Highly luminescent bis-diketone lanthanide complexes with triple-stranded dinuclear structure

A new bis-β-diketone, 3,3'-bis(4,4,4-trifluoro-1,3-dioxobutyl)biphenyl (BTB), has been designed and prepared for the synthesis of a series of dinuclear lanthanide complexes [Ln(2)(BTB)(3)(C(2)H(5)OH)(2)(H(2)O)(2)] [Ln = Eu (1), Gd (2)], [Ln(2)(BTB)(3)(DME)(2)] [Ln = Nd (3), Yb (4); DME = ethylene glycol dimethyl ether] and [Eu(2)(BTB)(3)(L)(2)] [L = 2,2-bipydine (5); 1,10-phenanthroline (6); 4,7-diphenyl-1,10-phenanthroline (7)]. Complexes 1-7 have been characterized by various spectroscopic techniques and their photophysical properties are investigated. X-ray crystallographical analysis reveals that complexes 1, 3 and 4 adopt triple-stranded dinuclear structures which are formed by three bis-bidentate ligands with two lanthanide ions. The complexes 1 and 3-7 display strong visible red or NIR luminescence upon irradiation at ligand band around 372 nm, depending on the choice of the lanthanide. The solid-state photoluminescence quantum yields and the lifetimes of Eu(3+) complexes are determined and described.     

Controlled assembly of luminescent racks based on heteroleptic dinuclear lanthanide complexes

Luminescent lanthanide racks are formed in solution through supramolecular assembly of lanthanide ions with a rigid bis-didentate sensitiser ligand and octadentate aminopolycarboxylate ligands.     

Slow magnetic relaxation in carbonato-bridged dinuclear lanthanide(III) complexes with 2,3-quinoxalinediolate ligands

The coordination chemistry of the 2,3-quinoxalinediolate ligand with different lanthanide(III) ions in basic media in air affords a new family of carbonato-bridged M(2)(III) compounds (M = Pr, Gd and Dy), the Dy(2)(III) analogue exhibiting slow magnetic relaxation behaviour typical of single-molecule magnets.     

Lanthanide directed self-assembly formations of Tb(III) and Eu(III) luminescent complexes from tryptophan based pyridyl amide ligands

The formation of self-assembly complexes between the ligands 1 (SS) and 2 (RR) and terbium or europium was undertaken and shown (using various spectroscopic titrations) to give rise to the exclusive formation of 2:1 (L:Ln) stoichiometry and not the anticipated 3:1 stoichiometry.     

Synthesis and luminescent properties of novel lanthanide(III) beta-diketone complexes with nitrogen p,p'-disubstituted aromatic ligands

Tris-beta-diketonate lanthanide(III) complexes (Ln = Eu, Er, Yb, Tb), of general formula [Ln(acac)3 L(m)], with chelating ligands such as 4,7-disubstituted-1,10-phenanthrolines and 4,4'-disubstituted-2,2'-bipyridines, have been synthesized and fully characterized. The inductive effects of the para-substituents on the aromatic N-donor ligands have been investigated both in the solid and in the solution states. Single-crystal X-ray structures have been determined for the diethyl 1,10-phenanthroline-4,7-dicarboxylate europium and 4,4'-dimethoxy-2,2'-bipyridine erbium derivatives, revealing a distorted square antiprismatic geometry around the lanthanide atom in both cases. The influence exerted by the p,p'-substituents with respect to the nitrogen coordinating atoms on the Ln-N bond distances is discussed comparing the geometrical parameters with those found for the crystal structures containing the fragments [Ln(III)(phen)] and [Ln(III)(bipy)] obtained from the Cambridge Structural Database. The influence exerted by the electron-attracting groups on the coordination ability of the ligands, that in some cases becomes lack of coordination of the lanthanide ions, has been also detected in solution where the loss of the ligand has been followed by UV-vis spectroscopy. Moreover, the use of relatively long alkoxy chains as substituents on the 1,10-phenanthroline ligand led to the formation of a promesogenic lanthanide complex, whose thermal behavior is encouraging for the synthesis of new lanthanide liquid-crystalline species.     

Selective reaction based on the linked diamido ligands of dinuclear lanthanide complexes

The dinuclear ytterbium pyridyl diamido complexes [Cp(2)Yb(THF)](2)[mu-eta(1):eta(2)-(NH)(2)(C(5)H(3)N-2,6)] (1a) and [Cp(2)Yb(THF)](2)[mu-eta(1):eta(2)-(NH)(2)(C(5)H(3)N-2,3)] (1b) are easily prepared by protonolysis of Cp(3)Yb with 0.5 equiv of the corresponding diaminopyridine in accepted yields, respectively. Treatment of 1a with 2 equiv of dicyclohexylcarbodiimide (CyN=C=NCy) in THF at low temperature leads to the isolation of the formal double N-H addition product (Cp(2)Yb)(2)[mu-eta(2):eta(2)-(CyN(CyNH)CN)(2)(C(5)H(3)N-2,6)] (2) in 42% yield. Compound 2 is unstable to heat and slowly isomerized to the mixed neutral/dianionic diguanidinate complex (Cp(2)Yb)(2)[mu-eta(2):eta(2)-(CyNH)(2)CN(C(5)H(3)N-2,6)NC(NCy)(2)](THF) (3) at room temperature. Similarly, treatment of 1b with 2 equiv of CyN=C=NCy gives the addition/ isomerization product (Cp(2)Yb)(2)[mu-eta(2):eta(2):eta(1)-(CyNH)(2)CN(C(5)H(3)N-2,3)NC(NCy)(2)] (4). Moreover, the reaction of various ytterbium aryl diamido complexes (prepared in situ from [Cp(2)YbMe](2) and aryldiamine, respectively) with CyN=C=NCy affords the corresponding addition products (Cp(2)Yb)(2)[mu-eta(2):eta(2)-{CyN(CyNH)CN}(2)(C(6)H(4)-1,4)] (5), (Cp(2)Yb)(2)[mu-eta(2):eta(2)-{CyN(CyNH)CN}(2)(C(6)H(4)-1,3)](6), and (Cp(2)Yb)(2)[mu-eta(2):eta(2)-{CyN(CyNH)CN}(2)(C(13)H(8)-2,7)] (7), respectively. In contrast to pyridyl-bridged bis(guanidinate monoanion) complexes, aryl-bridged bis(guanidinate monoanion) complexes 5-7 are stable even with prolonged heating at 110 degrees C. All the results not only demonstrate that the presence of the pyridyl bridge can impart the diamido complexes with a unique reactivity and initiate the unexpected reaction sequence but also indicate evidently that the number and distribution of negative charges of the diguanidinate ligand is tunable from double monoanionic units to mixed neutral/dianionic isomers. All the complexes are characterized by elemental analysis and IR spectroscopies. The structures of complexes 1a, 3, 5, 6, and 7 are also determined through X-ray single-crystal diffraction analysis.     

Luminescence tuning of imidazole-based lanthanide(III) complexes [Ln = Sm, Eu, Gd, Tb, Dy

To tune the lanthanide luminescence in related molecular structures, we synthesized and characterized a series of lanthanide complexes with imidazole-based ligands: two tripodal ligands, tris{[2-{(1-methylimidazol-2-yl)methylidene}amino]ethyl}amine (Me(3)L), and tris{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(3)L), and the dipodal ligand bis{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(2)L). The general formulas are [Ln(Me(3)L)(H(2)O)(2)](NO(3))(3)·3H(2)O (Ln = 3+ lanthanide ion: Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5)), [Ln(H(3)L)(NO(3))](NO(3))(2)·MeOH (Ln(3+) = Sm (6), Eu (7), Gd (8), Tb (9), and Dy (10)), and [Ln(H(2)L)(NO(3))(2)(MeOH)](NO(3))·MeOH (Ln(3+) = Sm (11), Eu (12), Gd (13), Tb (14), and Dy (15)). Each lanthanide ion is 9-coordinate in the complexes with the Me(3)L and H(3)L ligands and 10-coordinate in the complexes with the H(2)L ligand, in which counter anion and solvent molecules are also coordinated. The complexes show a screw arrangement of ligands around the lanthanide ions, and their enantiomorphs form racemate crystals. Luminescence studies have been carried out on the solid and solution-state samples. The triplet energy levels of Me(3)L, H(3)L, and H(2)L are 21?000, 22?700, and 23?000 cm(-1), respectively, which were determined from the phosphorescence spectra of their Gd(3+) complexes. The Me(3)L ligand is an effective sensitizer for Sm(3+) and Eu(3+) ions. Efficient luminescence of Sm(3+), Eu(3+), Tb(3+), and Dy(3+) ions was observed in complexes with the H(3)L and H(2)L ligands. Ligand modification by changing imidazole groups alters their triplet energy, and results in different sensitizing ability towards lanthanide ions.     

Facile preparation and photophysics of near-infrared luminescent lanthanide(III) monoporphyrinate complexes

The synthesis, characterization, and single crystal X-ray diffraction structures of a series of monoporphyrinate, trivalent lanthanide complexes with the monoanionic ligands hydridotris(1-pyrazolyl)borate (Tp) and (cyclopentadienyl)tris(diethylphosphinito)cobaltate (L(OEt)) having the general formulas M(TPP)(L) (M = Yb, Tm, Er, Ho, Nd, Pr; TPP = 5,10,15,20-tetraphenylporphyrinate; L = Tp, L(OEt)) are described. The photophysical properties of these complexes are also presented including their absorption, emission, and transient absorption properties.     

Memory devices based on lanthanide (Sm3+, Eu3+, Gd3+) complexes

Memory effects in single-layer organic light-emitting devices based on Sm3+, Gd3+, and Eu3+ rare earth complexes were realized. The device structure was indium-tin-oxide (ITO)/3,4-poly(ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT)/Poly(N-vinyl carbazole) (PVK): rare earth complex/LiF/Ca/Ag. It was found experimentally that all the devices exhibited two distinctive bistable conductivity states in current-voltage characteristics by applying negative starting voltage, and more than 10(6) write-read-erase-reread cycles were achieved without degradation. Our results indicate that the rare earth organic complexes are promising materials for high-density, low-cost memory application besides the potential application as organic light-emitting materials in display devices.     

Enhanced luminescent iridium(III) complexes bearing aryltriazole cyclometallated ligands

Herein we report the synthesis of 4-aryl-1-benzyl-1H-1,2,3-triazoles (atl), made via "Click chemistry" and their incorporation as cyclometallating ligands into new heteroleptic iridium(III) complexes containing diimine (N(^)N) ancillary ligands 2,2'-bipyridine (bpy) and 4,4'-di-tert-butyl-2,2'-bipyridine (dtBubpy). Depending on decoration, these complexes emit from the yellow to sky blue in acetonitrile (ACN) solution at room temperature (RT). Their emission energies are slightly blue-shifted and their photoluminescent quantum efficiencies are markedly higher (between 25 and 80%) than analogous (C(^)N)(2)Ir(N(^)N)(+) type complexes, where C(^)N is a decorated 2-phenylpyridinato ligand. This increased brilliance is in part due to the presence of the benzyl groups, which act to sterically shield the iridium metal center. X-ray crystallographic analyses of two of the atl complexes corroborate this assertion. Their electrochemistry is reversible, thus making these complexes amenable for inclusion in light-emitting electrochemical cells (LEECs). A parallel computational investigation supports the experimental findings and demonstrates that for all complexes included in this study, the highest occupied molecular orbital (HOMO) is located on both the aryl fragment of the atl ligands and the iridium metal while the lowest unoccupied molecular orbital (LUMO) is located essentially exclusively on the ancillary ligand.     

Two mono- and dinuclear Eu(iii) enantiomeric pairs based on chiral bis-bidentate bridging ligands: synthesis, structures, luminescent and ferroelectric properties

Using the enantiomeric bis-bidentate bridging ligands (+)/(-)-2,5-bis(4,5-pinene-2-pyridyl)pyrazine (L(S)/L(R)) and depending on the ratio control of reactants, two mono- and dinuclear Eu(iii)-based enantiomeric pairs with the formulae Eu(dbm)(3)L(R/S)·2H(2)O (L(R) in R-1, L(S) in S-1 and dbm = dibenzoylmethanato) and Eu(2)(dbm)(6)L(R/S)·H(2)O (L(R) in R-2 and L(S) in S-2) have been stereoselectively synthesized and structurally characterized. The circular dichroic (CD) spectra confirmed their chiroptical activities and enantiomeric natures. The homochiral dinuclear species represents the first example of a polynuclear lanthanide β-diketonate complexes with circular dichroic and crystallographic evidences. The photoluminescent properties studies revealed that both mono- and dinuclear Eu(iii) complexes exhibited the characteristic red emissions of Eu(iii) ions in the solid state (at 77 K and 300 K) and CH(2)Cl(2) solution. Notably, the photophysical properties of the mononuclear enantiomers were superior to the dinuclear species. Interestingly, R-2 displayed a ferroelectric property at room temperature, which was not observed for R-1 due to the lack of crystalline polarity. R/S-2 are the first examples of homochiral polynuclear lanthanide complexes with luminescence and ferroelectric properties, being potential multifunctional materials.     

Novel dinuclear luminescent compounds based on iridium(III) cyclometalated chromophores and containing bridging ligands with ester-linked chelating sites

The syntheses and study of the spectroscopic, redox, and photophysical properties of a new set of species based on Ir(III) cyclometalated building blocks are reported. This set includes three dinuclear complexes, that is, the symmetric (with respect to the bridging ligand) diiridium species [(ppy)(2)Ir(mu-L-OC(O)-C(O)O-L)Ir(ppy)(2)][PF(6)](2) (5; ppy = 2-phenylpyridine anion; L-OC(O)-C(O)O-L = bis[4-(6'-phenyl-2,2'-bipyridine-4'-yl)phenyl]-benzene-1,4-dicarboxylate), the asymmetric diiridium species [(ppy)(2)Ir(mu-L-OC(O)-L)Ir(ppy)(2)][PF(6)](2) (3; L-OC(O)-L = 4-([(6'-phenyl-2,2'-bipyridine-4'-yl)benzoyloxy]phenyl)-6'-phenyl-2,2'-bipyridine), and the mixed-metal Ir-Re species [(ppy)(2)Ir(mu-L-OC(O)-L)Re(CO)(3)Br][PF(6)] (4). Syntheses, characterization, and spectroscopic, photophysical, and redox properties of the model mononuclear compounds [Ir(ppy)(2)(L-OC(O)-L)][PF(6)] (2) and [Re(CO)(3)(L-COOH)Br] (6; L-COOH = 4'-(4-carboxyphenyl)-6'-phenyl-2,2'-bipyridine) are also reported, together with the syntheses of the new bridging ligands L-OC(O)-L and L-OC(O)-C(O)O-L. The absorption spectra of all the complexes are dominated by intense spin-allowed ligand-centered (LC) bands and by moderately intense spin-allowed metal-to-ligand charge-transfer (MLCT) bands. Spin-forbidden MLCT absorption bands are also visible as low-energy tails at around 470 nm for all the complexes. All the new species exhibit metal-based irreversible oxidation and bipyridine-based reversible reduction processes in the potential window investigated (between +1.80 and -1.70 V vs SCE). The redox behavior indicates that the metal-based orbitals are only weakly interacting in dinuclear systems, whereas the two chelating halves of the bridging ligands exhibit noticeable electronic interactions. All the complexes are luminescent both at 77 K and at room temperature, with emission originating from triplet MLCT states. The luminescence properties are temperature- and solvent-dependent, in accord with general theories: emission lifetimes and quantum yields increase on passing from acetonitrile to dichloromethane fluid solution and from room-temperature fluid solution to 77 K rigid matrix. In the dinuclear mixed-chromophore species 3 and 4, photoinduced energy transfer across the ester-linked bridging ligands seems to occur with low efficiency.     

Synthesis of stable monoporphyrinate lanthanide(III) complexes without ancillary ligands

A new type of porphyrin ligand bearing four triazole groups at the ortho-positions of phenyl rings in tetraphenylporphyrin was synthesized for the formation of monoporphyrinate lanthanide complexes without ancillary ligands.     

Synthesis and magnetism of μ-isophthalato dinuclear lanthanide(III) complexes

Seven new μ-isophthalato dinuclear lanthanide(III) complexes, namely [Ln₂(IPHTA)(Me₂-phen)₄-(ClO₄)₂](ClO₄)₂ (Ln=La, Nd, Sm, Eu, Gd, Ho, Er), where Me₂-phen denotes 2,9-dimethyl-1,10-phenanthroline (Me₂-phen), IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [ Gd₂ (IPHTA) (Me₂-phen)₄ ( ClO₄ )₂ ] ((ClO₄ )₂ complex were measured in the temperature range of 4–300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = -2JS₁. J₂. giving the exchange parameter J = -0.19 cm^?1. This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(III)-Gd(III) im within the complex.     

Efficient electroluminescence from new lanthanide (Eu3+, Sm3+) complexes

The syntheses, structures, and electroluminescent properties are described for two new lanthanide complexes Ln(HFNH)3phen [HFNH = 4,4,5,5,6,6,6-heptafluoro-1-(2-naphthyl)hexane-1,3-dione; phen = 1,10-phenanthroline; Ln = Eu3+ (1), Sm3+ (2)]. Both complexes exhibit bright photoluminescence at room temperature (RT) due to the characteristic emission of Eu3+ and Sm3+ ion. Several devices using the two complexes as emitters were fabricated. The performances of these devices are among the best reported for devices using europium complex and samarium complex as emitters. The device based on 1 with the structure ITO/TPD (50 nm)/1:CBP (10%, 40 nm)/BCP (20 nm)/AlQ (30 nm)/LiF (1 nm)/Al (200 nm) exhibits the maximum brightness of 957 cd/m2, current efficiency of 4.14 cd/A, and power efficiency of 2.28 lm/W with a pure red Eu3+ ion emission. Especially, at the high brightness of 200 cd/m2, the device of 1 still has a high current efficiency of 2.15 cd/A. The device of 2 with a three-layer structure of ITO/TPD (50 nm)/2 (50 nm)/BCP (20 nm)/LiF (1 nm)/Al (200 nm) gives the maximum brightness of 42 cd/m2, current efficiency of 0.18 cd/A. By the comparison of the electroluminescent properties of devices based on Eu(TTA3phen (TTA = 2-thenoyltrifluoroacteonate) and 1, we conclude that the polyfluoration on the alkyl group of the ligand and the introduction of the long conjugate naphthyl group into the ligand improve the efficiency of 1-doped devices, especially at high current densities.     

Synthesis and luminescence studies of mono- and C3-symmetric, tris(ligand) complexes of Sm(III), Y(III) and Eu(III) with sulfur-bridged binaphtholate ligands

A series of trivalent mono- and tris(ligand) lanthanide complexes of a sulfur-bridged binaphthol ligand [1,1'-S(2-HOC(10)H(4)Bu(t)(2)-3,6)(2)] H(2)L(SN), have been prepared and characterised both structurally and photophysically. The H(2)L(SN) ligand provides an increased steric bulk and offers an additional donor atom (sulfur) as compared with 1,1'-binaphthol (BINOL), a ligand commonly used to complex Lewis acidic lanthanide catalysts. Reaction of the diol H(2)L(SN) with [Sm[N(SiMe(3))(2)](3)] affords silylamido- and amino- derivatives [Sm(L(SN))[N(SiMe(3))(2)][HN(SiMe(3))(2)]] and the crystallographically characterised [Sm(L(SN))[N(SiMe(3))(2)](thf)(2)] with different degrees of structural rigidity, depending on the presence of coordinating solvents. The binaphthyl groups of the L(SN) ligand act as sensitisers of the metal centred emission, which is observed for the Eu(III) and Sm(III) complexes studied. We have therefore sought to use emission spectroscopy as a non-invasive technique to monitor a monomer-dimer equilibrium in these complexes. A dramatic difference between the emission properties of the unreactive dimeric Sm(III) aryloxide complex, the solvated monomeric analogues and the amido adduct demonstrated the potential use of such a technique. For a few representative lanthanides (Ln = Sm, Eu and Y) the reaction of the dilithium salt Li(2)L(SN) with either [Ln[N(SiMe(3))(2]3)] or [LnCl(3)(thf)(3)] affords only the homoleptic complex [Li(S)(3)][LnL(SN)(3)](S = thf or diethyl ether); we report the structural characterisation of the Sm complex. However, the reactions of this dipotassium salt K(2)L(SN) with [Sm[N(SiMe(3))(2)](3)] or [SmCl(3)(thf)(3)] give only [SmL(SN)N(SiMe(3))(2)], or intractable mixtures respectively, in which no (tris)binaphtholate is observed. The only isolable lanthanide-L(SN) halide adduct so far is [YbL(SN)I(thf)].     

Self-assembly of luminescent ternary complexes between seven-coordinate lanthanide(III) complexes and chromophore bearing carboxylates and phosphonates

Luminescent lanthanide complexes have been prepared by exploiting the interaction between lanthanide DO3A complexes and chromophore bearing carboxylates or phosphonates. This interaction can be utilised to probe the choice of sensitising chromophore suited to a given lanthanide. Furthermore, ternary complexes obtained from chromophore appended carboxylates dissociate in the presence of phosphate, while those obtained from phosphonates do not.     

Multinuclear NIR luminescent 1,4-BDC bridged Schiff-base complexes of Nd(III)

Solvent and reaction stoichiometry dictate the products isolated from reactions of the dinuclear precursor complex [ZnNdL(H₂O)(NO₃)₃] (H₂L = N,N′-bis(3-methoxy-salicylidene)ethylene-1,2-diamine) with the anionic multidentate linker 1,4-benzenedicarboxylate (1,4-BDC). With a 2:1 molar ratio of ZnNd:Na₂1,4-BDC in CH₃CN–EtOH the tetranuclear complex [Zn₂Nd₂L₂(1,4-BDC)(NO₃)₄(EtOH)₂] · 2MeCN (1) is produced while hexanuclear [Zn₄Nd₂L₄(1,4-BDC)₂] · (NO₃)₂ · 2Et₂O · 4H₂O (2) can be isolated from a DMF–EtOH mixture. A 4:1 mole ratio in DMF–EtOH gave the unusual polynuclear complex [Zn₄Nd₂L₄(1,4-BDC)₂] · [ZnNdL(NO₃)₃(OAc)]₂ (3). The NIR photophysical properties of the new compounds are reported.     

Synthesis, characterization and DNA-binding studies of 2-carboxybenzaldehydeisonicotinoylhydrazone and its La(III), Sm(III) and Eu(III) complexes

2-Carboxybenzaldehydeisonicotinoylhydrazone (HL), and its three lanthanide complexes, LnL(3).4H2O [Ln=La(1), Sm(2), Eu(3)], have been synthesized and characterized on the basis of elemental analyses, molar conductivities, IR spectra and thermal analyses. In addition, the DNA-binding properties of the ligand and its complexes have been investigated by absorption, fluorescence and viscosity measurements. The experimental results indicated that the complexes (2) and (3) can bind to DNA, but the ligand and the complex (1) cannot; the binding affinity of the complex (3) is higher than that of the complex (2) and the intrinsic binding constant Kb of the complex (3) is 7.86x10(4) M-1.