Synthesis,Crystal Structure,Fluorescent and Antioxidation Properties of Cerium(III) and Europium(III) Complexes with Bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine

Two aliphatic ether Schiff base lanthanide complexes (Ln = Eu, Ce) with bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine (Bod), were synthesized and characterized by physicochemical and spectroscopic methods. [Eu(Bod)(NO₃)₃] ( 1 ) is a discrete mononuclear species and [Ce(Bod)(NO₃)₃DMF]_∞ ( 2 ) exhibits an inorganic coordination polymer. In the two complexes, the metal ions both are ten‐coordinated and the geometric structure around the Ln^III atom can be described as distorted hexadecahedron. Under excitation at room temperature, the red shift in the fluorescence band of the ligand in the complexes compared with that of the free ligand can be attributed to coordination of the rare earth ions to the ligand. Moreover, the antioxidant activities of the two complexes were investigated. The results demonstrated that the complexes have better scavenging activity than both the ligand and the usual antioxidants on the hydroxyl and superoxide radicals.     

Self‐Assembled Triple‐Stranded Lanthanide Dimetallic Helicates with a Ditopic Ligand Derived from Bis(benzimidazole)pyridine and Featuring an (4‐Isothiocyanatophenyl)ethynyl Substituent

Bis(2‐{6‐(diethylcarbamoyl)‐4‐[(4‐isothiocyanatophenyl)ethynyl]pyridin‐2′‐yl}‐1‐ethylbenzimidazol‐5‐yl)methane ( L ^G ) reacts with trivalent lanthanide ions in acetonitrile to yield triple‐stranded dimetallic helicates [Ln₂( L ^G )₃]⁶⁺. ¹H‐NMR Data point to the helicates being the only species formed under stoichiometric conditions and having a time‐averaged D₃ symmetry on the NMR time scale. The photophysical properties of L ^G and its helicates are discussed with respect to the closely related ligands L ^B , L ^E , and their complexes, two ligands devoid of the isothiocyanatophenylethynyl substituent. The quantum yield of the ligand fluorescence is three times smaller compared to L ^E , while that of the Eu^III‐centered luminescence (1.1%) is three times larger. On the other hand, the luminescence of Tb^III is not sensitized by L ^G . This is explained in terms of energy differences between the singlet and triplet states on one hand, and between the 0‐phonon transition of the triplet state and the excited metal ion states on the other. This work demonstrates that bulky substituents in the 4‐position of the pyridine ring do not prevent the formation of triple‐stranded helicates, opening the way for luminescent probes that can easily be coupled to biological materials.     

Two Lanthanide(III) Complexes based on the Schiff Base N,N′‐Bis(salicylidene)‐1,5‐diamino‐3‐oxapentane: Synthesis,Characterization, DNA‐binding Properties,and Antioxidation

The Schiff base N,N′‐bis(salicylidene)‐1,5‐diamino‐3‐oxapentane (H₂L) and its lanthanide(III) complexes, PrL(NO₃)(DMF)(H₂O) ( 1 ) and Ho₂L₂(NO₃)₂ · 2H₂O ( 2 ), were synthesized and characterized by physicochemical and spectroscopic methods. Single crystal X‐ray structure analysis revealed that complex 1 is a discrete mononuclear species. The Pr^III ion is nine‐coordinate, forming a distorted capped square antiprismatic arrangement. Complex 2 is a centrosymmetric dinuclear neutral entity in which the Ho^III ion is eight‐coordinate with distorted square antiprismatic arrangement. The DNA‐binding properties of H₂L and its Ln^III complexes were investigated by spectrophotometric methods and viscosity measurements. The results suggest that the ligand H₂L and its Ln^III complexes both connect to DNA in a groove binding mode; the complexes bind more strongly to DNA than the ligand. Moreover, the antioxidant activities of the Ln^III complexes were in vitro determined by superoxide and hydroxyl radical scavenging methods, which indicate that complexes 1 and 2 have OH ^· and O₂^{– ·} radical scavenging activity.     

N,N′‐Bis(Salicylidene)‐1,2‐Cyclohexanediamine Lanthanide(III) Coordination Polymers: Syntheses,Crystal Structures,and Luminescence Properties

The salen‐type ligand H₂L [H₂L = N,N′‐bis(salicylidene)‐1,2‐cyclohexanediamine] was utilized for the synthesis of two lanthanide(III) coordination polymers [LnH₂L(NO₃)₃MeOH]_n [Ln = Eu ( 1 ) and Ln = Lu ( 2 )]. The single‐crystal X‐ray diffraction analyses of 1 and 2 revealed that they are isomorphous and exhibit one‐dimension neutral structure, in which H₂L effectively functions as a bridging ligand and give rise to a chain‐like polymer. The luminescent properties of polymers in solid state and in solution were investigated and 1 exhibits typical red luminescence of Eu^III ions in solid state and dichloromethane solution and 2 emits the ligand‐centered blue luminescence. The energy transfer mechanisms in these luminescent lanthanide polymers were described through calculation of the lowest triplet level of ligand H₂L.     

One‐dimensional Salen‐type Chain‐like Lanthanide(III) Coordination Polymers: Syntheses,Crystal Structures,and Fluorescence Properties

Four salen‐type lanthanide(III) coordination polymers [LnH₂L(NO₃)₃(MeOH)_x]_n [Ln = La ( 1 ), Ce ( 2 ), Sm ( 3 ), Gd ( 4 )] were prepared by reaction of Ln(NO₃)₃ · 6H₂O with H₂L [H₂L = N,N′‐bis(salicylidene)‐1,2‐cyclohexanediamine]. Single‐crystal X‐ray diffraction analysis revealed that H₂L effectively functions as a bridging ligand forming a series of 1D chain‐like polymers. The solid‐state fluorescence spectra of polymers 1 and 2 emit single ligand‐centered green fluorescence, whereas 3 exhibits typical red fluorescence of Sm^III ions. The lowest triplet level of ligand H₂L was calculated on the basis of the phosphorescence spectrum of Gd^III complex 4 . The energy transfer mechanisms in the lanthanide polymers were described and discussed.     

Two C3‐Symmetric Dy3III Complexes with Triple Di‐μ‐methoxo‐μ‐phenoxo Bridges,Magnetic Ground State,and Single‐Molecule Magnetic Behavior

Two series of isostructural C₃‐symmetric Ln₃ complexes Ln₃ ? [BPh₄] and Ln₃ ? 0.33[Ln(NO₃)₆] (in which Ln^III=Gd and Dy) have been prepared from an amino‐bis(phenol) ligand. X‐ray studies reveal that Ln^III ions are connected by one μ₂‐phenoxo and two μ₃‐methoxo bridges, thus leading to a hexagonal bipyramidal Ln₃O₅ bridging core in which Ln^III ions exhibit a biaugmented trigonal‐prismatic geometry. Magnetic susceptibility studies and ab initio complete active space self‐consistent field (CASSCF) calculations indicate that the magnetic coupling between the Dy^III ions, which possess a high axial anisotropy in the ground state, is very weakly antiferromagnetic and mainly dipolar in nature. To reduce the electronic repulsion from the coordinating oxygen atom with the shortest Dy?O distance, the local magnetic moments are oriented almost perpendicular to the Dy₃ plane, thus leading to a paramagnetic ground state. CASSCF plus restricted active space state interaction (RASSI) calculations also show that the ground and first excited state of the Dy^III ions are separated by approximately 150 and 177 cm^?1, for Dy₃ ? [BPh₄] and Dy₃ ? 0.33[Dy(NO₃)₆], respectively. As expected for these large energy gaps, Dy₃ ? [BPh₄] and Dy₃ ? 0.33[Dy(NO₃)₆] exhibit, under zero direct‐current (dc) field, thermally activated slow relaxation of the magnetization, which overlap with a quantum tunneling relaxation process. Under an applied H_dc field of 1000 Oe, Dy₃ ? [BPh₄] exhibits two thermally activated processes with U_eff values of 34.7 and 19.5 cm^?1, whereas Dy₃ ? 0.33[Dy(NO₃)₆] shows only one activated process with U_eff=19.5 cm^?1.     

N‐Heterocyclic Tridentate Aromatic Ligands Bound to [Ln(hexafluoroacetylacetonate)3] Units: Thermodynamic,Structural, and Luminescent Properties

Herein, we discuss how, why, and when cascade complexation reactions produce stable, mononuclear, luminescent ternary complexes, by considering the binding of hexafluoroacetylacetonate anions (hfac^?) and neutral, semi‐rigid, tridentate 2,6‐bis(benzimidazol‐2‐yl)pyridine ligands ( Lk ) to trivalent lanthanide atoms (Ln^III). The solid‐state structures of [Ln( Lk )(hfac)₃] (Ln=La, Eu, Lu) showed that [Ln(hfac)₃] behaved as a neutral six‐coordinate lanthanide carrier with remarkable properties: 1) the strong cohesion between the trivalent cation and the didentate hfac anions prevented salt dissociation; 2) the electron‐withdrawing trifluoromethyl substituents limited charge‐neutralization and favored cascade complexation with Lk ; 3) nine‐coordination was preserved for [Ln( Lk )(hfac)₃] for the complete lanthanide series, whilst a counterintuitive trend showed that the complexes formed with the smaller lanthanide elements were destabilized. Thermodynamic and NMR spectroscopic studies in solution confirmed that these characteristics were retained for solvated molecules, but the operation of concerted anion/ligand transfers with the larger cations induced subtle structural variations. Combined with the strong red photoluminescence of [Eu( Lk )(hfac)₃], the ternary system Ln^III/hfac^?/ Lk is a promising candidate for the planned metal‐loading of preformed multi‐tridentate polymers.     

Synthesis,Structure, and Luminescent Properties of Lanthanide Coordination Polymers Based on 5‐Hydroxyisophthalate and Phen Ligands

Three lanthanide coordination polymers incorporating 5‐hydroxyisophthalate ( L ) and phen ligands, [Eu( L )(phen)]_n ( 1 ) and [Ln( L )(phen)₂]_n [Ln = Sm ( 2 ) and Pr ( 3 )], were synthesized. X‐ray structural analysis reveals that 1 features a (3,6)‐connected 3D rtl topology. Complexes 2 and 3 are isostructural and have 2D sheets with 6³ topology. Comparison of the structural differences between 1 and 2 (or 3 ) suggests that the different metal sources play an important role in the formation of such coordination networks. Compounds 1 and 2 show photoluminescence and their emission properties are closely related to their corresponding central Ln^III atoms.     

Lanthanide(III) Complexes of Bis‐semicarbazone and Bis‐imine‐Substituted Phenanthroline Ligands: Solid‐State Structures,Photophysical Properties,and Anion Sensing

Phenanthroline‐based hexadentate ligands L¹ and L² bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La^III, Eu^III, Tb^III, Lu^III, and Y^III metal ions, were synthesized, and the crystal structures of [ML¹Cl₃] (M=La^III, Eu^III, Tb^III, Lu^III, or Y^III) complexes were determined. Solvent or water molecules act as coligands for the rare‐earth metals in addition to halide anions. The big Ln^III ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu^III, Tb^III, Lu^III, and Y^III centers with smaller ionic radii show CN=9. Complexes of L², namely [ML²Cl₃] (M=Eu^III, Tb^III, Lu^III, or Y^III) ions could also be prepared. Only the complex of Eu^III showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine‐5′‐triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine‐5′‐diphosphate (ADP) and adenosine‐5′‐monophosphate (AMP) was found. ³¹P NMR spectroscopic studies revealed the formation of a [EuL²(ATP)] coordination species.     

The Series of Rare Earth Complexes [Ln2Cl6(μ‐4,4′‐bipy)(py)6], Ln=Y,Pr, Nd,Sm‐Yb: A Molecular Model System for Luminescence Properties in MOFs Based on LnCl3 and 4,4′‐Bipyridine

A series of 12 dinuclear complexes [Ln₂Cl₆(μ‐4,4′‐bipy)(py)₆], Ln=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, ( 1 – 12 , respectively) was synthesized by an anhydrous solvothermal reaction in pyridine. The complexes contain a 4,4′‐bipyridine bridge and exhibit a coordination sphere closely related to luminescent lanthanide MOFs based on LnCl₃ and 4,4‐bipyridine. The dinuclear complexes therefore function as a molecular model system to provide a better understanding of the luminescence mechanisms in the Ln‐N‐MOFs ${\hbox{}{{\hfill 2\atop \hfill \infty }}}$ [Ln₂Cl₆(4,4′‐bipy)₃] ? 2(4,4′‐bipy). Accordingly, the luminescence properties of the complexes with Ln=Y, Sm, Eu, Gd, Tb, Dy, ( 1 , 4 – 8 ) were determined, showing an antenna effect through a ligand–metal energy transfer. The highest efficiency of luminescence is observed for the terbium‐based compound 7 displaying a high quantum yield (QY of 86 %). Excitation with UV light reveals typical emission colors of lanthanide‐dependent intra 4f–4f‐transition emissions in the visible range (Tb^III: green, Eu^III: red, Sm^III: salmon red, Dy^III: yellow). For the Gd^III‐ and Y^III‐containing compounds 6 and 1 , blue emission based on triplet phosphorescence is observed. Furthermore, ligand‐to‐metal charge‐transfer (LMCT) states, based on the interaction of Cl^? with Eu^III, were observed for the Eu^III compound 5 including energy‐transfer processes to the Eu^III ion. Altogether, the model complexes give further insights into the luminescence of the related MOFs, for example, rationalization of Ln‐independent quantum yields in the related MOFs.     

Luminescent Bimetallic Lanthanide Bioprobes for Cellular Imaging with Excitation in the Visible‐Light Range

A series of homoditopic ligands H₂L^CX (X=4–6) has been designed to self‐assemble with lanthanide ions (Ln^III), resulting in neutral bimetallic helicates of overall composition [Ln₂(L^CX)₃] with the aim of testing the influence of substituents on the photophysical properties, particularly the excitation wavelength. The complex species are thermodynamically stable in water (log β₂₃ in the range 26–28 at pH 7.4) and display a metal‐ion environment with pseudo‐D₃ symmetry and devoid of coordinated water molecules. The emission of Eu^III, Tb^III, and Yb^III is sensitised to various extents, depending on the properties of the ligand donor levels. The best helicate is [Eu₂(L^C5)₃] with excitation maxima at 350 and 365 nm and a quantum yield of 9 %. The viability of cervix cancer HeLa cells is unaffected when incubated with up to 500 μm of the chelate during 24 h. The helicate permeates into the cells by endocytosis and locates into lysosomes, which co‐localise with the endoplasmatic reticulum, as demonstrated by counterstaining experiments. The relatively long excitation wavelength allows easy recording of bright luminescent images on a confocal microscope (λ_exc=405 nm). The new lanthanide bioprobe remains undissociated in the cell medium, and is amenable to facile derivatisation. Examination of data for seven Eu^III and Tb^III bimetallic helicates point to shortcomings in the phenomenological rules of thumb between the energy gap ΔE(³ππ*–⁵D_J) and the sensitisation efficiency of the ligands.     

Syntheses,Structures, and Photoluminescence of Lanthanide Coordination Polymers Based on 4‐Oxo‐1,4‐dihydro‐2,6‐pyridinedicarboxylic acid

Investigating the coordination chemistry of H₂CDA (4‐oxo‐1,4‐dihydro‐2,6‐pyridinedicarboxylic acid) with rare earth salts Ln(NO₃)₃ under hydrothermal conditions, structure transformation phenomenon was observed. The ligand, H₂CDA charged to its position isomer, enol type structure, H₃CAM (4‐hydroxypyridine‐2,6‐dicarboxylic acid). Six new lanthanide(III) coordination polymers with the formulas [Ln(CAM)(H₂O)₃]_n [Ln = La ( 1 ), Pr, ( 2 )] and {[Ln(CAM)(H₂O)₃] · H₂O}_n [Ln = Nd, ( 3 ), Sm, ( 4 ), Eu, ( 5 ), Y, ( 6 )] were synthesized and characterized. The X‐ray structure analyses show two kinds of coordination structures. The complexes 1 and 2 and 3 – 6 are isostructural. Complexes 1 and 2 crystallize in the monoclinic C₂/c space group, whereas 3 – 6 crystallize in the monoclinic system with space group P2₁/n. In the two kinds of structures, H₃CAM displays two different coordination modes. The Sm^III and Eu^III complexes exhibit the corresponding characteristic luminescence in the visible region at an excitation of 376 nm.     

Hydrothermal Syntheses,Crystal Structures,and Luminescent Properties of Three Organic‐Lanthanide Complexes with 3‐Hydroxycinnamic Acid

Three new homodinuclear lanthanide(III) complexes [Ln₂(L)₆(2,2′‐bipy)₂] [Ln = Tb^III ( 1 ), Sm^III ( 2 ), Eu^III ( 3 ); HL = 3‐hydroxycinnamic acid (3‐HCA); 2,2′‐bipy = 2,2′‐bipyridine] were synthesized and characterized by IR spectroscopy, elemental analyses, and X‐ray diffraction techniques. Complexes 1 – 3 crystallize in triclinic system, space group P$\bar{1}$ . In all complexes the lanthanide ions are nine‐coordinate by two nitrogen atoms from the 2,2′‐bipy ligand and seven oxygen atoms from one chelating L ligands and four bridging L ligands, forming distorted tricapped trigonal prismatic arrangements. The lanthanide(III) ions are intramolecularly bridged by eight carboxylate oxygen atoms forming dimeric complexes with Ln ··· Ln distances of 3.92747(15), 3.9664(6), and 3.9415(4) Å for complexes 1 – 3 , respectively. The luminescent properties in the solid state of HL ligand and Eu^III complex are also discussed.     

Structure and Magnetic Properties of Two Lanthanide 1,4‐Phenylenediacetate Compounds

The reactions of Ln(NO₃)₃ with 1,4‐phenylenediacetic acid (H₂PDA) under hydrothermal conditions produced two isostructural lanthanide coordination polymers with the empirical formula [Ln₂(PDA)₃(H₂O)] · 2H₂O [Ln = Nd ( 1 ), Sm ( 2 )]. Single‐crystal X‐ray diffraction analyses revealed that both contain one‐dimensionalmetal carboxylato chains, which are further connected by the–CH₂C₆H₄CH₂– spacers of PDA^2– ligands to yield a three‐dimensional metal‐organic framework. Magnetic susceptibilities of 1 and 2 were measured. The experimental χ_mT value of both compounds decreases continuously with decreasing temperature over the whole temperature range. The best least‐squares fit of the experimental data of 1 to a theoretical equation in the temperature range of 70–300 K gives the zero‐field splitting parameter Δ = 2.21 cm^–1 and the magnetic interaction between the Nd^III ions 2zJ′ = –1.97 cm^–1, which indicates the presence of antiferromagnetic interaction between the Nd^III ions. The experimental χ_mT value of 2 at 2 K is much smaller than the expected value for two free Sm^III ions (⁶H_5/2, g = 2/7) in the ground state, indicating that an antiferromagnetic interaction possibly exists between Sm^III ions at low temperature. Fitting the magnetic data of 2 above 110 K based on an equation deduced from the Sm^III ion in a monomeric system with free‐ion approximation gave a spin‐orbit coupling parameter λ = 192(2) cm^–1     

Trinuclear [CoIII2–LnIII] (Ln=Tb,Dy) Single‐Ion Magnets with Mixed 6‐Chloro‐2‐Hydroxypyridine and Schiff Base Ligands

The Schiff base ligand N1,N3‐bis(3‐methoxysalicylidene)diethylenetriamine (H₂valdien) and the co‐ligand 6‐chloro‐2‐hydroxypyridine (Hchp) were used to construct two 3d–4f heterometallic single‐ion magnets [Co₂Dy(valdien)₂(OCH₃)₂(chp)₂] ? ClO₄ ? 5 H₂O ( 1 ) and [Co₂Tb(valdien)₂(OCH₃)₂(chp)₂] ? ClO₄ ? 2 H₂O ? CH₃OH ( 2 ). The two trinuclear [Co^III₂Ln^III] complexes behave as a mononuclear Ln^III magnetic system because of the presence of two diamagnetic cobalt(III) ions. Complex 1 has a molecular symmetry center, and it crystallizes in the C2/c space group, whereas complex 2 shows a lower molecular symmetry and crystallizes in the P2₁/c space group. Magnetic investigations indicated that both complexes are field‐induced single‐ion magnets, and the Co^III₂–Dy^III complex possesses a larger energy barrier [74.1(4.2) K] than the Co^III₂–Tb^III complex [32.3(2.6) K].     

Synthesis of LnII‐in‐Cryptand Complexes by Chemical Reduction of LnIII‐in‐Cryptand Precursors: Isolation of a NdII‐in‐Cryptand Complex

Lanthanide triflates have been used to incorporate Nd^III and Sm^III ions into the 2.2.2‐cryptand ligand (crypt) to explore their reductive chemistry. The Ln(OTf)₃ complexes (Ln=Nd, Sm; OTf=SO₃CF₃) react with crypt in THF to form the THF‐soluble complexes [Ln^III(crypt)(OTf)₂][OTf] with two triflates bound to the metal encapsulated in the crypt. Reduction of these Ln^III‐in‐crypt complexes using KC₈ in THF forms the neutral Ln^II‐in‐crypt triflate complexes [Ln^II(crypt)(OTf)₂]. DFT calculations on [Nd^II(crypt)]²⁺], the first Nd^II cryptand complex, assign a 4f⁴ electron configuration to this ion.     

Homo‐ and Heterodinuclear Helicates of Lanthanide(III), Zinc(II) and Aluminium(III) Based on 8‐Hydroxyquinoline Ligands

Homonuclear helicates with rare‐earth‐metal(III) ions or heteronuclear derivatives with rare‐earth‐metal and aluminium or zinc centres are obtained in alkali‐metal‐templated self‐assembly processes from isobutenylidene‐bridged homoditopic bis(2‐carbamido‐8‐hydroxyquinoline)‐derived ligands 1 ? H₂ and 2 ? H₂ or heteroditopic (8‐hydroxyquinoline)(2‐carbamido‐8‐hydroxyquinoline)‐derived ligands 3 ? H₂ and 4 ? H₂. Diamagnetic coordination compounds possess a high stability in organic solvents such as CDCl₃, [D₄]MeOH or [D₆]DMSO and can be well characterised by ¹H NMR spectroscopy by using methylene protons and the protons of the vinylic units of the ligand as stereochemical or symmetry probes, respectively. Some of the homonuclear complexes could be crystallised and were characterised by using X‐ray diffraction studies. The complexes adopt a triple‐stranded helical structure with a central templating cation encapsulated in their interior. An unusual orientation of the double bond of one spacer towards this cation is observed. The homo‐ and heterodinuclear helicates with ytterbium(III), neodymium(III) or erbium(III) of ligands 2 and 4 were of special interest owing to their near‐infrared (NIR) emitting properties, which were investigated depending on the lanthanide and on the encapsulated alkali‐metal cation.     

Modulation of the Lifetime of Water Bound to Lanthanide Metal Ions in Complexes with Ligands Derived from 1,4,7,10‐Tetraazacyclododecane Tetraacetate (DOTA)

A series of di‐ and tetraamide derivatives of DOTA were synthesized, and their lanthanide(III) complexes were examined by multinuclear ¹H‐, ¹³C‐, and ¹⁷O‐NMR spectroscopy, and compared with literature data of similar, known complexes (Table). All ligands formed structures similar to the parent [Ln^III(DOTA)]^? complexes, with four N‐atoms and four O‐atoms from DOTA and one O‐atom from the inner‐sphere water molecules. Interestingly, the lifetimes τ_M of the inner‐sphere, metal‐bound water molecules vary widely, ranging from nano‐ to milliseconds, depending on the identity of the pendent amide side chains. In general, positively charged [Ln^III(DOTA‐tetraamide)]³⁺ complexes display the longest residence times (high τ_M values), while complexes with additional charged functional groups on the extended amides display much smaller τ_M values, even when the side groups are not directly coordinated to the central Ln³⁺ ions. The design of novel [Ln^III(DOTA‐tetraamide)]³⁺ complexes with a wide, tunable range of τ_M values is of prime importance for the application of fast‐responding, paramagnetic chemical‐exchange‐saturation‐transfer (PARACEST) imaging agents used for the study of physiological and metabolic processes.     

Photoluminescence Properties of Lanthanide‐Organic Frameworks (LnOFs) with Thiophene‐2,5‐Dicarboxylate and Acetate

S‐heterocyclic dicarboxylic acid, thiophene‐2,5‐dicarboxylic acid (H₂TDC), was employed to construct a series of lanthanide‐organic frameworks (LnOFs) with coligand acetate, formulated as [Ln(TDC)(OAc)(H₂O)]_n [Ln = Eu ( 1 ), Tb ( 2 ), Gd ( 3 ), Dy ( 4 ), Sm ( 5 )] under hydrothermal conditions. Structure analysis reveals that 1 – 5 have dinuclear 3D metal organic frameworks (MOFs), in which TDC^2– and OAc^– display (κ¹‐κ¹)‐(κ¹–κ¹)‐μ₄ and (κ²‐κ¹)‐μ₂ coordination fashions, respectively. The dehydrated products of all compounds show high thermal stability above 410 °C. As for 1 , 2 , 4 , and 5 , the photoluminescence analyses exhibit characteristic luminescence emission bands of the corresponding lanthanide ions in the visible region. In particular, compound 2 displays bright green luminescence in the solid state with ⁵D₄ lifetime of 0.510 ms and relative high overall quantum yield of 16 %, based on an ideal energy gap between the lowest triplet state energy level of H₂TDC ligand and the ⁵D₄ state energy level of Tb³⁺. The energy transfer mechanisms in compounds 1 and 2 were also discussed.     

Syntheses,Structures, Photoluminescence,and Magnetism of a Series of Discrete Lanthanide Complexes based on 2,5‐Dichlorobenzoate and 1,10‐Phenanthroline

The syntheses and crystal structures of eight lanthanide complexes with formula [Ln(2,5‐DCB)_x(phen)_y] are reported, which are characterized via single‐crystal, powder X‐ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis, photoluminescence measurement, and DC/AC magnetic measurement. These eight complexes are isostructural, and possess a discrete dinuclear structure. The adjacent dinuclear molecules are linked by the hydrogen bonding interactions into a one‐dimensional (1D) supramolecular chain. The neighboring 1D chains are further extended into a two‐dimensional (2D) supramolecular layer by the π–π stacking interactions. The photoluminescent properties of complexes 1 (Nd^III), 2 (Sm^III), 3 (Eu^III), 5 (Tb^III), 6 (Dy^III), and 8 (Yb^III) were investigated. Magnetic investigations also reveal the presence of ferromagnetic interactions in complexes 4 (Gd^III), 6 (Dy^III), and 7 (Er^III). Additionally, complex 6 (Dy^III) demonstrates field‐induced slow magnetic relaxation behavior.