Preparation, characterization, and circularly polarized luminescence of lanthanum and europium 1,1'-binaphthyl-2,2'-diyl phosphate complexes.

Solvated tris-complexes of (R)- and (S)-1,1'-binaphthyl-2,2'-dyil phosphate with lanthanum(III) and europium(III) centers were prepared and characterized by spectroscopic methods and elemental analysis. Circularly polarized luminescence (CPL) spectra for the optically active isomers of the europium complexes are also reported.

Emission detected circular dichroism from long-lived excited states: application to chiral Eu(III) systems.

The measurement of the difference in intensity of luminescence following excitation with left and right circularly polarized light for racemic terdentate Eu(III) complexes with 2,6-pyridine dicarboxylic acids perturbed by the addition of (+)-dimethyltartrate and for tris chiral complexes of Eu(III) with (R,R)-N,N'-bis(1-phenylethyl)-2,6-pyridine-dicarboxamide are presented. The experimental technique used for these measurements is identical in design to fluorescence detected circular dichroism spectroscopy, but is referred to in this manuscript as emission detected circular dichroism (EDCD) because of the long lifetime of the Eu(III) excited state requiring specialized instrumentation. These measurements required relatively slow modulation of the incident circular polarization, which was accomplished with a liquid crystal polarizer. The results are compared with conventional CD measurements, and additional characteristics and potential applications of EDCD are presented.

Brilliant Sm, Eu, Tb, and Dy chiral lanthanide complexes with strong circularly polarized luminescence.

The synthesis, characterization, and luminescent behavior of trivalent Sm, Eu, Dy, and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, g(lum), recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments.

Use of induced circularly polarized luminescence (CPL) from racemic D(3) lanthanide complexes to determine the absolute configuration of amino acids.

The perturbation of the racemic equilibrium of luminescent D(3) lanthanide(III) complexes by added chiral agents, such as amino acids, may be a useful technique for determining the absolute configuration of the added species. It is shown in this work, however, that simple interpretation of the equilibrium shift of racemic tris-terdentate complexes of Tb(III) with 2,6-pyridine-dicarboxylate by amino acids, as measured by the sign of the resultant circularly polarized luminescence (CPL) in terms of specific structural characteristics is not possible. CPL results for a number of derivatized amino acids are also presented, and some insights into the nature of the chiral discriminatory forces that might be exploited in this kind of study are discussed.

The measurement of the fluorescence detected circular dichroism (FDCD) from a chiral Eu(III) system.

The first measurement of the fluorescence detected circular dichroism (FDCD) from a chiral Eu(III) system, made possible by use of a variable liquid crystal circular polarizer, is reported.

Lanthanide spectroscopic studies of the dinuclear and Mg(II)-dependent PvuII restriction endonuclease.

Type II restriction enzymes are homodimeric systems that bind four to eight base pair palindromic recognition sequences of DNA and catalyze metal ion-dependent phosphodiester cleavage. While Mg(II) is required for cleavage in these enzymes, in some systems Ca(II) promotes avid substrate binding and sequence discrimination. These properties make them useful model systems for understanding the roles of alkaline earth metal ions in nucleic acid processing. We have previously shown that two Ca(II) ions stimulate DNA binding by PvuII endonuclease and that the trivalent lanthanide ions Tb(III) and Eu(III) support subnanomolar DNA binding in this system. Here we capitalize on this behavior, employing a unique combination of luminescence spectroscopy and DNA binding assays to characterize Ln(III) binding behavior by this enzyme. Upon excitation of tyrosine residues, the emissions of both Tb(III) and Eu(III) are enhanced severalfold. This enhancement is reduced by the addition of a large excess of Ca(II), indicating that these ions bind in the active site. Poor enhancements and affinities in the presence of the active site variant E68A indicate that Glu68 is an important Ln(III) ligand, similar to that observed with Ca(II), Mg(II), and Mn(II). At low micromolar Eu(III) concentrations in the presence of enzyme (10-20 microM), Eu(III) excitation (7)F(0) --> (5)D(0) spectra yield one dominant peak at 579.2 nm. A second, smaller peak at 579.4 nm is apparent at high Eu(III) concentrations (150 microM). Titration data for both Tb(III) and Eu(III) fit well to a two-site model featuring a strong site (K(d) = 1-3 microM) and a much weaker site (K(d) approximately 100-200 microM). Experiments with the E68A variant indicate that the Glu68 side chain is not required for the binding of this second Ln(III) equivalent; however, the dramatic increase in DNA binding affinity around 100 microM Ln(III) for the wild-type enzyme and metal-enhanced substrate affinity for E68A are consistent with functional relevance for this weaker site. This discrimination of sites should make it possible to use lanthanide substitution and lanthanide spectroscopy to probe individual metal ion binding sites, thus adding an important tool to the study of restriction enzyme structure and function.

NMR and chiroptical examination of the diastereoisomers of (S)-Eu-EOB-DTPA.

The solution structure of the diastereoisomers of (S)-Eu--EOB--DTPA has been analysed by (1)H NMR, CD and CPL spectroscopy. Two major species exist which possess very similar (1)H NMR paramagnetic shifts and emission spectra, consistent with a 9-coordinate structure involving one bound water. Circularly polarised luminescence data are consistent with a common Lambda-helicity for each isomer; the isomers differ only in the absolute configuration of the central nitrogen atom.

Diastereoselective formation of chiral tris-cyclometalated iridium (III) complexes: characterization and photophysical properties.

Chiral, facial tris-cyclometalated Ir(III) complexes, fac-Delta-Ir(pppy)(3), fac-Lambda-Ir(pppy)(3), fac-Lambda-IrL (where pppy is (8R,10R)-2-(2'-phenyl)-4,5-pinenopyridine and L is a tripodal ligand comprising three pppy moieties connected through a mesityl spacer) have been synthesized and characterized. In IrL, NMR and CD studies indicate that only one diastereomer is formed, with the Lambda configuration at the metal center, whereas enantiopure pppy yields the fac-Lambda- and the fac-Delta-stereoisomer in a ratio 2:3. fac-Lambda-IrL was structurally characterized using X-ray crystallography. The luminescence properties including CPL, of the three complexes and their sensitivity to dioxygen were examined.

The first enantiomerically pure helical noncovalent tripod for assembling nine-coordinate lanthanide(III) podates.

Decomplexation of the trivalent lanthanide, Ln(III), from the racemic bimetallic triple-stranded helicates [LnCr(L8)(3)](6+) provides the inert chiral tripodal nonadentate receptor [Cr(L8)(3)](3+). Elution of the latter podand with Na(2)Sb(2)[(+)-C(4)O(6)H(2)](2).5H(2)O through a cation exchange column allows its separation into its inert helical enantiomers M-(+)(589)-[Cr(L8)(3)](3+) and P-(-)(589)-[Cr(L8)(3)](3+), whose absolute configurations are assigned by using CD spectroscopy and exciton theory. Recombination with Ln(III) restores the original triple-stranded helicates [LnCr(L8)(3)](6+), and the associated thermodynamic parameters unravel the contribution of electrostatic repulsion and preorganization to the complexation process. Combining M-(+)(589)-[Cr(L8)(3)](3+) with Eu(III) produces the enantiomerically pure d-f helicate MM-(-)(589)-[EuCr(L8)(3)](CF(3)SO(3))(6).4CH(3)CN, whose X-ray crystal structure (EuCrC(113)H(111)N(25)O(21)S(6)F(18), monoclinic, P2(1), Z = 2) unambiguously confirms the absolute left-handed configuration for the final helix. The associated ligand-centered and metal-centered chiro-optical properties recorded for the complexes MM-[LnCr(L8)(3)](6+) and PP-[LnCr(L8)(3)](6+) (Ln = Eu, Gd, Tb) show a strong effect of helicity on specific rotary dispersions, CD and CPL spectra.

Circularly polarized luminescence from bridged triarylamine helicenes.

The first examples of circularly polarized luminescence from chiral bridged triarylamine-based heterohelicene molecules are reported. The luminescence dissymmetry factors are approximately |0.001|.

First diastereoselective formation of lanthanide triple helical complexes with a terdentate chiral C2 symmetric ligand.

Steric interactions between three enantiopure terdentate ligands leads to the diastereoselective formation of luminescent triple helical lanthanide complexes.