flammability.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
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
A complex system is inherently high-dimensional.Recent studies indicate that,even without complete knowledge of its evolutionary dynamics,the future behavior of such a system can be predicted using time-series data(da...A complex system is inherently high-dimensional.Recent studies indicate that,even without complete knowledge of its evolutionary dynamics,the future behavior of such a system can be predicted using time-series data(data-driven prediction).This suggests that the essential dynamics of a complex system can be captured through a low-dimensional representation.Virus evolution and climate change are two examples of complex,time-varying systems.In this article,we show that mutations in the spike protein provide valuable data for predicting SARS-CoV-2 variants,forecasting the possible emergence of the new macro-lineage Q in the near future.Our analysis also demonstrates that carbon dioxide concentration is a reliable indicator for predicting the evolution of the climate system,extending global surface air temperature(GSAT)forecasts through 2500.展开更多
With the boom in maritime activities,the need for highly reliable maritime communication is becoming urgent,which is an important component of 5G/6G communication networks.However,the bandwidth reuse characteristic of...With the boom in maritime activities,the need for highly reliable maritime communication is becoming urgent,which is an important component of 5G/6G communication networks.However,the bandwidth reuse characteristic of 5G/6G networks will inevitably lead to severe interference,resulting in degradation in the communication performance of maritime users.In this paper,we propose a safe deep reinforcement learning based interference coordination scheme to jointly optimize the power control and bandwidth allocation in maritime communication systems,and exploit the quality-of-service requirements of users as the risk value references to evaluate the communication policies.In particular,this scheme designs a deep neural network to select the communication policies through the evaluation network and update the parameters using the target network,which improves the communication performance and speeds up the convergence rate.Moreover,the Nash equilibrium of the interference coordination game and the computational complexity of the proposed scheme are analyzed.Simulation and experimental results verify the performance gain of the proposed scheme compared with benchmarks.展开更多
Image-maps,a hybrid design with satellite images as background and map symbols uploaded,aim to combine the advantages of maps’high interpretation efficiency and satellite images’realism.The usability of image-maps i...Image-maps,a hybrid design with satellite images as background and map symbols uploaded,aim to combine the advantages of maps’high interpretation efficiency and satellite images’realism.The usability of image-maps is influenced by the representations of background images and map symbols.Many researchers explored the optimizations for background images and symbolization techniques for symbols to reduce the complexity of image-maps and improve the usability.However,little literature was found for the optimum amount of symbol loading.This study focuses on the effects of background image complexity and map symbol load on the usability(i.e.,effectiveness and efficiency)of image-maps.Experiments were conducted by user studies via eye-tracking equipment and an online questionnaire survey.Experimental data sets included image-maps with ten levels of map symbol load in ten areas.Forty volunteers took part in the target searching experiments.It has been found that the usability,i.e.,average time viewed(efficiency)and average revisits(effectiveness)of targets recorded,is influenced by the complexity of background images,a peak exists for optimum symbol load for an image-map.The optimum levels for symbol load for different image-maps also have a peak when the complexity of the background image/image map increases.The complexity of background images serves as a guideline for optimum map symbol load in image-map design.This study enhanced user experience by optimizing visual clarity and managing cognitive load.Understanding how these factors interact can help create adaptive maps that maintain clarity and usability,guiding AI algorithms to adjust symbol density based on user context.This research establishes the practices for map design,making cartographic tools more innovative and more user-centric.展开更多
The Jiuyishan granitic complex,located in the Nanling Range,South China,is composed of five granitic plutons(Xuehuading,Jinjiling,Pangxiemu,Shaziling and Xishan).Zircon U-Pb dating of four plutons(Jinjiling,Pangxiemu,...The Jiuyishan granitic complex,located in the Nanling Range,South China,is composed of five granitic plutons(Xuehuading,Jinjiling,Pangxiemu,Shaziling and Xishan).Zircon U-Pb dating of four plutons(Jinjiling,Pangxiemu,Shaziling and Xishan)yielded similar ages of approximately 153 Ma,indicating indistinguishable ages within error.Three plutons except the Shaziling pluton,have consistentε_(Nd)(t)(-7.8 to-5.8)andε_(Hf)(t)(-9.1 to-2.2)values,which are similar to those of the lower crustal granulitic metasedimentary and meta-igneous rocks in South China.Compared to other three plutons,the Shaziling pluton has consistentε_(Nd)(t)(-7.4 to-6.8)andε_(Hf)(t)(-7.5 to-4.7)values and shows similar source,but the Shaziling mafic microgranular enclaves(MMEs)show variableε_(Hf)(t)(-14.2 to 4.8)values,indicating a remarkable mantle magma injection of the Shaziling pluton.Zircon Ce/Sm-Yb/Gd,whole-rock CaO-P_(2)O_(5)and CaO-TiO_(2)linear trends reveal that from the Xishan to the Shaziling and from the Jinjiling to the Pangxiemu granites,they experienced apatite and titanite fractionation,respectively.Zircon Th,U,Nb,Ta,Hf,Ti,Y,P and rare earth element(REE)contents and whole-rock Sr,Ba and Rb contents also show that the Shaziling,Xishan,Jinjiling and Pangxiemu granites followed a discontinuous evolutionary series,but the Pangxiemu granites exhibit highly evolved nature.Four main controlling factors of W-Sn and rare metal mineralization in granitic rocks were discussed,and we found that the mineralization in Jiuyishan granitic complex was mainly controlled by the fractionation degree and crystallization temperature,but were rarely affected by oxygen fugacity and mantle material input.The Pangxiemu granites show particularly higher Rb and Ta contents than the other three plutons,implying that the ore deposits developed in the Jiuyishan Complex were directly related to the most evolved Pangxiemu pluton,with the occurrence of Rb and Ta as the most likely rare metal mineralization in the Jiuyishan District.A crystal mush model is proposed to interpret the petrogenetic and mineralizing processes of the Jiuyishan granitic complex.展开更多
Smart molecules have attracted increasing attention due to their transformative role in creating the next generation of smart structures and devices.Smart bistable coordination complexes are a class of functional comp...Smart molecules have attracted increasing attention due to their transformative role in creating the next generation of smart structures and devices.Smart bistable coordination complexes are a class of functional complexes which have two stable states that can be reversibly switched in response to external stimuli.Such bistable molecules play a vital role in various applications,such as sensors,data storage,spintronics,smart windows,optical switches,information encryption and decryption,displays,actuators,etc.Herein,the recent research studies into the development of these smart bistable metal coordination complexes are reviewed.According to the different external stimuli,these smart bistable coordination systems have been classified and summarized,including light-responsive systems,thermally-responsive systems,electrically-responsive systems,mechanicallyresponsive systems,and some other cases.These systems are further subdivided according to the changes in signals(e.g.,color,fluorescence,spin state,crystalline phase)under external stimuli.The design principles of each type of smart bistable metal complexes as well as their broad and innovative applications are comprehensively described.Finally,the challenges and opportunities in this field are briefly analyzed and discussed.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
A phenylphenothiazine anchored Tb(Ⅲ)-cyclen complex PTP-Cy-Tb for hypochlorite ion(ClO^(-))detection has been designed and prepared.PTP-Cy-Tb shows a weak Tb-based emission with AIE-characteristics in aqueous solutio...A phenylphenothiazine anchored Tb(Ⅲ)-cyclen complex PTP-Cy-Tb for hypochlorite ion(ClO^(-))detection has been designed and prepared.PTP-Cy-Tb shows a weak Tb-based emission with AIE-characteristics in aqueous solutions.After addition of ClO^(-),the fluorescence of PTP-Cy-Tb gives a large enhancement for oxidization the thioether to sulfoxide group.The detection limit of PTP-Cy-Tb toward ClO^(-)is as low as 8.85 nmol/L.The sensing mechanism was detailedly investigated by time of flight mass spectrometer(TOF-MS),Fourier transform infrared spectroscopy(FT-IR)and density functional theory(DFT)calculation.In addition,PTP-Cy-Tb has been successfully used for on-site and real-time detection of ClO^(-)in real water samples by using the smartphone-based visualization method and test strips.展开更多
Studying the coupling coordination development of new energy vehicles(NEVs)and the ecological environment in China is helpful in promoting the development of NEVs in the country and is of great significance in promoti...Studying the coupling coordination development of new energy vehicles(NEVs)and the ecological environment in China is helpful in promoting the development of NEVs in the country and is of great significance in promoting high-quality development of new energy in China.This paper constructs an evaluation index system for the development of NEVs and the ecological environment.It uses game theory combining weighting model,particle swarm optimized projection tracking evaluation model,coupling coordination degree model,and machine learning algorithms to calculate and analyze the level of coupling coordination development of NEVs and the ecological environment in China from 2010 to 2021,and identifies the driving factors.The research results show that:(i)From 2010 to 2021,the development index of NEVs in China has steadily increased from 0.085 to 0.634,while the ecological environment level index significantly rose from 0.170 to 0.884,reflecting the continuous development of China in both NEVs and the ecological environment.(ii)From 2010 to 2012,the two systems—new energy vehicle(NEV)development and the ecological environment—were in a period of imbalance and decline.From 2013 to 2016,they underwent a transition period,and from 2017 to 2021,they entered a period of coordinated development showing a trend of benign and continuous improvement.By 2021,they reached a good level of coordination.(iii)Indicators such as the number of patents granted for NEVs,water consumption per unit of GDP,and energy consumption per unit of GDP are the main driving factors affecting the coupling coordination development of NEVs and the ecological environment in China.展开更多
One Yb(Ⅲ)-based coordination polymer,{[Yb(H_(2)dhtp)1.5(H_(2)O)_(4)]·3H_(2)O}n(1)(H_(4)dhtp=2,5-dihydroxytere-phthalic acid),was fabricated and structurally characterized by single-crystal X-ray diffraction,IR,p...One Yb(Ⅲ)-based coordination polymer,{[Yb(H_(2)dhtp)1.5(H_(2)O)_(4)]·3H_(2)O}n(1)(H_(4)dhtp=2,5-dihydroxytere-phthalic acid),was fabricated and structurally characterized by single-crystal X-ray diffraction,IR,powder X-ray diffraction,X-ray diffraction,and elemental analysis.Complex 1 displays a 1D chain structure,and belongs to P1 group.The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm(λex=408 nm).It exhibited the emission characteristic of the H_(4)dhtp ligand.The fluorescence of 1 in water displayed the stron-gest intensity.In detecting various metal ions,adding Zr^(4+)led to a blue shift in fluorescence,accompanied by an increase in intensity,whereas the presence of Fe^(3+)resulted in a decrease in luminescence.The changes observed in the IR spectrum indicate an interaction between Fe^(3+)/Zr^(4+)and complex 1,resulting in the variation of luminescence properties.展开更多
Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic...Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic coor-dination polymer[Cd(bcbpy)I_(2)]·2H_(2)O(1)was constructed.Complex 1 displays a 1D chain structure and exhibits thermochromic behavior.Under different temperature stimulation,the complex(ground)slowly changed from green to yellow-green,and with the increase of temperature,the color of complex 1 gradually deepened,and finally became orange-yellow.Therefore,complex 1 was prepared as a thermochromic film.In addition,we also performed electrochemical tests on complex 1,which showed that the complex is a semiconductor material.CCDC:2391802.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
Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation,fast response,high spatial resolution,and so on,for which the luminescent thermometers are the key.Here,a...Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation,fast response,high spatial resolution,and so on,for which the luminescent thermometers are the key.Here,a 1D complex[Tb_(4)(HTC4A)(TC4A)(OBBA)_(2)(CH_(3)OH)_(4)(μ4-OH)]n(1)was obtained by solvothermal synthesis,where H 4TC4A=p-tert-butylthiacalix[4]arene,and H_(2)OBBA=4,4'-oxybisbenzoic acid.This complex is featured with a chain-like polymer constructed by bridging some sandwich-like Tb_(4)-(TC4A)_(2)entities through OBBA2-ligands.It exhibited the characteristic emission of the Tb^(3+)ion.Both fluorescence intensity and lifetime decreased with increasing temperature.The relative sensitivity was up to 8.743%·K^(-1)at 473 K,indicating it is a good ratiometric luminescent thermometer.This complex had good stability under different pH values and in common solvents.CCDC:2392643.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
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
文摘Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.
基金financially supported by the National Natural Science Foundation of China(Nos.22271021,21971024,22201021)the Doctoral Scientific Research Foundation of Liaoning Province(No.2022-BS-302)。
文摘Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature is challenging but highly desired.In this work,two novel 2D cobalt metal-organic complexes,namely[Co(L)(5-HIP)]·2H_(2)O(Co-MOC-1)and[Co(L)(BTEC)_(0.5)]·H_(2)O(Co-MOC-2)(L=(E)-4,4-(ethene-1,2-diyl))bis(N-(pyridin-3-yl)benzamide;5-H_(2)HIP=5-hydroxyisophthalic acid;H4BTEC=pyromellitic acid)were designed and synthesized through hydrothermal method,which exhibited different metal coordination modes(4-coordinate and 5-coordinate,respectively)and 2D layer structures directed by different carboxylates co-ligands.Two Co-MOCs can serve as heterogeneous catalysts for the selective oxidation of olefins to epoxides at room temperature using O_(2)as oxidant.Furthermore,a higher catalysis activity of Co-MOC-1 than Co-MOC-2(96.7%vs.90.2%yield of 1,2-epoxycyclooctane)was observed,which may be attributed to the coordination unsaturated Co centers,the less coordination number and larger interlayer spacing of Co-MOC-1.
文摘Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins.However,the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mononuclear complex due to the difference of their electronegativities,and coordination capabilities.Herein,we report a novel sulfur-phosphine co-coordinated heterogeneous Rh mononuclear complex catalyst(Rh_(1)/POPs-PPh_(3)&S),which exhibits an unexpected 1.5–2.0 times catalytic activity for hydroformylation of olefins(C_(3)=,C_(5)=–C_(8)=),in comparison with the solely phosphine-coordinated Rh mononuclear complex catalyst(Rh_(1)/POPs-PPh_(3)).In contrast,sulfur coordination alone leads to severe sulfur poisoning with significantly inhibited catalytic performance.Experimental and theoretical analyses reveal that phosphine coordination promotes catalytic activity via its strong electron-donating ability,while sulfur occupies a coordination site and reduces the electronic density of Rh ions.The synergistical coordination of sulfur and phosphine optimizes the electronic density of active Rh ions and decreases the energy barrier of the rate-determining step of olefin insertion,thus enhancing the hydroformylation activity,regioselectivity and stability of Rh_(1)/POPs-PPh_(3)&S.
基金supported by the National Natural Science Foundation of China (22275131)the Institutional Research Fund from Sichuan University (2021SCUNL201)+1 种基金the 111 Project (B20001)the Fundamental Research Funds for the Central Universities。
文摘With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion of commonly used polyolefin separators at high temperatures,as well as narrow usable temperature range and high flammability of conventionally commercialized liquid electrolytes.In this work,we report a multifunctional separator mainly consisting of Zn^(2+)-phytate coordination complex nanoparticles and bacterial cellulose nanofibers,named the BZP separator,which possesses high porosity,excellent thermotolerance,good flame retardancy,abilities of anion binding and Ni^(2+)capturing.Through cooperating with the fluoride-free wide-temperature-range electrolyte,Li//LiFePO_(4) cells not only deliver discharge capacities of 110.39 mA h g^(-1)and 113.25 mA h g^(-1)after 2200 cycles (2 C) and1600 cycles (5 C) at 25℃,with capacity retentions of 76.59%and 86.09%,respectively,but also exhibit excellent cycling performance at 80℃ and-40℃.Significantly,the Li//NCM811 cell with a loading of7.8 mg cm^(-2)delivers a discharge capacity of 146.64 mA h g^(-1)after 200 cycles at 0.5 C,with a capacity retention of 89.03%.In addition,pouch cells can work at 120℃ and have low flammability.
文摘To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
基金Natural science foundation of Inner Mongolia(2024LHMS06018)The basic scientific research funding for directly affiliated universities in the Inner Mongolia(JY20250094)。
文摘A complex system is inherently high-dimensional.Recent studies indicate that,even without complete knowledge of its evolutionary dynamics,the future behavior of such a system can be predicted using time-series data(data-driven prediction).This suggests that the essential dynamics of a complex system can be captured through a low-dimensional representation.Virus evolution and climate change are two examples of complex,time-varying systems.In this article,we show that mutations in the spike protein provide valuable data for predicting SARS-CoV-2 variants,forecasting the possible emergence of the new macro-lineage Q in the near future.Our analysis also demonstrates that carbon dioxide concentration is a reliable indicator for predicting the evolution of the climate system,extending global surface air temperature(GSAT)forecasts through 2500.
文摘With the boom in maritime activities,the need for highly reliable maritime communication is becoming urgent,which is an important component of 5G/6G communication networks.However,the bandwidth reuse characteristic of 5G/6G networks will inevitably lead to severe interference,resulting in degradation in the communication performance of maritime users.In this paper,we propose a safe deep reinforcement learning based interference coordination scheme to jointly optimize the power control and bandwidth allocation in maritime communication systems,and exploit the quality-of-service requirements of users as the risk value references to evaluate the communication policies.In particular,this scheme designs a deep neural network to select the communication policies through the evaluation network and update the parameters using the target network,which improves the communication performance and speeds up the convergence rate.Moreover,the Nash equilibrium of the interference coordination game and the computational complexity of the proposed scheme are analyzed.Simulation and experimental results verify the performance gain of the proposed scheme compared with benchmarks.
基金National Natural Science Foundation of China(No.42301518)Hubei Key Laboratory of Regional Development and Environmental Response(No.2023(A)002)Key Laboratory of the Evaluation and Monitoring of Southwest Land Resources(Ministry of Education)(No.TDSYS202304).
文摘Image-maps,a hybrid design with satellite images as background and map symbols uploaded,aim to combine the advantages of maps’high interpretation efficiency and satellite images’realism.The usability of image-maps is influenced by the representations of background images and map symbols.Many researchers explored the optimizations for background images and symbolization techniques for symbols to reduce the complexity of image-maps and improve the usability.However,little literature was found for the optimum amount of symbol loading.This study focuses on the effects of background image complexity and map symbol load on the usability(i.e.,effectiveness and efficiency)of image-maps.Experiments were conducted by user studies via eye-tracking equipment and an online questionnaire survey.Experimental data sets included image-maps with ten levels of map symbol load in ten areas.Forty volunteers took part in the target searching experiments.It has been found that the usability,i.e.,average time viewed(efficiency)and average revisits(effectiveness)of targets recorded,is influenced by the complexity of background images,a peak exists for optimum symbol load for an image-map.The optimum levels for symbol load for different image-maps also have a peak when the complexity of the background image/image map increases.The complexity of background images serves as a guideline for optimum map symbol load in image-map design.This study enhanced user experience by optimizing visual clarity and managing cognitive load.Understanding how these factors interact can help create adaptive maps that maintain clarity and usability,guiding AI algorithms to adjust symbol density based on user context.This research establishes the practices for map design,making cartographic tools more innovative and more user-centric.
基金financially supported by the Provincial Natural Science Foundation of Hunan(Nos.2019JJ50831,2023JJ30505 and 2023JJ40541)the China Postdoctoral Science Foundation(Nos.2017M622597 and 2021M690591)+2 种基金the Open Research Fund Program of Fundamental Science on Radioactive Geology and Exploration Technology Laboratory(East China University of Technology)(No.2022RGET04)the National Foreign Expert Project(No.G2022029012L)the National Nature Science Foundation of China(No.41002022)。
文摘The Jiuyishan granitic complex,located in the Nanling Range,South China,is composed of five granitic plutons(Xuehuading,Jinjiling,Pangxiemu,Shaziling and Xishan).Zircon U-Pb dating of four plutons(Jinjiling,Pangxiemu,Shaziling and Xishan)yielded similar ages of approximately 153 Ma,indicating indistinguishable ages within error.Three plutons except the Shaziling pluton,have consistentε_(Nd)(t)(-7.8 to-5.8)andε_(Hf)(t)(-9.1 to-2.2)values,which are similar to those of the lower crustal granulitic metasedimentary and meta-igneous rocks in South China.Compared to other three plutons,the Shaziling pluton has consistentε_(Nd)(t)(-7.4 to-6.8)andε_(Hf)(t)(-7.5 to-4.7)values and shows similar source,but the Shaziling mafic microgranular enclaves(MMEs)show variableε_(Hf)(t)(-14.2 to 4.8)values,indicating a remarkable mantle magma injection of the Shaziling pluton.Zircon Ce/Sm-Yb/Gd,whole-rock CaO-P_(2)O_(5)and CaO-TiO_(2)linear trends reveal that from the Xishan to the Shaziling and from the Jinjiling to the Pangxiemu granites,they experienced apatite and titanite fractionation,respectively.Zircon Th,U,Nb,Ta,Hf,Ti,Y,P and rare earth element(REE)contents and whole-rock Sr,Ba and Rb contents also show that the Shaziling,Xishan,Jinjiling and Pangxiemu granites followed a discontinuous evolutionary series,but the Pangxiemu granites exhibit highly evolved nature.Four main controlling factors of W-Sn and rare metal mineralization in granitic rocks were discussed,and we found that the mineralization in Jiuyishan granitic complex was mainly controlled by the fractionation degree and crystallization temperature,but were rarely affected by oxygen fugacity and mantle material input.The Pangxiemu granites show particularly higher Rb and Ta contents than the other three plutons,implying that the ore deposits developed in the Jiuyishan Complex were directly related to the most evolved Pangxiemu pluton,with the occurrence of Rb and Ta as the most likely rare metal mineralization in the Jiuyishan District.A crystal mush model is proposed to interpret the petrogenetic and mineralizing processes of the Jiuyishan granitic complex.
基金supported by the National Natural Science Foundation of China(Grant Nos.22271139)the Fundamental Research Funds for the Central Universities(020514380294).
文摘Smart molecules have attracted increasing attention due to their transformative role in creating the next generation of smart structures and devices.Smart bistable coordination complexes are a class of functional complexes which have two stable states that can be reversibly switched in response to external stimuli.Such bistable molecules play a vital role in various applications,such as sensors,data storage,spintronics,smart windows,optical switches,information encryption and decryption,displays,actuators,etc.Herein,the recent research studies into the development of these smart bistable metal coordination complexes are reviewed.According to the different external stimuli,these smart bistable coordination systems have been classified and summarized,including light-responsive systems,thermally-responsive systems,electrically-responsive systems,mechanicallyresponsive systems,and some other cases.These systems are further subdivided according to the changes in signals(e.g.,color,fluorescence,spin state,crystalline phase)under external stimuli.The design principles of each type of smart bistable metal complexes as well as their broad and innovative applications are comprehensively described.Finally,the challenges and opportunities in this field are briefly analyzed and discussed.
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.
基金supported by the National Nature Science Foundation of China(Nos.22061028 and 22361028)Jiangxi Provincial Natural Science Foundation(No.20224ACB203012)。
文摘A phenylphenothiazine anchored Tb(Ⅲ)-cyclen complex PTP-Cy-Tb for hypochlorite ion(ClO^(-))detection has been designed and prepared.PTP-Cy-Tb shows a weak Tb-based emission with AIE-characteristics in aqueous solutions.After addition of ClO^(-),the fluorescence of PTP-Cy-Tb gives a large enhancement for oxidization the thioether to sulfoxide group.The detection limit of PTP-Cy-Tb toward ClO^(-)is as low as 8.85 nmol/L.The sensing mechanism was detailedly investigated by time of flight mass spectrometer(TOF-MS),Fourier transform infrared spectroscopy(FT-IR)and density functional theory(DFT)calculation.In addition,PTP-Cy-Tb has been successfully used for on-site and real-time detection of ClO^(-)in real water samples by using the smartphone-based visualization method and test strips.
基金Supported by the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX24_0102)the China Scholarship Council Program(202406190114)。
文摘Studying the coupling coordination development of new energy vehicles(NEVs)and the ecological environment in China is helpful in promoting the development of NEVs in the country and is of great significance in promoting high-quality development of new energy in China.This paper constructs an evaluation index system for the development of NEVs and the ecological environment.It uses game theory combining weighting model,particle swarm optimized projection tracking evaluation model,coupling coordination degree model,and machine learning algorithms to calculate and analyze the level of coupling coordination development of NEVs and the ecological environment in China from 2010 to 2021,and identifies the driving factors.The research results show that:(i)From 2010 to 2021,the development index of NEVs in China has steadily increased from 0.085 to 0.634,while the ecological environment level index significantly rose from 0.170 to 0.884,reflecting the continuous development of China in both NEVs and the ecological environment.(ii)From 2010 to 2012,the two systems—new energy vehicle(NEV)development and the ecological environment—were in a period of imbalance and decline.From 2013 to 2016,they underwent a transition period,and from 2017 to 2021,they entered a period of coordinated development showing a trend of benign and continuous improvement.By 2021,they reached a good level of coordination.(iii)Indicators such as the number of patents granted for NEVs,water consumption per unit of GDP,and energy consumption per unit of GDP are the main driving factors affecting the coupling coordination development of NEVs and the ecological environment in China.
文摘One Yb(Ⅲ)-based coordination polymer,{[Yb(H_(2)dhtp)1.5(H_(2)O)_(4)]·3H_(2)O}n(1)(H_(4)dhtp=2,5-dihydroxytere-phthalic acid),was fabricated and structurally characterized by single-crystal X-ray diffraction,IR,powder X-ray diffraction,X-ray diffraction,and elemental analysis.Complex 1 displays a 1D chain structure,and belongs to P1 group.The solid-state luminescent spectrum of 1 showed an emission band with the maximum at 508 nm(λex=408 nm).It exhibited the emission characteristic of the H_(4)dhtp ligand.The fluorescence of 1 in water displayed the stron-gest intensity.In detecting various metal ions,adding Zr^(4+)led to a blue shift in fluorescence,accompanied by an increase in intensity,whereas the presence of Fe^(3+)resulted in a decrease in luminescence.The changes observed in the IR spectrum indicate an interaction between Fe^(3+)/Zr^(4+)and complex 1,resulting in the variation of luminescence properties.
文摘Under the condition of solvothermal synthesis,the viologen ligand 1,1′-bis(3-carboxyphenyl)-(4,4′-bipyri-dine)dichloride(H_(2)bcbpy·2Cl)and KI are coordinated with the metal cadmium ions.A case of thermochromic coor-dination polymer[Cd(bcbpy)I_(2)]·2H_(2)O(1)was constructed.Complex 1 displays a 1D chain structure and exhibits thermochromic behavior.Under different temperature stimulation,the complex(ground)slowly changed from green to yellow-green,and with the increase of temperature,the color of complex 1 gradually deepened,and finally became orange-yellow.Therefore,complex 1 was prepared as a thermochromic film.In addition,we also performed electrochemical tests on complex 1,which showed that the complex is a semiconductor material.CCDC:2391802.
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Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation,fast response,high spatial resolution,and so on,for which the luminescent thermometers are the key.Here,a 1D complex[Tb_(4)(HTC4A)(TC4A)(OBBA)_(2)(CH_(3)OH)_(4)(μ4-OH)]n(1)was obtained by solvothermal synthesis,where H 4TC4A=p-tert-butylthiacalix[4]arene,and H_(2)OBBA=4,4'-oxybisbenzoic acid.This complex is featured with a chain-like polymer constructed by bridging some sandwich-like Tb_(4)-(TC4A)_(2)entities through OBBA2-ligands.It exhibited the characteristic emission of the Tb^(3+)ion.Both fluorescence intensity and lifetime decreased with increasing temperature.The relative sensitivity was up to 8.743%·K^(-1)at 473 K,indicating it is a good ratiometric luminescent thermometer.This complex had good stability under different pH values and in common solvents.CCDC:2392643.
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.
