Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6...Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.展开更多
Partitioning of actinides from lanthanides is pivotal for advancing nuclear waste management and sustaining nuclear energy development,yet it remains a formidable challenge due to the intricate chemical behaviors of t...Partitioning of actinides from lanthanides is pivotal for advancing nuclear waste management and sustaining nuclear energy development,yet it remains a formidable challenge due to the intricate chemical behaviors of these f-block elements.In this study,we introduce 3,6-di-2-pyridyl-1,2,4,5-tetrazine(L1),whose hydrolysis product of pyridine-2-carbox-aldehyde(pyridine-2-carbonyl)-hydrazone(L2)can fractionally crystallize U(Ⅵ)ions over Ln(Ⅲ)cations with high selectivity and efficiency.Through hydrolysis-induced C–N bond cleavage,L2 acts as a tetradentate ligand,coordinating with two UO_(2)^(2+) ions in a planar arrangement to form a zerodimensional cluster,[(UO_(2))2(μ_(3)-O)(L2)(CH_(3)COO)]·DMF(U-L2),while lanthanide ions(Ln=La,Pr,Nd,Sm,Eu,Gd,Tb,Yb,and Lu)remain in solution due to their inability to achieve similar coordination.This selective crystallization strategy yields exceptional separation factors(SFs)between U(Ⅵ)and Ln(Ⅲ),with a value of 756276 between U(Ⅵ)and Sm(Ⅲ),the highest reported to date.Furthermore,this fractional crystallization separation process can be achieved under mild ambient conditions with high SFs,enabling the development of a rapid,safe and energy-efficient strategy for once-through separation of high oxidation state actinides from lanthanides.展开更多
Rare-earth supramolecular compounds,such as lanthanide organic polyhedrons(LOPs),are of particular interest due to their many possible applications in various fields.Here we report the first syntheses of Ln_(4)(L^(...Rare-earth supramolecular compounds,such as lanthanide organic polyhedrons(LOPs),are of particular interest due to their many possible applications in various fields.Here we report the first syntheses of Ln_(4)(L^(·+))_(4)-type(Ln,lanthanides;L^(·+),radical ligand)radical-bridged lanthanide organic tetrahedrons by self-assembly of face-capping triphenylamine(TPA)-cored radical ligand with different lanthanide ions.Remarkable coordination enhanced radical stability has been observed,with half-life times(t_(1/2))for L_(1)^(·+),La_(4)(L_(1)^(·+))_(4),Eu_(4)(L_(1)^(·+))_(4),Gd_(4)(L_(1)^(·+))_(4),Tb_(4)(L_(1)^(·+))_(4)and Lu_(4)(L_(1)^(·+))_(4)estimated to be 53 min,482 min,624 min,1248 min,822 min and 347 min,respectively.The TPA radical in Ln_(4)(L_(1)^(·+))_(4)containing paramagnetic Ln ions(Ln=Eu^(Ⅲ),Gd^(Ⅲ)and Tb^(Ⅲ))is observed to be more stable than that in Ln_(4)(L_(1)^(·+))_(4)(Ln=La^(Ⅲ)and Lu^(Ⅲ))constructed by diamagnetic Ln ions.This difference in radical stability is possibly due to the magnetic interactions between paramagnetic Ln^(Ⅲ)ions and L_(1)^(·+)ligands,as confirmed by electron paramagnetic resonance(EPR)in La_(4)(L)_(4)(L=L_(1)and L_(1)^(·+))and Tb_(4)(L)_(4)(L=L_(1)and L_(1)^(·+)),and magnetic susceptibility measurements in Tb·_(4)(L)_(4)(L=L_(1)and L_(1)^(·+)).Our study reveals the coordination of radical ligands with lanthanide ions can improve the radical stability,which is crucial for their applications.展开更多
Mixed-lanthanide(Ln) luminescent materials have important application values in ratiometric temperature sensing.Hydrogen-bonded organic frameworks(HOFs) offer a self-supporting network to conveniently tune multiple Ln...Mixed-lanthanide(Ln) luminescent materials have important application values in ratiometric temperature sensing.Hydrogen-bonded organic frameworks(HOFs) offer a self-supporting network to conveniently tune multiple Ln^(3+)ions,but challenges still exist in material design.In this work,we selected two simple organic molecules as hydrogen-bonded building blocks,which are melamine(MA) and 2,5-pyridinedicarboxylic acid(PDC) owning the suitable energy to sensitize Tb^(3+)and Eu^(3+)ions.MA assists PDC molecules to support the network in a new HOF(MA-PDC),where the abundant carboxylic groups enable Ln^(3+)ions to combine with the HOF.Based on the effective energy transfer process,the emission of Tb^(3+)and Eu^(3+)from TbxEu1-x@MA-PDC(x=0.75,0.85,0.90) shows the obvious temperature dependence,which benefits ratiometric temperature detection.Taking Tb0.85Eu0.15@MA-PDC as an example,when temperature varies from 303 to 443 K,the intensity ratio exhibits distinct S-type response based on Mott-Seitz model.It also behaves good relative sensitivity(1.03%/K at 383 K),low temperature resolution(0.059 K) and large reproducibility(>96%).This work demonstrates that functionalization of a simple-component HOF with mixed Ln^(3+)ions is a fantastic strategy to develop novel ratiometric thermometers of both low cost and good performance.展开更多
Given customizable crystal structure and intriguing optical properties,lanthanide titanium-oxygen clusters(LTOCs)with atomic-level accuracy have gained a lot of interest.In this study,we prepared[Ln_(9)Ti_(2)(μ4-O)(...Given customizable crystal structure and intriguing optical properties,lanthanide titanium-oxygen clusters(LTOCs)with atomic-level accuracy have gained a lot of interest.In this study,we prepared[Ln_(9)Ti_(2)(μ4-O)(μ3-OH)_(14)(acac)_(17)(CH_(3)O)_(2)(CH_(3)OH)_(3)](Ln=Tb_(x)Eu_(9−x)(x=0,4,6,7,8,9),Hacac=acetylacetone),Tb^(3+)and Eu^(3+)co-doped LTOCs,to modify the optical properties for the luminescence thermometer.In detail,the serial LTOCs display dual characteristic emission peaks of ^(5)D_(4)→^(7)F_(5) for Tb^(3+)and^(5)D_(0)→^(7)F_(2) for Eu^(3+)at 548 and 616 nm,respectively,under 330 nm excitation.Effective energy transfer(ET)between Tb^(3+)ions and Eu^(3+)ions was revealed in terms of both emission spectra and luminescence lifetime.The ^(5)D_(0)→^(7)F_(2) emission intensity of Eu^(3+)ions at 616 nm is maximally enhanced(by a factor of 11.2)with a change in the relative molar ratio of Tb^(3+)to Eu^(3+),along with a change in the ET efficiency of Tb^(3+)→Eu^(3+).In addition,the luminescent color changes from red,orange,yellow,to green.This precise control of the ET process between rare-earth ions allows{Tb_(6)Eu_(3)Ti_(2)}to reach a maximum relative sensitivity of 1.241 K^(−1) at 355 K,which is an enhancement of up to 4.6-fold with respect to the previously reported homonuclear emission,holding great potential in the optical thermometers.展开更多
Lanthanide-sensitized upconverting nanoparticles(UCNPs)are widely studied because of their unusual optical characteristics,such as large antenna-generated anti-Stokes shifts,high photostability,and narrow emission ban...Lanthanide-sensitized upconverting nanoparticles(UCNPs)are widely studied because of their unusual optical characteristics,such as large antenna-generated anti-Stokes shifts,high photostability,and narrow emission bandwidths,which can be harnessed for a variety of applications including bioimaging,sensing,information security and high-level anticounterfeiting.The diverse requirements of these applications typically require precise control over upconversion luminescence(UCL).Recently,the concept of energy migration upconversion has emerged as an effective approach to modulate UCL for various lanthanide ions.Moreover,it provides valuable insights into the fundamental comprehension of energy transfer mechanisms on the nanoscale,thereby contributing to the design of efficient lanthanide-sensitized UCNPs and their practical applications.Here we present a comprehensive overview of the latest developments in energy migration upconversion in lanthanide-sensitized nanoparticles for photon upconversion tuning,encompassing design strategies,mechanistic investigations and applications.Additionally,some future prospects in the field of energy migration upconversion are also discussed.展开更多
Benefiting from their large molar extinction coefficient,high carrier mobility,narrow and tunable emissions,inorganic metal halide perovskites(IMHPs) demonstrate great potential in various optoelectrical devices inclu...Benefiting from their large molar extinction coefficient,high carrier mobility,narrow and tunable emissions,inorganic metal halide perovskites(IMHPs) demonstrate great potential in various optoelectrical devices including solar cells,light emitting diodes and photodetectors in the past few years.Metal ions doping,well-known as a modification method of semiconductors,has been extensively applied in IMHPs as well.Diverse metal ions have been doped in IMHPs including alkali metals,alkali earth metals,transition metals and lanthanide metals,which either improve their optical performances or induce intriguing brand-new properties.Among them,lanthanide metals feature plentiful energy levels and stable optical properties and are one of the most noteworthy species.Here we review recent progress in lanthanide ions doped IMHPs.We summarize Yb,Eu or Er ions singly doping in detail,which was the most investigated species in IMHPs.Other lanthanide ions are also reviewed synoptically.Furthermore,we introduce lanthanide ions multi-doped IMHPs and at last we put forward several potential development directions.As the interests in lanthanide ions doped IMHPs rise,researchers have made some achievements in the field.Still though,there are more unexplored issues.Although there are review articles focusing on metal ions doped IMHPs or lanthanide ions doped perovskites,this review aims to provide an overall introduction of lanthanide ions doped IMHPs.This review may help researchers learn about lanthanide ions doped IMHPs and is to inspire researchers to make further promotion in this field.展开更多
Lanthanides(Ln(Ⅲ))based compounds as light-emitting materials have emerged as successful agents in high-performance defense and lighting systems,magnets,bio-markers,and circuitry.Therefore,they have recently gained m...Lanthanides(Ln(Ⅲ))based compounds as light-emitting materials have emerged as successful agents in high-performance defense and lighting systems,magnets,bio-markers,and circuitry.Therefore,they have recently gained much attention as energy-saving and cost-effective luminescent materials and their applications in analyte detection.The present review summarizes powerful features and recent developments of organo-lanthanide complexes in lighting applications with a particular focus on visible light emitters,including Eu(Ⅲ),Tb(Ⅲ),Sm(Ⅲ),and Dy(Ⅲ)ions.In addition,this review discusses the most relevant aspects of photosensitization,such as the structure,property,functionalization of primary and secondary ligands,and molecular geometry.In addition,coordination sites of organo-lanthanide complexes and their applications collectively contribute to the improved performance of innovative luminescent materials.Finally,the current challenges and key recommendations for advancing organolanthanides in material science are provided.展开更多
Lanthanide complex-based materials with magnetic and luminescent properties have received a great deal of attention,owing to their importantly potential applications in diverse fields.In this work,the 9-anthracenecarb...Lanthanide complex-based materials with magnetic and luminescent properties have received a great deal of attention,owing to their importantly potential applications in diverse fields.In this work,the 9-anthracenecarboxylic acid(9-Haca)as bridging ligand was applied in combination with optically activeπ-conjugated 2,4,6-tri(2-pyridyl)-1,3,5-triazine(tptz)to construct a series of new di-nuclear and tetranuclear lanthanide 9-anthracenecarboxylates[La_(2)(9-aca)_(6)(tptz)_(2)(μ-H_(2)O)]·0.25H_(2)O(1),[Ln_(2)(9-aca)_(6)(tptz)_(2)(H_(2)O)_(2)]·0.5AQ·CH_(3)COOH_(2)H_(2)O[Ln=Sm(2a),Eu(2b),Gd(2c),Tb(2d),Dy(2e),Tm(2f);AQ=9,10-anthracenedione]and[Ln_(4)(9-aca)_(10)(tptz)_(2)(CH3COO)2]·H_(2)O[Ln=Eu(3a),Gd(3b),Dy(3c)].1 displays a di-nuclear centrosymmetric moiety[La_(2)(9-aca)_(6)(tptz)_(2)(μ-H_(2)O)]built up from two complex[La(9-aca)_(2)(tptz)]groups bridged by one H_(2)O molecule and two syn-syn-μ2-η1:η1-9-aca-bridging ligands,while 2a-2f are isostructural and co mprise another di-nuclear centrosymmetric moieties[Ln_(2)(9-aca)_(6)(tptz)_(2)(H_(2)O)_(2)]based on two complex[Ln(9-aca)_(2)(tptz)(H_(2)O)]groups connected by two syn-syn-μ2-η1:η1-9-aca-bridging ligands,3a-3c are isostructural and show tetra-nuclear centro symmetric moieties[Ln4(9-aca)10(tptz)2(CH3COO)2]containing three types of coordination modes of 9-aca-ligands.The present compounds offer the only examples of lanthanide 9-anthracenecarboxylates decorated by optically active tptz.Magnetic investigations of 2a,2c-2f,and 3b-3c indicate that 3c is typical of slow relaxation of the magnetization,while 2c and 3b show significant magnetocaloric effect(MCE)with the value of-ΔSm of 5.26 J/(kg·K)at 4 K and 15.65 J/(kg·K)at 2 K(ΔH=7 T),respectively.The luminescent properties were also studied and reveal that the characteristic luminescent properties of the 7r-conjugated aromatic ligands are introduced into magnetic lanthanide 9-anthracenecarboxylates,simultaneously exhibiting slow magnetic relaxation(or MCE)and luminescent properties.展开更多
Luminescent hydrogels have received considerable attention in the application of sensors.Nitroaro matics are harmful to human health and can be carcinogenic.Some skin allergies and central nervous system injuries may ...Luminescent hydrogels have received considerable attention in the application of sensors.Nitroaro matics are harmful to human health and can be carcinogenic.Some skin allergies and central nervous system injuries may also be attributed to the over exposure to nitroaromatics.Thus,nitroaromatics sensor with fast detection and low detection limit is highly desirable.Herein,novel tough hydrogels were prepared by introducing hydrogen bonds and covalent bonds into the interpenetrating networks of modified chitosan and poly(vinyl alcohol)(PVA) via frozen-thawing induced chemical cross-linking.The synthesized hydrogels exhibit high mechanical strength(0.23 MPa tensile strength at 140% tensile strain,1.0 MPa compressive strength at 80% compressive strain).Strong green emission was realized by energy transfer from the modified chitosan to Tb^(3+)via the so-called "antenna effect." The prepared luminescent hydrogels show an excellent detection effect on nitroaromatic compounds and its detection limit can reach ppm-level.The hydrogels also exhibit good reversibility and a fast "off-on" fluorescence switching process.This work may open up a new way for the development of stable,rapid,and reusable sensors for the detection of harmful nitroaromatics.展开更多
Twelve novel transition-rare-earth metal clusters,formulated as [Ni_(18)Pr_(14)(μ_(3)OH)_(14)(dmpa)_(10)(mmt)_(10)(SO_(4))_(4)(CH_(3)COO)_(16)]·9CH_(3)OH·5H_(2)O(1,H_(3)dmpa=dimethylolpropionic acid,and Hmm...Twelve novel transition-rare-earth metal clusters,formulated as [Ni_(18)Pr_(14)(μ_(3)OH)_(14)(dmpa)_(10)(mmt)_(10)(SO_(4))_(4)(CH_(3)COO)_(16)]·9CH_(3)OH·5H_(2)O(1,H_(3)dmpa=dimethylolpropionic acid,and Hmmt=2-me rcapto-5-methyl-1,3,4-thiadiazole) [Ni_(36)RE_(102)(OH)_(138)(mmt)_(18)(Hdmpa)_(30)(H_(2)dmpa)_(12)(CH_(3)COO)_(72)(NO_(3))_(36)(SO_(4))_(18)(H_(2)O)_(30)]·Br_(6)(RE=Nd(2),Sm(3),Eu(4) and Gd(5))[Ni_(12)RE_(10)(μ_(3)-OH)_(10)(dmpa)_(8)(mmt)_(8)(S(_(4))2(CH_(3)COO)_(8)(H_(2)O)_(4)]·8CH_(3)OH·7H_(2)O(RE = Tb(6),Dy(7),Ho(8),Er(9) and Y(10)) [Ni_(8)Pr_(8)(μ_(3)-OH)_(8)(mmt)_(8)(Hdpga)_(16)(CH3COO)_(8)]·8CH_(3)OH(11,H_(2)dpga=diphe nyl-glycolic acid),and [Ni_(16)Tb_(6)(μ_(3)-OH)_(24)(mmt)_(8)(Hdpga)_(4)(dpga)_(4)(CH_(3)COO)_(2)(NO_(3))_(4)(H_(2)O)_(2)]·12CH_(3)OH·5H_(2)O(12),were synthesized solvothermally by using different ligand combinations and rare earth nitrates.X-ray crystal structure analyses reveal that complexes 1 and 12 possess sandwich-like structure.Compounds 2-5 are isostructural and feature a hexagonal structure,shaped like a "Star of David".Isostructural 6-10 present ring-like structure,as well as the cluster 11.The structural variations of these complexes can be attributed to the effect of lanthanide contraction.Moreover,the template effect of SO_(4)^(2-) anion derived from the slow decomposition of Hmmt ligand also plays a significant role in the formation of cluster skeletons.The insitu mechanism for the generation of sulfate anion is briefly discussed.Meanwhile,the magnetic properties of complexes 2-11 were studied which show typical antiferromagnetic interactions.展开更多
The toxicity of lead ions has become the severe challenge for the all-inorganic lead halide p erovskite materials,although some works have rep orted the lead-free perovskite nanocrystals(NCs),the photoluminescence qua...The toxicity of lead ions has become the severe challenge for the all-inorganic lead halide p erovskite materials,although some works have rep orted the lead-free perovskite nanocrystals(NCs),the photoluminescence quantum yield(PLQY)of these materials is still unsatisfactory.Meanwhile,because the halogen ions can be easily exchanged,the controllable multicolor emission in perovskite NCs is difficult to realize in current reports.In this work,we introduced lanthanide ions into lead-free Cs_(3)Sb_(2)Cl_(9) perovskite NCs.Benefitting from the energy transfer between Cs_(3)Sb_(2)Cl_(9) perovskite NC host and lanthanide ions,the multicolor emission was realized.Based on controlling the doping concentration of Tb^(3+)and Eu^(3+)ions,the white light emission under UV excitation would be turned easily in the Tb^(3+)/Eu^(3+)codoped NCs.In addition,efficient energy transfer from perovskite NCs to Tb^(3+)or Eu^(3+)ions is beneficial to improving the optical properties of lead-free perovskite NCs,resulting in maximum PLQYs of red,green and white light emission of 22.6%,19.7%and 28.5%,respectively.Finally,a white light emitting device(WLED)was fabricated with a power efficiency of 18.5 lm/W,which presents the Commission Internationale de l'Eclairage(CIE)of(0.33,0.35).展开更多
The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential...The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential applications of lanthanide-organic cages in biological imaging applications are promising,but only a few corresponding explorations have been reported.He rein,we introduced a series of lanthanide tetrahedral cages,(Eu_(n)Gd_(4-n)L_(4))(sol)_8(n=0,1,2,3 and 4,where L=(4,4',4"-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine,and sol=dimethyl sulfoxide and methanol),with potential applications in biological imaging.Given the good luminescent and magnetic properties of Eu^(3+) and Gd^(3+) ions,Eu_(4)L_(4) and Gd_(4)L_(4) complexes show a high luminescence quantum yield of 29% in DMSO and large longitudinal relaxivity(r_(1)) of 11.4(mmol/L)^(-1)/s at 0.5 T in water containing 1 vol% DMSO,respectively.The heterobimetallic Eu-Gd complexes achieve a dual imaging mode by combining luminescent and magnetic centers in one cage.When the Gd:Eu ratio increases from 1:3 to 3:1,the r_(1) values increases from 5.33 to 8.64(mmoI/L)^(-1)/s,higher than that of commercial contrast agent Gd-DOTA(3.23(mmol/L)^(-1)/s).Owing to their low toxicity and good cell imaging ability toward ECA 109 cells,the selfassembled Eu-Gd heterobimetallic tetrahedral cages could be potential candidates for the multimodal imaging contrast agent.展开更多
Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hy...Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.展开更多
Present-day advanced technologies heavily rely on the exciting magnetic and spectroscopic properties of lanthanide ions. In particular, their ability to generate well-characterized and intense near-infrared (NIR) lumi...Present-day advanced technologies heavily rely on the exciting magnetic and spectroscopic properties of lanthanide ions. In particular, their ability to generate well-characterized and intense near-infrared (NIR) luminescence is exploited in any modern fiber-optic telecommunication network. In this feature article, we first summarize the whereabouts underlying the design of highly luminescent NIR molecular edifices and materials. We then focus on describing the main trends in three applications related to this spectral range: telecommunications, biosciences, and solar energy conversion. In telecommunications, efforts concentrate presently on getting easily processable polymer-based waveguide amplifiers. Upconversion nanophosphors emitting in the visible after NIR excitation are now ubiquitous in many bioanalyses while their application to bio-imaging is still in its early stages; however, highly sensitive NIR-NIR systems start to be at hand for both in vitro and in vivo imaging, as well as dual probes combining magnetic resonance and optical imaging. Finally, both silicon-based and dye-sensitized solar cells benefit from the downconversion and upconversion capabilities of lanthanide ions to harvest UV and NIR solar light and to boost the overall quantum efficiency of these next-generation devices.展开更多
Trivalent lanthanide ions display fascinating optical properties. The discovery of the corresponding elements and their first industrial uses were intimately linked to their optical properties. This relationship has b...Trivalent lanthanide ions display fascinating optical properties. The discovery of the corresponding elements and their first industrial uses were intimately linked to their optical properties. This relationship has been kept alive until today when many high-technology applications of lanthanide-containing materials such as energy-saving lighting devices, displays, optical fibers and amplifiers, lasers, responsive luminescent stains for biomedical analyses and in cellulo sensing and imaging, heavily rely on the brilliant and pure-color emission of lanthanide ions. In this review we first outlined the basics of lanthanide luminescence with emphasis on f-f transitions, the sensitization mechanisms, and the assessment of the luminescence efficiency of lanthanide-containing emissive molecular edifices. Emphasis was then put on two fast developing aspects of lanthanide luminescence： materials for telecommunications and light emitting diodes, and biomedical imaging and sensing. Recent advances in NIR-emitting materials for plastic amplifiers and waveguides were described, together with the main solutions brought by researchers to minimize non-radiative deactivation of excited states. The demonstration in 1999 that erbium tris（8-hydroxyquinolinate） displayed a bright green emission suitable for organic light emitting diodes （OLEDs） was followed by realizing that in OLEDs, 25% of the excitation energy leads to singlet states and 75% to triplet states. Since lanthanide ions are good triplet quenchers, they now also play a key role in the development of these lighting devices. Luminescence analyses of biological molecules are among the most sensitive analytical techniques known. The long lifetime of the lanthanide excited states allows time-resolved spectroscopy to be used, suppressing the sample autofluorescence and reaching very low detection limits. Not only visible lanthanide sensors are now ubiquitously provided in medical diagnosis and in cell imaging, but the feasibility of using NIR emission of ions such as YbⅢ is now being tested because of deeper penetration in biological tissues.展开更多
Interest in lanthanide complexes in the synthetic clays remains growing considerably during the last decades because of the attractive features of the individuals. Synthetic clays like Laponite~? and Aminoclay show gr...Interest in lanthanide complexes in the synthetic clays remains growing considerably during the last decades because of the attractive features of the individuals. Synthetic clays like Laponite~? and Aminoclay show great potentials in building up the luminescent hybrid materials due to their obvious advantages such as high purity, high dispersibility(or solubility) in water to yield translucent gels and clear aqueous solution. Additionally, their strong adsorption capacity for non-polar molecules or complexes is favorable to the formation of water-soluble and aqueous processable luminescent materials. This feature article summarizes the latest developments in the design and preparation of highly luminescent organicinorganic hybrid materials with excellent aqueous process ability based on lanthanide complexes intercalated synthetic clays.展开更多
The second near-infrared(NIR-Ⅱ,1000-1700 nm)window provides a superior optical platform with high resolution,deep penetration and high signal-to-noise ratios(SNRs),which results from the intrinsic low scattering and ...The second near-infrared(NIR-Ⅱ,1000-1700 nm)window provides a superior optical platform with high resolution,deep penetration and high signal-to-noise ratios(SNRs),which results from the intrinsic low scattering and auto fluorescence in biological tissues.As one of the promising NIR-Ⅱemitting probes,lanthanide based nanoparticles(LnNPs)exhibit high photo stability and chemostability,long photoluminescence lifetimes,low long-term cytotoxicity and narrow emission bandwidths.All these merits have spurred the evolution of related bio-optics and a variety of biomedical applications of LnNPs.This mini-review discusses the most recent advances in both the design-the composition and surface modifications-and the applications of NIR-Ⅱemitting LnNPs in bioimaging,disease diagnosis and therapy.We also summarize the current limits and challenges facing the applications of LnNPs as well as discuss the directions of future development.展开更多
Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be exte...Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be extended to further enhance their photocatalytic activity for H_(2)evolution.Herein,we present a successful attempt to selectively dope lanthanide ions into the{101}facets of ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets through a facile one-step solvothermal method.The lanthanide doping slightly extended the light-harvesting region and markedly improved the charge-separated states of the TiO_(2)nanosheets as evidenced by UV-vis absorption and steady-state/transient photoluminescence spectra.Upon simulated sunlight irradiation,we observed a 4.2-fold enhancement in the photocatalytic H_(2)evolution activity of optimal Yb^(3+)-doped TiO_(2)nanosheets compared to that of their undoped counterparts.Furthermore,when Pt nanoparticles were used as cocatalysts to reduce the H_(2)overpotential in this system,the photocatalytic activity enhancement factor increased to 8.5.By combining these results with those of control experiments,we confirmed that the extended charge-separated states play the main role in the enhancement of the photocatalytic H_(2)evolution activity of lanthanide-doped TiO_(2)nanosheets with coexposed{001}/{101}facets.展开更多
Persistent luminescence nanoparticles(PLNPs)are a kind of phosphors that can remain luminescent for seconds to several days after the stoppage of excitation.Lanthanides show the special capability to largely broaden t...Persistent luminescence nanoparticles(PLNPs)are a kind of phosphors that can remain luminescent for seconds to several days after the stoppage of excitation.Lanthanides show the special capability to largely broaden the emission range and enhance the luminescence intensity of PLNPs due to their dense energy structure and unique electronic configurations.In the past decades,various methods have been developed for the synthesis of lanthanide-based PLNPs with excellent pe rsistent luminescence propertie s,and the lanthanide-based PLNPs are widely studied in areas including biome dicine,energy,and information storage.In this review,we summarized the research progress in the synthe sis of lanthanidebased PLNPs and outline d several typical synthesis methods.We discussed the fundamental concepts of preparation methods as well as the advantages and drawbacks of the typical synthetic approache s.Moreove r,the current challenges and the potential solutions for the development of lanthanide-based PLNP s are also discussed in an attempt to provide strate gies to further improve the optical properties of lanthanide-based PLNPs.We hope this review can contribute to the design of lanthanide-based PLNPs with desired properties and further promote their applications in biomedicine,energy,and information science.展开更多
文摘Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.
基金supported by the National Natural Science Foundation of China(U22B20139,22322609,22076152,and 22476158).
文摘Partitioning of actinides from lanthanides is pivotal for advancing nuclear waste management and sustaining nuclear energy development,yet it remains a formidable challenge due to the intricate chemical behaviors of these f-block elements.In this study,we introduce 3,6-di-2-pyridyl-1,2,4,5-tetrazine(L1),whose hydrolysis product of pyridine-2-carbox-aldehyde(pyridine-2-carbonyl)-hydrazone(L2)can fractionally crystallize U(Ⅵ)ions over Ln(Ⅲ)cations with high selectivity and efficiency.Through hydrolysis-induced C–N bond cleavage,L2 acts as a tetradentate ligand,coordinating with two UO_(2)^(2+) ions in a planar arrangement to form a zerodimensional cluster,[(UO_(2))2(μ_(3)-O)(L2)(CH_(3)COO)]·DMF(U-L2),while lanthanide ions(Ln=La,Pr,Nd,Sm,Eu,Gd,Tb,Yb,and Lu)remain in solution due to their inability to achieve similar coordination.This selective crystallization strategy yields exceptional separation factors(SFs)between U(Ⅵ)and Ln(Ⅲ),with a value of 756276 between U(Ⅵ)and Sm(Ⅲ),the highest reported to date.Furthermore,this fractional crystallization separation process can be achieved under mild ambient conditions with high SFs,enabling the development of a rapid,safe and energy-efficient strategy for once-through separation of high oxidation state actinides from lanthanides.
基金supported by National Key Research and Development Program of China(Nos.2021YFA1500400 and 2022YFA1503300)the National Natural Science Foundation of China(Nos.21825107,21971237,22171264 and 22301301)the Science Foundation of the Fujian Province(No.2021J02016)。
文摘Rare-earth supramolecular compounds,such as lanthanide organic polyhedrons(LOPs),are of particular interest due to their many possible applications in various fields.Here we report the first syntheses of Ln_(4)(L^(·+))_(4)-type(Ln,lanthanides;L^(·+),radical ligand)radical-bridged lanthanide organic tetrahedrons by self-assembly of face-capping triphenylamine(TPA)-cored radical ligand with different lanthanide ions.Remarkable coordination enhanced radical stability has been observed,with half-life times(t_(1/2))for L_(1)^(·+),La_(4)(L_(1)^(·+))_(4),Eu_(4)(L_(1)^(·+))_(4),Gd_(4)(L_(1)^(·+))_(4),Tb_(4)(L_(1)^(·+))_(4)and Lu_(4)(L_(1)^(·+))_(4)estimated to be 53 min,482 min,624 min,1248 min,822 min and 347 min,respectively.The TPA radical in Ln_(4)(L_(1)^(·+))_(4)containing paramagnetic Ln ions(Ln=Eu^(Ⅲ),Gd^(Ⅲ)and Tb^(Ⅲ))is observed to be more stable than that in Ln_(4)(L_(1)^(·+))_(4)(Ln=La^(Ⅲ)and Lu^(Ⅲ))constructed by diamagnetic Ln ions.This difference in radical stability is possibly due to the magnetic interactions between paramagnetic Ln^(Ⅲ)ions and L_(1)^(·+)ligands,as confirmed by electron paramagnetic resonance(EPR)in La_(4)(L)_(4)(L=L_(1)and L_(1)^(·+))and Tb_(4)(L)_(4)(L=L_(1)and L_(1)^(·+)),and magnetic susceptibility measurements in Tb·_(4)(L)_(4)(L=L_(1)and L_(1)^(·+)).Our study reveals the coordination of radical ligands with lanthanide ions can improve the radical stability,which is crucial for their applications.
基金Project supported by the Zhejiang Provincial Natural Science Foundation of China (LY24E020005)Industrial Key Projects of Jinhua City(2023-1-090)。
文摘Mixed-lanthanide(Ln) luminescent materials have important application values in ratiometric temperature sensing.Hydrogen-bonded organic frameworks(HOFs) offer a self-supporting network to conveniently tune multiple Ln^(3+)ions,but challenges still exist in material design.In this work,we selected two simple organic molecules as hydrogen-bonded building blocks,which are melamine(MA) and 2,5-pyridinedicarboxylic acid(PDC) owning the suitable energy to sensitize Tb^(3+)and Eu^(3+)ions.MA assists PDC molecules to support the network in a new HOF(MA-PDC),where the abundant carboxylic groups enable Ln^(3+)ions to combine with the HOF.Based on the effective energy transfer process,the emission of Tb^(3+)and Eu^(3+)from TbxEu1-x@MA-PDC(x=0.75,0.85,0.90) shows the obvious temperature dependence,which benefits ratiometric temperature detection.Taking Tb0.85Eu0.15@MA-PDC as an example,when temperature varies from 303 to 443 K,the intensity ratio exhibits distinct S-type response based on Mott-Seitz model.It also behaves good relative sensitivity(1.03%/K at 383 K),low temperature resolution(0.059 K) and large reproducibility(>96%).This work demonstrates that functionalization of a simple-component HOF with mixed Ln^(3+)ions is a fantastic strategy to develop novel ratiometric thermometers of both low cost and good performance.
基金supported by the National Natural Science Foundation of China(Nos.12174151 and 12304448)the Specific Research Fund of the Innovation Platform for Academicians of Hainan Province(No.YSPTZX202208)+3 种基金Hainan Province Clinical Medical Center(No.QWYH_(2)022341)the Key Laboratory of New Energy and Rare Earth Resource Utilization of the State People’s Committee of China(No.NERE202206)the Department of Science and Technology of Jilin Province(No.20220101059JC)the Key Laboratory of the Ministry of Education for First Aid and Trauma Research(No.KLET-202218).
文摘Given customizable crystal structure and intriguing optical properties,lanthanide titanium-oxygen clusters(LTOCs)with atomic-level accuracy have gained a lot of interest.In this study,we prepared[Ln_(9)Ti_(2)(μ4-O)(μ3-OH)_(14)(acac)_(17)(CH_(3)O)_(2)(CH_(3)OH)_(3)](Ln=Tb_(x)Eu_(9−x)(x=0,4,6,7,8,9),Hacac=acetylacetone),Tb^(3+)and Eu^(3+)co-doped LTOCs,to modify the optical properties for the luminescence thermometer.In detail,the serial LTOCs display dual characteristic emission peaks of ^(5)D_(4)→^(7)F_(5) for Tb^(3+)and^(5)D_(0)→^(7)F_(2) for Eu^(3+)at 548 and 616 nm,respectively,under 330 nm excitation.Effective energy transfer(ET)between Tb^(3+)ions and Eu^(3+)ions was revealed in terms of both emission spectra and luminescence lifetime.The ^(5)D_(0)→^(7)F_(2) emission intensity of Eu^(3+)ions at 616 nm is maximally enhanced(by a factor of 11.2)with a change in the relative molar ratio of Tb^(3+)to Eu^(3+),along with a change in the ET efficiency of Tb^(3+)→Eu^(3+).In addition,the luminescent color changes from red,orange,yellow,to green.This precise control of the ET process between rare-earth ions allows{Tb_(6)Eu_(3)Ti_(2)}to reach a maximum relative sensitivity of 1.241 K^(−1) at 355 K,which is an enhancement of up to 4.6-fold with respect to the previously reported homonuclear emission,holding great potential in the optical thermometers.
基金supported by Senior Talent Fund of Jiangsu University(No.5501310021)China Postdoctoral Science Foundation(No.2023M741419)+1 种基金the Young Elite Scientist Sponsorship Program by ZJAST(No.G301310002)Research Fund for International Scientists(No.22350710187).
文摘Lanthanide-sensitized upconverting nanoparticles(UCNPs)are widely studied because of their unusual optical characteristics,such as large antenna-generated anti-Stokes shifts,high photostability,and narrow emission bandwidths,which can be harnessed for a variety of applications including bioimaging,sensing,information security and high-level anticounterfeiting.The diverse requirements of these applications typically require precise control over upconversion luminescence(UCL).Recently,the concept of energy migration upconversion has emerged as an effective approach to modulate UCL for various lanthanide ions.Moreover,it provides valuable insights into the fundamental comprehension of energy transfer mechanisms on the nanoscale,thereby contributing to the design of efficient lanthanide-sensitized UCNPs and their practical applications.Here we present a comprehensive overview of the latest developments in energy migration upconversion in lanthanide-sensitized nanoparticles for photon upconversion tuning,encompassing design strategies,mechanistic investigations and applications.Additionally,some future prospects in the field of energy migration upconversion are also discussed.
基金Project supported by the National Natural Science Foundation of China(52272270,51972084)the Young Scientist Workshop(Harbin Institute of Technology)(AUGA5710094420)the Fundamental Research Funds for the Central Universities,China(AUGA5710052614)。
文摘Benefiting from their large molar extinction coefficient,high carrier mobility,narrow and tunable emissions,inorganic metal halide perovskites(IMHPs) demonstrate great potential in various optoelectrical devices including solar cells,light emitting diodes and photodetectors in the past few years.Metal ions doping,well-known as a modification method of semiconductors,has been extensively applied in IMHPs as well.Diverse metal ions have been doped in IMHPs including alkali metals,alkali earth metals,transition metals and lanthanide metals,which either improve their optical performances or induce intriguing brand-new properties.Among them,lanthanide metals feature plentiful energy levels and stable optical properties and are one of the most noteworthy species.Here we review recent progress in lanthanide ions doped IMHPs.We summarize Yb,Eu or Er ions singly doping in detail,which was the most investigated species in IMHPs.Other lanthanide ions are also reviewed synoptically.Furthermore,we introduce lanthanide ions multi-doped IMHPs and at last we put forward several potential development directions.As the interests in lanthanide ions doped IMHPs rise,researchers have made some achievements in the field.Still though,there are more unexplored issues.Although there are review articles focusing on metal ions doped IMHPs or lanthanide ions doped perovskites,this review aims to provide an overall introduction of lanthanide ions doped IMHPs.This review may help researchers learn about lanthanide ions doped IMHPs and is to inspire researchers to make further promotion in this field.
基金Project supported by the Human Resource Development Group(HRDG)Council of Scientific&Industrial Research(CSIR),New Delhi,India(09/105(0266)-2018-EMR-1)。
文摘Lanthanides(Ln(Ⅲ))based compounds as light-emitting materials have emerged as successful agents in high-performance defense and lighting systems,magnets,bio-markers,and circuitry.Therefore,they have recently gained much attention as energy-saving and cost-effective luminescent materials and their applications in analyte detection.The present review summarizes powerful features and recent developments of organo-lanthanide complexes in lighting applications with a particular focus on visible light emitters,including Eu(Ⅲ),Tb(Ⅲ),Sm(Ⅲ),and Dy(Ⅲ)ions.In addition,this review discusses the most relevant aspects of photosensitization,such as the structure,property,functionalization of primary and secondary ligands,and molecular geometry.In addition,coordination sites of organo-lanthanide complexes and their applications collectively contribute to the improved performance of innovative luminescent materials.Finally,the current challenges and key recommendations for advancing organolanthanides in material science are provided.
基金Project supported by the National Natural Science Foundation of China(21671029)Innovation andEntrepreneurship Team of Inorganic Optoelectronic Functional Materials for Chongqing Yingcai(cstc2021ycjh-bgzxm0131)+3 种基金MajorProject of the Science and Technology Research Program of Chongqing Education Commission of China(KJZD-M202100501)theInnovation Program for Chongqing’s Overseas Returnees(cx2019037)Natural Science Foundation of Chongqing,China(cstc2021jcyj-msxmX0380)Chongqing Normal University(21XLB034)。
文摘Lanthanide complex-based materials with magnetic and luminescent properties have received a great deal of attention,owing to their importantly potential applications in diverse fields.In this work,the 9-anthracenecarboxylic acid(9-Haca)as bridging ligand was applied in combination with optically activeπ-conjugated 2,4,6-tri(2-pyridyl)-1,3,5-triazine(tptz)to construct a series of new di-nuclear and tetranuclear lanthanide 9-anthracenecarboxylates[La_(2)(9-aca)_(6)(tptz)_(2)(μ-H_(2)O)]·0.25H_(2)O(1),[Ln_(2)(9-aca)_(6)(tptz)_(2)(H_(2)O)_(2)]·0.5AQ·CH_(3)COOH_(2)H_(2)O[Ln=Sm(2a),Eu(2b),Gd(2c),Tb(2d),Dy(2e),Tm(2f);AQ=9,10-anthracenedione]and[Ln_(4)(9-aca)_(10)(tptz)_(2)(CH3COO)2]·H_(2)O[Ln=Eu(3a),Gd(3b),Dy(3c)].1 displays a di-nuclear centrosymmetric moiety[La_(2)(9-aca)_(6)(tptz)_(2)(μ-H_(2)O)]built up from two complex[La(9-aca)_(2)(tptz)]groups bridged by one H_(2)O molecule and two syn-syn-μ2-η1:η1-9-aca-bridging ligands,while 2a-2f are isostructural and co mprise another di-nuclear centrosymmetric moieties[Ln_(2)(9-aca)_(6)(tptz)_(2)(H_(2)O)_(2)]based on two complex[Ln(9-aca)_(2)(tptz)(H_(2)O)]groups connected by two syn-syn-μ2-η1:η1-9-aca-bridging ligands,3a-3c are isostructural and show tetra-nuclear centro symmetric moieties[Ln4(9-aca)10(tptz)2(CH3COO)2]containing three types of coordination modes of 9-aca-ligands.The present compounds offer the only examples of lanthanide 9-anthracenecarboxylates decorated by optically active tptz.Magnetic investigations of 2a,2c-2f,and 3b-3c indicate that 3c is typical of slow relaxation of the magnetization,while 2c and 3b show significant magnetocaloric effect(MCE)with the value of-ΔSm of 5.26 J/(kg·K)at 4 K and 15.65 J/(kg·K)at 2 K(ΔH=7 T),respectively.The luminescent properties were also studied and reveal that the characteristic luminescent properties of the 7r-conjugated aromatic ligands are introduced into magnetic lanthanide 9-anthracenecarboxylates,simultaneously exhibiting slow magnetic relaxation(or MCE)and luminescent properties.
基金Project supported by the National Natural Science Foundation of China(21661034)Reserve Talents Project for Youth and Middle-Aged Academic and Technical Leaders of Yunnan Province(202205AC160032)。
文摘Luminescent hydrogels have received considerable attention in the application of sensors.Nitroaro matics are harmful to human health and can be carcinogenic.Some skin allergies and central nervous system injuries may also be attributed to the over exposure to nitroaromatics.Thus,nitroaromatics sensor with fast detection and low detection limit is highly desirable.Herein,novel tough hydrogels were prepared by introducing hydrogen bonds and covalent bonds into the interpenetrating networks of modified chitosan and poly(vinyl alcohol)(PVA) via frozen-thawing induced chemical cross-linking.The synthesized hydrogels exhibit high mechanical strength(0.23 MPa tensile strength at 140% tensile strain,1.0 MPa compressive strength at 80% compressive strain).Strong green emission was realized by energy transfer from the modified chitosan to Tb^(3+)via the so-called "antenna effect." The prepared luminescent hydrogels show an excellent detection effect on nitroaromatic compounds and its detection limit can reach ppm-level.The hydrogels also exhibit good reversibility and a fast "off-on" fluorescence switching process.This work may open up a new way for the development of stable,rapid,and reusable sensors for the detection of harmful nitroaromatics.
基金Project supported by the National Natural Science Foundation of China (21971203)Support Plan of Shaanxi Province for Young Topnotch TalentFundamental Research Funds for Central Universities。
文摘Twelve novel transition-rare-earth metal clusters,formulated as [Ni_(18)Pr_(14)(μ_(3)OH)_(14)(dmpa)_(10)(mmt)_(10)(SO_(4))_(4)(CH_(3)COO)_(16)]·9CH_(3)OH·5H_(2)O(1,H_(3)dmpa=dimethylolpropionic acid,and Hmmt=2-me rcapto-5-methyl-1,3,4-thiadiazole) [Ni_(36)RE_(102)(OH)_(138)(mmt)_(18)(Hdmpa)_(30)(H_(2)dmpa)_(12)(CH_(3)COO)_(72)(NO_(3))_(36)(SO_(4))_(18)(H_(2)O)_(30)]·Br_(6)(RE=Nd(2),Sm(3),Eu(4) and Gd(5))[Ni_(12)RE_(10)(μ_(3)-OH)_(10)(dmpa)_(8)(mmt)_(8)(S(_(4))2(CH_(3)COO)_(8)(H_(2)O)_(4)]·8CH_(3)OH·7H_(2)O(RE = Tb(6),Dy(7),Ho(8),Er(9) and Y(10)) [Ni_(8)Pr_(8)(μ_(3)-OH)_(8)(mmt)_(8)(Hdpga)_(16)(CH3COO)_(8)]·8CH_(3)OH(11,H_(2)dpga=diphe nyl-glycolic acid),and [Ni_(16)Tb_(6)(μ_(3)-OH)_(24)(mmt)_(8)(Hdpga)_(4)(dpga)_(4)(CH_(3)COO)_(2)(NO_(3))_(4)(H_(2)O)_(2)]·12CH_(3)OH·5H_(2)O(12),were synthesized solvothermally by using different ligand combinations and rare earth nitrates.X-ray crystal structure analyses reveal that complexes 1 and 12 possess sandwich-like structure.Compounds 2-5 are isostructural and feature a hexagonal structure,shaped like a "Star of David".Isostructural 6-10 present ring-like structure,as well as the cluster 11.The structural variations of these complexes can be attributed to the effect of lanthanide contraction.Moreover,the template effect of SO_(4)^(2-) anion derived from the slow decomposition of Hmmt ligand also plays a significant role in the formation of cluster skeletons.The insitu mechanism for the generation of sulfate anion is briefly discussed.Meanwhile,the magnetic properties of complexes 2-11 were studied which show typical antiferromagnetic interactions.
基金Project supported by the National Natural Science Foundation of China(U21A2068,11974142,11874181,12204248)the Fundamental Research Funds for the Central UniversitiesJiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB399)。
文摘The toxicity of lead ions has become the severe challenge for the all-inorganic lead halide p erovskite materials,although some works have rep orted the lead-free perovskite nanocrystals(NCs),the photoluminescence quantum yield(PLQY)of these materials is still unsatisfactory.Meanwhile,because the halogen ions can be easily exchanged,the controllable multicolor emission in perovskite NCs is difficult to realize in current reports.In this work,we introduced lanthanide ions into lead-free Cs_(3)Sb_(2)Cl_(9) perovskite NCs.Benefitting from the energy transfer between Cs_(3)Sb_(2)Cl_(9) perovskite NC host and lanthanide ions,the multicolor emission was realized.Based on controlling the doping concentration of Tb^(3+)and Eu^(3+)ions,the white light emission under UV excitation would be turned easily in the Tb^(3+)/Eu^(3+)codoped NCs.In addition,efficient energy transfer from perovskite NCs to Tb^(3+)or Eu^(3+)ions is beneficial to improving the optical properties of lead-free perovskite NCs,resulting in maximum PLQYs of red,green and white light emission of 22.6%,19.7%and 28.5%,respectively.Finally,a white light emitting device(WLED)was fabricated with a power efficiency of 18.5 lm/W,which presents the Commission Internationale de l'Eclairage(CIE)of(0.33,0.35).
基金Project supported by the National Natural Science Foundation of China(52062034)the National Key Research and Development Program of China(2019YFC0605002)。
文摘The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential applications of lanthanide-organic cages in biological imaging applications are promising,but only a few corresponding explorations have been reported.He rein,we introduced a series of lanthanide tetrahedral cages,(Eu_(n)Gd_(4-n)L_(4))(sol)_8(n=0,1,2,3 and 4,where L=(4,4',4"-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine,and sol=dimethyl sulfoxide and methanol),with potential applications in biological imaging.Given the good luminescent and magnetic properties of Eu^(3+) and Gd^(3+) ions,Eu_(4)L_(4) and Gd_(4)L_(4) complexes show a high luminescence quantum yield of 29% in DMSO and large longitudinal relaxivity(r_(1)) of 11.4(mmol/L)^(-1)/s at 0.5 T in water containing 1 vol% DMSO,respectively.The heterobimetallic Eu-Gd complexes achieve a dual imaging mode by combining luminescent and magnetic centers in one cage.When the Gd:Eu ratio increases from 1:3 to 3:1,the r_(1) values increases from 5.33 to 8.64(mmoI/L)^(-1)/s,higher than that of commercial contrast agent Gd-DOTA(3.23(mmol/L)^(-1)/s).Owing to their low toxicity and good cell imaging ability toward ECA 109 cells,the selfassembled Eu-Gd heterobimetallic tetrahedral cages could be potential candidates for the multimodal imaging contrast agent.
文摘Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.
基金Project supported through grants from the Swiss National Science Foundationthe WCU program from the National Science Foundation of Korea for grant R31-10035
文摘Present-day advanced technologies heavily rely on the exciting magnetic and spectroscopic properties of lanthanide ions. In particular, their ability to generate well-characterized and intense near-infrared (NIR) luminescence is exploited in any modern fiber-optic telecommunication network. In this feature article, we first summarize the whereabouts underlying the design of highly luminescent NIR molecular edifices and materials. We then focus on describing the main trends in three applications related to this spectral range: telecommunications, biosciences, and solar energy conversion. In telecommunications, efforts concentrate presently on getting easily processable polymer-based waveguide amplifiers. Upconversion nanophosphors emitting in the visible after NIR excitation are now ubiquitous in many bioanalyses while their application to bio-imaging is still in its early stages; however, highly sensitive NIR-NIR systems start to be at hand for both in vitro and in vivo imaging, as well as dual probes combining magnetic resonance and optical imaging. Finally, both silicon-based and dye-sensitized solar cells benefit from the downconversion and upconversion capabilities of lanthanide ions to harvest UV and NIR solar light and to boost the overall quantum efficiency of these next-generation devices.
基金Project supported by the Swiss National Science Foundation
文摘Trivalent lanthanide ions display fascinating optical properties. The discovery of the corresponding elements and their first industrial uses were intimately linked to their optical properties. This relationship has been kept alive until today when many high-technology applications of lanthanide-containing materials such as energy-saving lighting devices, displays, optical fibers and amplifiers, lasers, responsive luminescent stains for biomedical analyses and in cellulo sensing and imaging, heavily rely on the brilliant and pure-color emission of lanthanide ions. In this review we first outlined the basics of lanthanide luminescence with emphasis on f-f transitions, the sensitization mechanisms, and the assessment of the luminescence efficiency of lanthanide-containing emissive molecular edifices. Emphasis was then put on two fast developing aspects of lanthanide luminescence： materials for telecommunications and light emitting diodes, and biomedical imaging and sensing. Recent advances in NIR-emitting materials for plastic amplifiers and waveguides were described, together with the main solutions brought by researchers to minimize non-radiative deactivation of excited states. The demonstration in 1999 that erbium tris（8-hydroxyquinolinate） displayed a bright green emission suitable for organic light emitting diodes （OLEDs） was followed by realizing that in OLEDs, 25% of the excitation energy leads to singlet states and 75% to triplet states. Since lanthanide ions are good triplet quenchers, they now also play a key role in the development of these lighting devices. Luminescence analyses of biological molecules are among the most sensitive analytical techniques known. The long lifetime of the lanthanide excited states allows time-resolved spectroscopy to be used, suppressing the sample autofluorescence and reaching very low detection limits. Not only visible lanthanide sensors are now ubiquitously provided in medical diagnosis and in cell imaging, but the feasibility of using NIR emission of ions such as YbⅢ is now being tested because of deeper penetration in biological tissues.
基金Project support by the National Natural Science Foundation of China(21171046,21502039,21271060)the Natural Science Foundation of Hebei Province(No.B2016202147,B2016202149,B2017202048)+2 种基金Educational Committee of Hebei Province(LJRC021,QN2015172)Hebei Provincial College of Science and Technology Research Project(BJ2018054)Tianjin Natural Science Foundation(18JCYBJC17200)
文摘Interest in lanthanide complexes in the synthetic clays remains growing considerably during the last decades because of the attractive features of the individuals. Synthetic clays like Laponite~? and Aminoclay show great potentials in building up the luminescent hybrid materials due to their obvious advantages such as high purity, high dispersibility(or solubility) in water to yield translucent gels and clear aqueous solution. Additionally, their strong adsorption capacity for non-polar molecules or complexes is favorable to the formation of water-soluble and aqueous processable luminescent materials. This feature article summarizes the latest developments in the design and preparation of highly luminescent organicinorganic hybrid materials with excellent aqueous process ability based on lanthanide complexes intercalated synthetic clays.
基金Project supported by the National Key R&D Program of China(2017YFA0207303)National Science Fund for Distinguished Young Scholars(21725502)+1 种基金Key Basic Research Program of Science and Technology Commission of Shanghai Municipality(17JC1400100)Intergovernmental International Cooperation Project of Science and Technology Commission of Shanghai Municipality(19490713100)。
文摘The second near-infrared(NIR-Ⅱ,1000-1700 nm)window provides a superior optical platform with high resolution,deep penetration and high signal-to-noise ratios(SNRs),which results from the intrinsic low scattering and auto fluorescence in biological tissues.As one of the promising NIR-Ⅱemitting probes,lanthanide based nanoparticles(LnNPs)exhibit high photo stability and chemostability,long photoluminescence lifetimes,low long-term cytotoxicity and narrow emission bandwidths.All these merits have spurred the evolution of related bio-optics and a variety of biomedical applications of LnNPs.This mini-review discusses the most recent advances in both the design-the composition and surface modifications-and the applications of NIR-Ⅱemitting LnNPs in bioimaging,disease diagnosis and therapy.We also summarize the current limits and challenges facing the applications of LnNPs as well as discuss the directions of future development.
文摘Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be extended to further enhance their photocatalytic activity for H_(2)evolution.Herein,we present a successful attempt to selectively dope lanthanide ions into the{101}facets of ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets through a facile one-step solvothermal method.The lanthanide doping slightly extended the light-harvesting region and markedly improved the charge-separated states of the TiO_(2)nanosheets as evidenced by UV-vis absorption and steady-state/transient photoluminescence spectra.Upon simulated sunlight irradiation,we observed a 4.2-fold enhancement in the photocatalytic H_(2)evolution activity of optimal Yb^(3+)-doped TiO_(2)nanosheets compared to that of their undoped counterparts.Furthermore,when Pt nanoparticles were used as cocatalysts to reduce the H_(2)overpotential in this system,the photocatalytic activity enhancement factor increased to 8.5.By combining these results with those of control experiments,we confirmed that the extended charge-separated states play the main role in the enhancement of the photocatalytic H_(2)evolution activity of lanthanide-doped TiO_(2)nanosheets with coexposed{001}/{101}facets.
基金Project supported by the National Key R&D Program of China(2021YFA1202400,2017YFA0208000)the National Natural Science Foundation of China(21925401,21904033,51902177)the Fundamental Research Funds for the Central Universities(2042021 kf0036)。
文摘Persistent luminescence nanoparticles(PLNPs)are a kind of phosphors that can remain luminescent for seconds to several days after the stoppage of excitation.Lanthanides show the special capability to largely broaden the emission range and enhance the luminescence intensity of PLNPs due to their dense energy structure and unique electronic configurations.In the past decades,various methods have been developed for the synthesis of lanthanide-based PLNPs with excellent pe rsistent luminescence propertie s,and the lanthanide-based PLNPs are widely studied in areas including biome dicine,energy,and information storage.In this review,we summarized the research progress in the synthe sis of lanthanidebased PLNPs and outline d several typical synthesis methods.We discussed the fundamental concepts of preparation methods as well as the advantages and drawbacks of the typical synthetic approache s.Moreove r,the current challenges and the potential solutions for the development of lanthanide-based PLNP s are also discussed in an attempt to provide strate gies to further improve the optical properties of lanthanide-based PLNPs.We hope this review can contribute to the design of lanthanide-based PLNPs with desired properties and further promote their applications in biomedicine,energy,and information science.
