Dataset Information

Sparkle/PM7 Lanthanide Parameters for the Modeling of Complexes and Materials.

ABSTRACT: The recently published Parametric Method number 7, PM7, is the first semiempirical method to be successfully tested by modeling crystal structures and heats of formation of solids. PM7 is thus also capable of producing results of useful accuracy for materials science, and constitutes a great improvement over its predecessor, PM6. In this article, we present Sparkle Model parameters to be used with PM7 that allow the prediction of geometries of metal complexes and materials which contain lanthanide trications. Accordingly, we considered the geometries of 224 high-quality crystallographic structures of complexes for the parameterization set and 395 more for the validation of the parameterization for the whole lanthanide series, from La(III) to Lu(III). The average unsigned error for Sparkle/PM7 for the distances between the metal ion and its coordinating atoms is 0.063Å for all lanthanides, ranging from a minimum of 0.052Å for Tb(III) to 0.088Å for Ce(III), comparable to the equivalent errors in the distances predicted by PM7 for other metals. These distance deviations follow a gamma distribution within a 95% level of confidence, signifying that they appear to be random around a mean, confirming that Sparkle/PM7 is a well-tempered method. We conclude by carrying out a Sparkle/PM7 full geometry optimization of two spatial groups of the same thulium-containing metal organic framework, with unit cells accommodating 376 atoms, of which 16 are Tm(III) cations; the optimized geometries were in good agreement with the crystallographic ones. These results emphasize the capability of the use of the Sparkle Model for the prediction of geometries of compounds containing lanthanide trications within the PM7 semiempirical model, as well as the usefulness of such semiempirical calculations for materials modeling. Sparkle/PM7 is available in the software package MOPAC2012, at no cost for academics and can be obtained from http://openmopac.net.

SUBMITTER: Dutra JD

PROVIDER: S-EPMC3806451 | biostudies-literature | 2013 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Similar Datasets

Project description:Heteroleptic homo dinuclear complexes [Sm(fod)3(μ-bpp)Sm(fod)3] and [Eu(fod)3(μ-bpp)Eu(fod)3] and their diamagnetic analogue [Lu(fod)3(μ-bpp)Lu(fod)3] (fod is the anion of 6,6,7,7,8,8,8- heptafluoro-2,2-dimethyl-3,5-octanedione (Hfod) and bpp is 2,3-bis(2-pyridyl)pyrazine) are synthesized and thoroughly characterized. The lanthanum gave a 1:1 adduct of La(fod)3 and bpp with the molecular formula of [La(fod)3bpp]. The 1H NMR and 1H-1H COSY spectra of the complexes were used to assign the proton resonances. In the case of paramagnetic Sm3+ and Eu3+ complexes, the methine (of the fod moiety) and the bpp resonances are shifted in the opposite direction and the paramagnetic shifts are dipolar in nature, which decrease with increasing distance of the proton from the metal ion. The single-crystal X-ray analyses reveal that the complexes (Sm3+ and Eu3+) are dinuclear and crystallize in the triclinic P1 space group. Each metal in a given complex is eight coordinate by coordinating with six oxygen atoms of three fod moieties and two nitrogen atoms of the bpp. Of the two metal centers, in a given complex, one has a distorted square antiprism arrangement and the other acquires a distorted dodecahedron geometry. The Sparkle RM1 and PM7 optimized structures of the complexes are also presented and compared with the crystal structure. Theoretically observed bond distances are in excellent agreement with the experimental values, and the RMS deviations for the optimized structures are 2.878, 2.217, 2.564, and 2.675 Å. The photophysical properties of Sm3+ and Eu3+ complexes are investigated in different solvents, solid, and PMMA-doped thin hybrid films. The spectroscopic parameters (the Judd-Ofelt intensity parameters, radiative parameters, and intrinsic quantum yield) of each Eu3+ sites are calculated using the overlap polyhedra method. The theoretically obtained parameters are close to the experimental results. The lifetime of the excited state is 38.74 μs for Sm3+ and 713.62 μs for the Eu3+ complex in the solid state.

Project description:The chiral nonaazamacrocyclic amine L, which is a reduction product of the 3 + 3 Schiff base macrocycle, wraps around the lanthanide(III) ions to form enantiopure helical complexes. These Ce(III), Pr(III), Nd(III), Eu(III), Gd(III), Tb(III), Er(III), Yb(III) and Lu(III) complexes have been isolated in enantiopure form and have been characterized by spectroscopic methods. X-ray crystal structures of the Ln(III) complexes with L show that the thermodynamic product of the complexation of the RRRRRR-isomer of the macrocycle is the (M)-helical complex in the case of Ce(III), Pr(III), Nd(III) and Eu(III). In contrast, the (P)-helical complex is the thermodynamic product in the case of Yb(III) and Lu(III). The NMR and CD spectra show that the (M)-helicity for the kinetic complexation product of the RRRRRR-isomer of the macrocycle is preferred for all investigated lanthanide(III) ions, while the preferred helicity of the thermodynamic product is (M) for the early lanthanide(III) ions and (P) for the late lanthanide(III) ions. In the case of the late lanthanide(III) ions, a slow inversion of helicity between the kinetic (M)-helical product and the thermodynamic (P)-helical product is observed in solution. For Er(III), Yb(III) and Lu(III) both forms have been isolated in pure form and characterized by NMR and CD. The analysis of 2D NMR spectra of the Lu(III) complex reveals the NOE correlations that prove that the helical structure is retained in solution. The NMR spectra also reveal large isotopic effect on the 1H NMR shifts of paramagnetic Ln(III) complexes, related to NH/ND exchange. Photophysical measurements show that L(RRRRRR) appears to favor an efficient 3pipi*-to-Ln energy transfer process taking place for Eu(III) and Tb(III), but these Eu(III)- and Tb(III)-containing complexes with L(RRRRRR) lead to small luminescent quantum yields due to an incomplete intersystem crossing (isc) transfer, a weak efficiency of the luminescence sensitization by the ligand, and/or efficient nonradiative deactivation processes. Circularly polarized luminescence on the MeOH solutions of Eu(III) and Tb(III) complexes confirms the presence of stable chiral emitting species and the observation of almost perfect mirror-image CPL spectra for these compounds with both enantiomeric forms of L.

Dataset Information

Sparkle/PM7 Lanthanide Parameters for the Modeling of Complexes and Materials.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets