Sparkle model for the calculation of lanthanide complexes: AM1 parameters for Eu(III), Gd(III), and Tb(III)

Our previously defined Sparkle model (Inorg. Chem. 2004, 43, 2346) has been reparameterized for Eu(III) as well as newly parameterized for Gd(III) and Tb(III). The parameterizations have been carried out in a much more extensive manner, aimed at producing a new, more accurate model called Sparkle/AM1, mainly for the vast majority of all Eu(III), Gd(III), and Tb(III) complexes, which possess oxygen or nitrogen as coordinating atoms. All such complexes, which comprise 80% of all geometries present in the Cambridge Structural Database for each of the three ions, were classified into seven groups. These were regarded as a "basis" of chemical ambiance around a lanthanide, which could span the various types of ligand environments the lanthanide ion could be subjected to in any arbitrary complex where the lanthanide ion is coordinated to nitrogen or oxygen atoms. From these seven groups, 15 complexes were selected, which were defined as the parameterization set and then were used with a numerical multidimensional nonlinear optimization to find the best parameter set for reproducing chemical properties. The new parameterizations yielded an unsigned mean error for all interatomic distances between the Eu(III) ion and the ligand atoms of the first sphere of coordination (for the 96 complexes considered in the present paper) of 0.09 A, an improvement over the value of 0.28 A for the previous model and the value of 0.68 A for the first model (Chem. Phys. Lett. 1994, 227, 349). Similar accuracies have been achieved for Gd(III) (0.07 A, 70 complexes) and Tb(III) (0.07 A, 42 complexes). Qualitative improvements have been obtained as well; nitrates now coordinate correctly as bidentate ligands. The results, therefore, indicate that Eu(III), Gd(III), and Tb(III) Sparkle/AM1 calculations possess geometry prediction accuracies for lanthanide complexes with oxygen or nitrogen atoms in the coordination polyhedron that are competitive with present day ab initio/effective core potential calculations, while being hundreds of times faster.     

Synthesis and luminescence properties of new red-shifted absorption lanthanide(III) chelates suitable for peptide and protein labelling

The synthesis and photo-physical properties of an original bis-pyridinylpyrazine chromophore efficiently sensitising europium(III) and samarium(III) are described. The corresponding lanthanide(III) complexes display in aqueous solutions a maximum excitation wavelength which is significantly red-shifted compared to the usual terpyridine-based chelates, and a valuable luminescence brightness above 2,000 dm(3) mol(-1) cm(-1) at 345 nm was obtained with a europium(III) derivative. Further functionalisation with three different bioconjugatable handles was also investigated and their ability to efficiently label a model hexapeptide was evaluated and compared. Finally, the best bioconjugatable europium(III) chelate was used in representative labelling experiments involving monoclonal antibodies and the luminescence features of the corresponding bioconjugates remained satisfactory.     

Luminescent lanthanide complexes with liquid crystalline properties

Lewis-base adducts of tris(β -diketonato)lanthanide(III) complexes were prepared, where the β -diketone is para -alkoxy-substituted 1,3-diphenyl-1,3-propanedione. These compounds are the first examples of liquid crystalline lanthanide complexes in which the mesomorphism is introduced via a β -diketonate ligand. Depending on the type of the Lewis base, the metallomesogens exhibit a monotropic smectic A or a monotropic highly ordered smectic phase. Intense photoluminescence was observed for the europium(III) complexes at room temperature.     

Luminescent lanthanide complexes with liquid crystalline properties

Lewis-base adducts of tris( β-diketonato)lanthanide(III) complexes were prepared, where the β-diketone is para -alkoxy-substituted 1,3-diphenyl-1,3-propanedione. These compounds are the first examples of liquid crystalline lanthanide complexes in which the mesomorphism is introduced via a β-diketonate ligand. Depending on the type of the Lewis base, the metallomesogens exhibit a monotropic smectic A or a monotropic highly ordered smectic phase. Intense photoluminescence was observed for the europium(III) complexes at room temperature.     

Photo and electroluminescence of lanthanide(III) complexes

Major classes of coordination compounds used as electroluminescent materials are surveyed, and their advantages and disadvantages are discussed. The strategy of the directed synthesis of lanthanide(III) complexes promising for use as electroluminescent materials is formulated. The results of studies dealing with the design of electroluminescent devices based on europium(III), terbium(III), and thulium(III) complexes are considered.     

Solution studies of trimetallic lanthanide luminescent anion sensors: towards ratiometric sensing using an internal reference channel

Luminescent europium and terbium complexes and a mixed Eu(III)-Tb(III) complex were prepared, each with three macrocycles coordinating to a single lanthanide ion to form a trimetallic system, and can be used for the ratiometric sensing of anions in the case of the mixed complex.     

Synthesis and characterization of lanthanide complexes of DO3A-alkylphosphonates

Eight DO3A-based lanthanide(III) complexes bearing ester protected and unprotected phosphonate groups at variable distances from the macrocyclic moiety have been synthesized and analyzed. The ligands were made by straightforward four-step synthetic procedures and purified with preparative RP-HPLC, after which they were used to prepare gadolinium(III) and europium(III) complexes. Relaxometric experiments were performed on the Gd(III) complexes at 300 MHz, varying the pH of the solutions or the concentration of human serum albumin (HSA). It was found that when the pH of the medium was changed from neutral to pH 4 the longitudinal relaxivity of GdDO3A-ethylphosphonate and GdDO3A-propylphosphonate complexes increased by 50% and 60%, respectively. Diethyl esters of these complexes did not change longitudinal relaxivity in the same pH range but their transverse relaxivity increased upon binding to HSA. 31P NMR experiments on Eu(III) complexes showed a change in the chemical shift of both acid complexes in the same region where the highest relaxivity changes were observed and proved the stability of the complexes in the investigated pH range, while no shift was observed for the diester complexes. Luminescence studies on europium(III) complexes additionally supported observations obtained by NMR methods. The change in the form of the luminescence emission spectra, and the reduction in the q value upon addition of HSA proved the ternary adduct formation between the charge neutral diester complexes and HSA. Similarly, the change in the emission spectra showing a phosphonate bound structure at pH 7 to a species where the phosphonate oxygen is not coordinated at pH 4 in parallel with the increase of q value is supporting the hypothesis that the deprotonation of phosphonates is the main reason for the distinct relaxivity change from slightly acidic to the neutral solution media.     

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.     

On the calculation of electric dipole strengths of 4f→4f transitions in lanthanide complexes

Electric dipole strengths calculated with the combined static coupling (SC)/dynamic coupling (DC) intensity model for 4f → 4f transitions in lanthanide complexes contain SC/DC cross-term (“interference”) contributions which may add to or subtract front the purely static and dynamic contributions. Calculations for europium (III) complexes show that cross- terms cannot be neglected in characterizing 4f→4f intensities.     

AM1 Sparkle modeling of Er(III) and Ce(III) coordination compounds

The recently defined Sparkle/AM1 model is now extended to Er(III) and Ce(III), using the same parameterization scheme. Thus, a set of fifteen complexes for each lanthanide ion, with various representative ligands of high crystallographic quality (R factor < 0.05 Å), and which possess oxygen and/or nitrogen as coordinating atoms, was used as the training set. In the validation procedure we used a set of twenty-two more complex structures for the Ce(III) ion and twenty-four more for the Er(III) ion, all of high crystallographic quality. For the thirty-seven cerium(III) complexes and thirty-nine erbium(III) complexes considered, the Sparkle/AM1 unsigned mean error, for all interatomic distances between the Ln(III) ion and the ligand atoms of the first sphere of coordination, is 0.08 and 0.06 Å, a level of accuracy comparable to present day ab initio/ECP geometries, while being hundreds of times faster. The Sparkle/AM1 model may thus prove useful for luminescent complex design.     

Molecular mechanical calculations of the molecular structure of eight-coordinate europium complexes

Molecular mechanics methods were applied to the determination of the structure of eight-coordinate europium complexes: tris(acetylacetonato)Eu(III) trihydrate, tris(acetylacetonato) (1,10-phenanthroline)Eu(III), and tetrakis(benzoylacetonato)Eu(III). Optimization of MM2 force-field parameters and improvement of the calculation method were carried out using models of the complexes based on X-ray structural investigations. Steric ligandligand interactions in the first coordination sphere were treated as dominant for the lanthanide complexes. The major contributions to the energy are those of nonbonded 1,3-interactions between the atoms directly bound to the europium atom. The results of the calculations agree well with the crystal structures of the mentioned complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1555–1559, September, 1993.     

Synthesis and characterisation of bis-cyclen based dinuclear lanthanide complexes

The design and synthesis of several bis-macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) ligands and their corresponding lanthanum or europium complexes is described; these dinuclear lanthanide systems were made by connecting two macrocyclic cyclen moieties through a rigid, covalent, p-xylylenediamide bridge or a flexible aliphatic hexane bridge. These ligands were subsequently functionalised with six acetamide pendant arms (CONR1R2: R1 = R2 = H or CH3, or R1 = H, R2 = CH3). The corresponding lanthanide bis-complexes were then formed by reaction with La(III) and Eu(III) triflates, yielding overall cationic (+VI charged) complexes.     

Rare-Earth complexes of ferrocene-containing ligands: visible-light excitable luminescent materials

The ferrocene-derivatives bis(ferrocenyl-ethynyl)-1,10-phenanthroline (Fc(2)phen) and ferrocenoyltrifluoroacetone (Hfta) have been used to synthesize ferrocene-containing rare-earth beta-diketonate complexes. The complexes [Ln(tta)(3)(Fc(2)phen)] and [Ln(fta)(3)(phen)] (where Ln = La, Nd, Eu, Yb) show structural similarities to the tris(2-thenoyltrifluoroacetonate)(1,10-phenanthroline)lanthanide(III) complexes, [Ln(tta)(3)(phen)]. The coordination number of the lanthanide ion is 8, and the coordination sphere can be described as a distorted dodecahedron. However, the presence of the ferrocene moieties shifts the ligand absorption bands of the rare-earth complexes to longer wavelengths so that the complexes can be excited not only by ultraviolet radiation but also by visible light of wavelengths up to 420 nm. Red photoluminescence is observed for the europium(III) complexes and near-infrared photoluminescence for the neodymium(III) and ytterbium(III) complexes. The presence of the ferrocene groups makes the rare-earth complexes hydrophobic and well-soluble in apolar organic solvents.     

Listening to Lanthanide Complexes: Determination of the Intrinsic Luminescence Quantum Yield by Nonradiative Relaxation

The photophysical properties of lanthanide complexes have been studied extensively; however, fundamental parameters such as the intrinsic quantum yield as well as radiative and nonradiative decay rates are difficult or even impossible to measure experimentally. Herein, a photoacoustic (PA) method is proposed to determine the intrinsic quantum yield of lanthanide complexes with lifetimes in the order of milliseconds. This method is used to determine the intrinsic quantum yields for europium(III)‐containing metallomesogens as well as terbium(III) complexes. The results show that the PA signal is sensitive to both the lifetime and the ratio of the fast‐to‐slow heat component of the samples. It is found that there is an efficient ligand sensitization and a moderate intrinsic quantum yield for the complexes. The intrinsic quantum yield of Eu³⁺ in the metallomesogens exhibits an obvious increase upon the isotropic liquid to smectic A transition. The proposed PA method is quite simple, and can contribute to a clearer understanding of the photophysical processes in luminescent lanthanide complexes.     

Synthesis and spectroscopic properties of lanthanide nitrate complexes with a new amide-based quinoxaline-2,3-dione ligand

Solid complexes of lanthanide nitrate with 1,4-di(N,N-di-n-butyl-acetamido)-quinoxaline-2,3-dione (L), [Ln(N03)3L.H2O] (Ln=La, Nd, Eu, Gd, Tb, Er), have been prepared and characterized by elemental analysis, IR, UV-vis spectra and conductivity measurements. The fluorescence property of the europium complex in solid state and in MeCN, acetone, AcOEt and THF was studied. Under the excitation, the europium complex exhibited characteristic emissions of europium. The result indicates that the triplet state energy level of the ligand matches better to the resonance level of Eu(III) than Tb(III) ion.     

Structure and emission spectra of dinuclear lanthanide(III) β-diketonate complexes with a bridging 2,2′-bipyrimidine ligand

The 2,2′-bipyrimidine (bpm) adducts of the β-diketonate complexes of Eu(III), Sm(III), or Yb(III) with 2,2′,6,6′-tetramethyl-2,4-heptanedione (tmhd) resulted in the formation of dinuclear species. The synthesis and X-ray structure of these three new dinuclear lanthanide complexes are found to be similar. Each lanthanide ion is eight coordinate, bound to six O-atoms from the β-diketonates and 2N atoms from the bridging bpm ligand. They exhibit Ln–Ln distances (Sm(III): 6.935 Å, Eu(III): 6.901 Å, Yb(III): 6.679 Å) and Ln–ligand distances that are consistent with the decrease in radii across the lanthanide series. Absorption spectra of the complexes are dominated by ligand absorptions. Both the solution and solid state emission spectra of the complexes resemble ordinary monomeric lanthanide species, indicating independent ions in the dinuclear species. Cyclic voltammetry of all the complexes appear almost identical with discernable ligand centered redox reactions. The complex with Eu(III) ions, having the lowest possible lanthanide redox potential, was not found to display a signal corresponding to metal reduction.     

Effect of Aliphatic Chain Length in the Ligand on Photophysical Properties and Thin Films Morphology of the Europium Complexes

Chelating ligands based on polydentate diamides of 2,2'-bipyridyl-6,6'-dicarboxylic acid with a high affinity for lanthanide ions have been synthesized. The effect of the size of lipophilic aliphatic substituents in the ligand on the photophysical characteristics of europium complexes in acetonitrile solutions and in the solid state, as well as on the morphology of thin films obtained by the spin-coating method, was studied. The external and internal luminescence quantum yields have been measured, the luminescence lifetimes at 300 and 77 K were determined, and the sensitization efficiency values for europium complexes were calculated. The phosphorescence of gadolinium(III) complexes was used to determine the energy difference between the triplet level of the ligand and the resonance level of europium.     

Towards a force field based on density fitting

Total intermolecular interaction energies are determined with a first version of the Gaussian electrostatic model (GEM-0), a force field based on a density fitting approach using s-type Gaussian functions. The total interaction energy is computed in the spirit of the sum of interacting fragment ab initio (SIBFA) force field by separately evaluating each one of its components: electrostatic (Coulomb), exchange repulsion, polarization, and charge transfer intermolecular interaction energies, in order to reproduce reference constrained space orbital variation (CSOV) energy decomposition calculations at the B3LYP/aug-cc-pVTZ level. The use of an auxiliary basis set restricted to spherical Gaussian functions facilitates the rotation of the fitted densities of rigid fragments and enables a fast and accurate density fitting evaluation of Coulomb and exchange-repulsion energy, the latter using the overlap model introduced by Wheatley and Price [Mol. Phys. 69, 50718 (1990)]. The SIBFA energy scheme for polarization and charge transfer has been implemented using the electric fields and electrostatic potentials generated by the fitted densities. GEM-0 has been tested on ten stationary points of the water dimer potential energy surface and on three water clusters (n = 16,20,64). The results show very good agreement with density functional theory calculations, reproducing the individual CSOV energy contributions for a given interaction as well as the B3LYP total interaction energies with errors below kBT at room temperature. Preliminary results for Coulomb and exchange-repulsion energies of metal cation complexes and coupled cluster singles doubles electron densities are discussed.     

Identification of emissive lanthanide complexes suitable for cellular imaging that resist quenching by endogenous anti-oxidants

Excited state quenching by urate and ascorbate of selected europium and terbium(III) macrocyclic complexes has been assessed and related to the ease of complex visualisation by optical microscopy inside various living cells, e.g. CHO, COS and NIH 3T3. It is the relative insensitivity of certain sterically encumbered complexes to dynamic quenching by urate that favours their usage for in cellulo applications. Non-covalent binding of the complex by protein also shields the excited lanthanide(III) ion from collisional quenching; this effect is most marked for a cationic triamide complex, [Ln.1](3+), consistent with its ease of visualisation by luminescence microscopy.