First Tribo-Excited Chemical Reaction of a Stacked Lanthanide Coordination Polymer with an in Situ Reaction Monitor

A tribo-excited chemical reaction using a stacked lanthanide coordination polymer is demonstrated for the first time. The polymer is composed of a Eu^III ion, hexafluoroacetylacetonato ligands, and an anthracene-based phosphine oxide bridge. The tightly stacked structure with hydrogen bonding was characterized by X-ray crystal structure analysis. The mechanical stimulus leads to tribo-excited oxidation in the Eu^III coordination polymer. Electron ionization mass spectroscopy and photo-spectroscopic analysis reveal that the chemical product afforded by tribo-oxidation is different from that obtained by photo-oxidation.     

High‐Performance Magnetic Refrigerant Featuring One‐Dimensional Gd‐O Chains and O‐Gd3 Triangles

Magnetic cooling at low temperature has attracted intensive interest in cryogenics research, which may become important as cooling medium for long‐wave photon detectors to support space exploration. Here, we report a Gd‐based quaternary magnetic refrigerant material, Gd₅BSi₂O₁₃, containing chains of face‐shared GdO₉ polyhedra and geometrically frustrated OGd₃ triangles. Magnetic measurements indicate that Gd₅BSi₂O₁₃ exhibits a large magnetocaloric effect (MCE) about 1.74 times that of the practical magnetic refrigerant GGG (−ΔS_m=67.0 J kg⁻¹ K⁻¹). We analyzed the origin of the large MCE by comparing Gd^III‐containing compounds with different structures and concentrations of Gd^III.     

Luminescent Europium(III) Coordination Zippers Linked with Thiophene‐Based Bridges

Novel Eu^III coordination polymers [Eu(hfa)₃(dpt)]_n (dpt: 2,5‐bis(diphenylphosphoryl)thiophene) and [Eu(hfa)₃(dpedot)]_n (dpedot: 2,5‐bis(diphenylphosphoryl)ethylenedioxythiophene) with hydrogen‐bonded zipper structures are reported. The coordination polymers are composed of Eu^III ions, hexafluoroacetylacetonato ligands, and thiophene‐based phosphine oxide bridges. The zig‐zag orientation of single polymer chains induced the formation of densely packed coordination structures with multiple intermolecular interactions, resulting in thermal stability above 300 °C. They exhibit a high intrinsic emission quantum yield (ca. 80 %) due to their asymmetrical and low‐vibrational coordination structures around Eu^III ions. Furthermore, the characteristic alternative orientation of substituents also contributes to the dramatically high ligand‐to‐metal energy transfer efficiencies of up to 80 % in the solid state.     

Comparing the 2,2′‐Biphenylenedithiophosphinate Binding of Americium with Neodymium and Europium

Advancing our understanding of the minor actinides (Am, Cm) versus lanthanides is key for developing advanced nuclear‐fuel cycles. Herein, we describe the preparation of (NBu₄)Am[S₂P(^tBu₂C₁₂H₆)]₄ and two isomorphous lanthanide complexes, namely one with a similar ionic radius (i.e., Nd^III) and an isoelectronic one (Eu^III). The results include the first measurement of an Am?S bond length, with a mean value of 2.921(9) Å, by single‐crystal X‐ray diffraction. Comparison with the Eu^III and Nd^III complexes revealed subtle electronic differences between the complexes of Am^III and the lanthanides.     

Chemiluminescence and catalysis of decomposition of dispiro(diadamantane-1,2-dioxetane) in solutions of lanthanide perchlorates

Chemiluminescence (CL) accompanying the decomposition of dispiro(diadamantane-1,2-dioxetane) (1) in acetonitrile solutions of Eu^III, Gd^III, Tb^III, Pr^III, and Ce^III perchlorates was studied. In the presence of Eu^III, Tb^III, and Pr^III ions, the chemiluminescence spectra contain the luminescence bands of these ions. In the cases of Gd^III and Ce^III, the chemiluminescence is caused by deactivation of singlet-excited adamantanone (2). The excitation of the lanthanide ion depends on the existence of suitable energy levels at which intracomplex excitation transfer from the³n,π^* of ketone is possible. Chemiluminescence of1 increases in solutions of Eu^III and Tb^III. The yields of CL and excitation of the lanthanide ions in the decomposition of1 in the1·Eu^III and1\Tb^III complexes were determined: φ_Eu · =0.013 ± 0.003 and φ_Tb · =0.08±0.02. The fact that the efficiency for the population of the⁵D₄-level of Tb^III is higher than that for the⁵D₁ and⁵D₀-levels of Eu^III is related to the difference in the energy gap between the triplet level of2 and the excited levels of the lanthanides. For Part I, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 730–735, April, 1997.     

Metal‐Ion Sensing Europium(III) Complexes with Bidentate Phosphine Oxide Ligands Containing a 2,2′‐Bipyridine Framework

Novel Eu^III complexes with bidentate phosphine oxide ligands containing a bipyridine framework, i.e., [3,3′‐bis(diphenylphosphoryl)‐2,2′‐bipyridine]tris(hexafluoroacetylacetonato)europium(III) ([Eu(hfa)₃(BIPYPO)]) and [3,3′‐bis(diphenylphosphoryl)‐6,6′‐dimethyl‐2,2′‐bipyridine]tris(hexafluoroacetylacetonato)europium(III) ([Eu(hfa)₃(Me‐BIPYPO)]), were synthesized for lanthanide‐based sensor materials having high emission quantum yields and effective chemosensing properties. The emission quantum yields of [Eu(hfa)₃(BIPYPO)] and [Eu(hfa)₃(Me‐BIPYPO)] were 71 and 73%, respectively. Metal‐ion sensing properties of the Eu^III complexes were also studied by measuring the emission spectra of Eu^III complexes in the presence of Zn^II or Cu^II ions. The metal‐ion sensing and the photophysical properties of luminescent Eu^III complexes with a bidentate phosphine oxide containing 2,2′‐bipyridine framework are demonstrated for the first time.     

Luminescence of Eu3+ and Tb3+ Complexes of Two Macrobicyclic Ligands Derived from a Tetralactam Ring and a Chromophoric Antenna

Two macrobicyclic ligands derived from an 18‐membered tetralactam ring and 2,2′‐bipyridine or 2,6‐bis(pyrazol‐1‐yl)pyridine moieties, 1 and 2 , respectively, form stable complexes with Gd^III, Eu^III, and Tb^III ions in aqueous solution. The ligand‐based luminescence is retained in the Gd^III cryptates, whereas this radiative deactivation is quenched in the Eu^III and Tb^III cryptates by ligand‐to‐metal energy transfer, resulting in the usual metal‐centered emission spectra. Singlet‐ and triplet‐state energies, emission‐decay lifetimes, and luminescence yields were measured. [Tb⊂ 1 ]³⁺ cryptate shows a long luminescence lifetime (τ=1.12 ms) and a very high metal luminescence quantum yield (Φ=0.25) in comparison with those reported in the literature for Tb³⁺ complexes sensitized by a bipyridine chromophore. By comparison to [Ln⊂ 1 ]³⁺, [Ln⊂ 2 ]³⁺ presents markedly lower luminescence properties, due to worse interaction between the 2,6‐bis(pyrazol‐1‐yl)pyridine unit and the metal ion. Moreover, the luminescent metal and the triplet ligand energy levels of [Eu⊂ 2 ]³⁺ do not match. The effects of H₂O molecules coordinated to the metal centre and of thermally activated decay processes on nonradiative deactivation to the ground‐state are also reported.     

Low‐Dimensional Carboxylate‐Bridged GdIII Complexes for Magnetic Refrigeration

Four carboxylate‐bridged Gd^III complexes ( 1 – 4 ) with 1D/2D structures have been synthesized by using the hydrothermal reaction of Gd₂O₃ with various carboxylate ligands. Compounds 1 and 2 contained the same [2n] Gd^III? OH ladders, but with different crystallographically independent Gd^III ions, whilst the structures of compounds 3 and 4 were composed of [Gd₄(μ₃‐OH)₂(piv)₈(H₂O)₂]²⁺ units and 1D ladder Gd^III chains, respectively. Antiferromagnetic interactions occurred in compounds 1 – 3 , owing to their small Gd? O? Gd angles, whereas ferromagnetic coupling occurred in compound 4 , in which the Gd? O? Gd angles were larger. These complexes exhibited a distinct magnetocaloric effect (MCE), which was affected by their different magnetic densities and exchange interactions. Among these compounds, complex 4 presented the largest MCE (?ΔS_m^max=43.6 J kg^?1 K^?1), the lowest M_w/N_Gd ratio (the highest magnetic density), and weak ferromagnetic coupling. Therefore, a lower M_w/N_Gd ratio and weaker exchange interactions (a smaller absolute value of θ) between Gd^III ions resulted in a larger MCE for the Gd^III complexes.     

Coordinated lanthanide metal complexes ofN-benzoylglycine hydrazide

Summary N-benzoylglycine hydrazide (BzGH) reacts with trivalent lanthanide metal ions forming complexes of the type [Ln(BzGH)₂Cl(H₂O)₂]Cl₂·nH₂O, where Ln=La^III, Pr^III, Nd^III, Sm^III, Eu^III, Gd^III, Tb^III, Dy^III, or Y^III;n=1 or 2. The structures of the complexes have been studied by conductance, magnetic, electronic, i.r.,¹H n.m.r. and¹³C n.m.r. spectral techniques. The nephelauxetic ratio, the bonding parameter, Sinha's parameter and the covalency angular overlap parameter have been calculated from the electronic spectra of Pr^III, Nd^III and Sm^III complexes. Seven-coordination is proposed in the Nd^III complex. The i.r. and¹H n.m.r. spectral data suggest bidentate BzGH in all the complexes.     

Comparison of the Electronic and Vibrational Optical Activity of a Europium(III) Complex

The geometry and the electronic structure of chiral lanthanide(III) complexes are traditionally probed by electronic methods, such as circularly polarised luminescence (CPL) and electronic circular dichroism (ECD) spectroscopy. The vibrational phenomena are much weaker. In the present study, however, significant enhancements of vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectral intensities were observed during the formation of a chiral bipyridine–Eu^III complex. The ten‐fold enhancement of the vibrational absorption and VCD intensities was explained by a charge‐transfer process and the dominant effect of the nitrate ion on the spectra. A much larger enhancement of the ROA and Raman intensities and a hundred‐fold increase of the circular intensity difference (CID) ratio were explained by the resonance of the λ=532 nm laser light with the ⁷F₀ → ⁵D₀ transitions. This phenomenon is combined with a chirality transfer, and mixing of the Raman and luminescence effects involving low‐energy ⁷F states of europium. The results thus indicate that the vibrational optical activity (VOA) may be a very sensitive tool for chirality detection and probing of the electronic structure of Eu^III and other coordination compounds.     

Photocytotoxicity of Oligothienyl-Functionalized Chelates That Sensitize LnIII Luminescence and Generate 1O2

Three new compounds containing a heptadentate lanthanide (Ln^III) ion chelator functionalized with oligothiophenes, n Thept(COOH)₄ (n=1, 2, or 3), were isolated. Their Ln^III complexes not only display the characteristic metal-centered emission in the visible or near-infrared (NIR) but also generate singlet oxygen (¹O₂). Luminescence efficiencies (ϕ^Ln) for [Eu 1 Thept(COO)₄ ]⁻ and [Eu 2 Thept(COO)₄ ]⁻ are ϕ^Eu=3 % and 0.5 % in TRIS buffer and 33 % and 3 % in 95 % ethanol, respectively. 3 Thept(COO)₄ ⁴⁻ does not sensitize Eu^III emission due to its low-lying triplet state. Near infra-red (NIR) luminescence is observed for all NIR-emitting Ln^III and ligands with efficiencies of ϕ^Yb=0.002 %, 0.005 % and 0.04 % for [Yb n Thept(COO)₄ ]⁻ (n=1, 2, or 3), and ϕ^Nd=0.0007 %, 0.002 % and 0.02 % for [Nd n Thept(COO)₄ ]⁻ (n=1, 2, or 3) in TRIS buffer. In 95 % ethanol, quantum yields of NIR luminescence increase and are ϕ^Yb=0.5 %, 0.31 % and 0.05 % for [Yb n Thept(COO)₄ ]⁻ (n=1, 2, or 3), and ϕ^Nd=0.40 %, 0.45 % and 0.12 % for [Nd n Thept(COO)₄ ]⁻ (n=1, 2, or 3). All complexes are capable of generating ¹O₂ in 95 % ethanol with ϕ_1Ο2 efficiencies which range from 2 % to 29 %. These complexes are toxic to HeLa cells when irradiated with UV light (λ_exc=365 nm) for two minutes. IC₅₀ values for the Ln^III complexes are in the range 15.2–16.2 μm ; the most potent compound is [Nd 2 Thept(COO)₄ ]⁻. The cell death mechanisms are further explored using an Annexin V—propidium iodide assay which suggests that cell death occurs through both apoptosis and necrosis.     

Multifunctionality in Bimetallic LnIII[WV(CN)8]3− (Ln=Gd,Nd) Coordination Helices: Optical Activity,Luminescence, and Magnetic Coupling

Two chiral luminescent derivatives of pyridine bis(oxazoline) (Pybox), (SS/RR)‐iPr‐Pybox (2,6‐bis[4‐isopropyl‐2‐oxazolin‐2‐yl]pyridine) and (SRSR/RSRS)‐Ind‐Pybox (2,6‐bis[8H‐indeno[1,2‐d]oxazolin‐2‐yl]pyridine), have been combined with lanthanide ions (Gd³⁺, Nd³⁺) and octacyanotungstate(V) metalloligand to afford a remarkable series of eight bimetallic CN^?‐bridged coordination chains: {[Ln^III(SS/RR‐iPr‐Pybox)(dmf)₄]₃[W^V(CN)₈]₃}_n ? dmf ? 4 H₂O (Ln=Gd, 1 ‐SS and 1 ‐RR; Ln=Nd, 2 ‐SS and 2 ‐RR) and {[Ln^III(SRSR/RSRS‐Ind‐Pybox)(dmf)₄][W^V(CN)₈]}_n ? 5 MeCN ? 4 MeOH (Ln=Gd, 3 ‐SRSR and 3 ‐RSRS; Ln=Nd, 4 ‐SRSR and 4 ‐RSRS). These materials display enantiopure structural helicity, which results in strong optical activity in the range 200–450 nm, as confirmed by natural circular dichroism (NCD) spectra and the corresponding UV/Vis absorption spectra. Under irradiation with UV light, the Gd^III‐W^V chains show dominant ligand‐based red phosphorescence, with λ_max≈660 nm for 1 ‐(SS/RR) and 680 nm for 3 ‐(SRSR/RSRS). The Nd^III‐W^V chains, 2 ‐(SS/RR) and 4 ‐(SRSR/RSRS), exhibit near‐infrared luminescence with sharp lines at 986, 1066, and 1340 nm derived from intra‐f ⁴F_3/2→⁴I_{9/2,11/2,13/2} transitions of the Nd^III centers. This emission is realized through efficient ligand‐to‐metal energy transfer from the Pybox derivative to the lanthanide ion. Due to the presence of paramagnetic lanthanide(III) and [W^V(CN)₈]^3? moieties connected by cyanide bridges, 1 ‐(SS/RR) and 3 ‐(SRSR/RSRS) are ferrimagnetic spin chains originating from antiferromagnetic coupling between Gd^III (S_Gd=7/2) and W^V (S_W=1/2) centers with J _{1 ‐(SS)}=?0.96(1) cm^?1, J _{1 ‐(RR)}=?0.95(1) cm^?1, J _{3 ‐(SRSR)}=?0.91(1) cm^?1, and J _{3 ‐(RSRS)}=?0.94(1) cm^?1. 2 ‐(SS/RR) and 4 ‐(SRSR/RSRS) display ferromagnetic coupling within their Nd^III‐NC‐W^V linkages.     

A linear Cu-Gd-Cu-Gd complex derived from the assembly reaction of [NaCuH3L] and [Gd(thd)3(H2O)2] (H3L = meso-1,2-diphenyl-1-(2-oxybenzamido)-2-(2-oxy-3-ethoxybenzylideneamino)ethane and Hthd = 2,2,6,6-tetra-methyl-3,5-heptanedione)

A linear tetranuclear Cu^II-Gd^III-Cu^II-Gd^III complex [Cu^IIL^dpen(meso)Gd^III(thd)₂(H₂O)]₂ was synthesized from the reaction of [NaCu^IIL^dpen(meso)(DMF)] with [Gd^III(thd)₃(H₂O)₂], and the structures and magnetic properties were investigated, where H₃L^dpen(meso) = meso-1,2-diphenyl-1-(2-hydroxybenzamido)-2-(2-hydroxy-3-ethoxybenzylideneamino)ethane and Hthd = 2,2,6,6-tetramethyl-3,5-heptanedione. The Cu^II complex component [NaCu^IIL^dpen(meso)(DMF)] has a one-dimensional (1D) chain structure, in which the Na⁺ ion is coordinated by two phenoxo and an ethoxy oxygen atoms of a Cu^II complex and an amido oxygen atom of the adjacent Cu^II unit to produce the 1D structure, in which the diphenylethylenediamine moieties have the array of {(1R,2S)-Na-(1S,2R)}_1∞. The assembly reaction of the Cu^II and Gd^III components gave a linear complex with the array of Cu(1)-Gd(1)-Cu(2)-Gd(2), in which two diphenylethylenediamine moieties have the same chirality of (1R,2S)-(1R,2S) or (1S,2R)-(1S,2R). Two linear Cu(1)-Gd(1)-Cu(2)-Gd(2) units are linked by hydrogen bonds through two water molecules to give a cyclic structure with a center of symmetry. The temperature dependence of the magnetic susceptibilities and field-dependent magnetization revealed the ferromagnetic interaction between the Cu^II and Gd^III ions within the linear chain.     

Boronate Covalent and Hybrid Organic Frameworks Featuring PIII and P=O Lewis Base Sites

Two covalent organic frameworks comprising Lewis basic P^III centers and Lewis acidic boron atoms were prepared by poly-condensation reactions of newly obtained tris(4-diisopropoxyborylphenyl)phosphine with 2,3,6,7,10,11-hexahydroxytriphenylene and 2,3,6,7-tetrahydroxy-9,10-dimethylanthracene. Obtained materials exhibit significant sorption of dihydrogen (100 cm³ g⁻¹ at 1 bar at 77 K), methane (20 cm³ g⁻¹ at 1 bar at 273 K) and carbon dioxide (50 cm³ g⁻¹ at 1 bar at 273 K). They were exploited as solid-state ligands for coordination of Pd⁰ centers. Alternatively, in a bottom-up approach, boronated phosphine was treated with Pd₂dba₃ and poly-condensated, yielding hybrid materials where the polymer networks are formed by means of covalent boronate linkages and coordination P−Pd bonds. In addition, the analogous materials based on phosphine oxide were synthesized. The DFT calculations on framework–guest interactions revealed that the behavior of adjacent boron and phosphorus/phosphine oxide centers is reminiscent of that found in Frustrated Lewis Pairs and may improve sorption of selected molecules.     

Lanthanide complexes of the monovacant Dawson polyoxotungstate [α2-As2W17O61] with 1D chain: Synthesis, structures, and photoluminescence properties

Six new lanthanide complexes, (H₃O)[Ln₃(H₂O)₁₇(α₂-As₂W₁₇O₆₁)]·nH₂O ((1) Ln=Ce^III and n≈13; (2) Ln=Pr^III and n≈9; (3) Ln=Nd^III and n≈14; (4) Ln=Sm^III and n≈8; (5) Ln=Eu^III and n≈4; (6) Ln=Gd^III and n≈7), have been isolated by conventional solution method and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. All the complexes are isomorphic and crystallize in the triclinic space group P-1. These complexes are 1D chain-like structures constructed by lanthanide cations and monovacant Dawson-type [α₂-As₂W₁₇O₆₁]¹⁰⁻ polyoxoanions. The striking feature of the structures is that there are three kinds of coordination environments for lanthanide cations, which are responsible for the formation of polymeric structures. Photoluminescence measurements reveal that 4 and 5 exhibit orange and red fluorescent emission at room temperature, respectively.     

pH‐Responsive Relaxometric Behaviour of Coordination Polymer Nanoparticles Made of a Stable Macrocyclic Gadolinium Chelate

Lanthanide‐containing nanoscale particles have been widely explored for various biomedical purposes, however, they are often prone to metal leaching. Here we have created a new coordination polymer (CP) by applying, for the first time, a stable Gd^III chelate as building block in order to prevent any fortuitous release of free lanthanide(III) ion. The use of the Gd‐DOTA‐4AmP complex as a design element in the CP allows not only for enhanced relaxometric properties (maximum r₁=16.4 mm ^?1 s^?1 at 10 MHz), but also for a pH responsiveness (Δr₁=108 % between pH 4 and 6.5), beyond the values obtained for the low molecular weight Gd‐DOTA‐4AmP itself. The CP can be miniaturised to the nanoscale to form colloids that are stable in physiological saline solution and in cell culture media and does not show cytotoxicity.     

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.     

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.     

Self‐Aggregated Dinuclear Lanthanide(III) Complexes as Potential Bimodal Probes for Magnetic Resonance and Optical Imaging

Homodinuclear lanthanide complexes (Ln=La, Eu, Gd, Tb, Yb and Lu) derived from a bis‐macrocyclic ligand featuring two 2,2′,2′′‐(1,4,7,10‐tetraazacyclododecane‐1,4,7‐triyl)triacetic acid chelating sites linked by a 2,6‐bis(pyrazol‐1‐yl)pyridine spacer (H₂L³) were prepared and characterized. Luminescence lifetime measurements recorded on solutions of the Eu^III and Tb^III complexes indicate the presence of one inner‐sphere water molecule coordinated to each metal ion in these complexes. The overall luminescence quantum yields were determined (?=0.01 for [Eu₂(L³)] and 0.50 for [Tb₂(L³)] in 0.01 M TRIS/HCl, pH 7.4; TRIS=tris(hydroxymethyl)aminomethane), pointing to an effective sensitization of the metal ion by the bispyrazolylpyridyl unit of the ligand, especially with Tb. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd₂(L³)] are characteristic of slowly tumbling systems, showing a low‐field plateau and a broad maximum around 30 MHz. This suggests the occurrence of aggregation of the complexes giving rise to slowly rotating species. A similar behavior is observed for the analogous Gd^III complex containing a 4,4′‐dimethyl‐2,2′‐bipyridyl spacer ([Gd₂(L¹)]). The relaxivity of [Gd₂(L³)] recorded at 0.5 T and 298 K (pH 6.9) amounts to 13.7 mM ^?1 s^?1. The formation of aggregates has been confirmed by dynamic light scattering (DLS) experiments, which provided mean particle sizes of 114 and 38 nm for [Gd₂(L¹)] and [Gd₂(L³)], respectively. TEM images of [Gd₂(L³)] indicate the formation of nearly spherical nanosized aggregates with a mean diameter of about 41 nm, together with some nonspherical particles with larger size.     

Variable Luminescence and Chromaticity of Homoleptic Frameworks of the Lanthanides together with Pyridylpyrazolates

Homoleptic, 3D coordination polymers of the formula ³³_∞[Ln(3-PyPz)₃] and ³_∞[Ln(4-PyPz)₃], (3-PyPz)⁻=3-(3-pyridyl)pyrazolate anion, (4-PyPz)⁻=3-(4-pyridyl)pyrazolate anion, both C₈H₆N₃⁻, Ln=Sm, Eu, Gd, Tb, Dy, were obtained as highly luminescent frameworks by reaction of the lanthanide metals (Ln) with the aromatic heterocyclic amine ligands 3-PyPzH and 4-PyPzH. The compounds form two isotypic series of 3D coordination polymers and exhibit fair thermal stability up to 360 °C. The luminescence properties of all ten compounds were determined in the solid state, with an antenna effect through ligand–metal energy transfer leading to high efficiency of the luminescence displayed by good quantum yields of up to 74 %. The emission is mainly based on ion-specific lanthanide-dependent intra 4 f–4 f transitions for Tb³⁺: green, Dy³⁺: yellow, Sm³⁺: orange-red, Eu³⁺: red. For the Gd³⁺-containing compounds, the yellow emission of ligand triplet-based phosphorescence is observed at room temperature and 77 K. Co doping of the Gd-containing frameworks with Eu³⁺ and Tb³⁺ allow further shifting of the chromaticity towards white light emission.