Sparkle/RM1 parameters for the semiempirical quantum chemical calculation of lanthanide complexes

Abstract

In this article, we present Sparkle Model parameters to be used with RM1, presently one of the most accurate and widely used semiempirical molecular orbital models based exclusively on monoatomic parameters, for systems containing H, C, N, O, P, S, F, Cl, Br, and I. Accordingly, we used the geometries of 169 high quality crystallographic structures of complexes for the training set, and 435 more for the validation of the parameterization for the whole lanthanide series, from La(III) to Lu(III). The distance deviations appear to be random around a mean for all lanthanides. The average unsigned error for Sparkle/RM1 for the distances between the metal ion and its coordinating atoms is 0.065 Å for all lanthanides, ranging from a minimum of 0.056 Å for Pm(III) to 0.074 Å for Ce(III), making Sparkle/RM1 a balanced method across the lanthanide series. Moreover, a detailed analysis of all results indicates that Sparkle/RM1 is particularly accurate in the prediction of lanthanide cation-coordinating atom distances, making it a suitable method for the design of luminescent lanthanide complexes. We illustrate the potential of Sparkle/RM1 by carrying out a Sparkle/RM1 full geometry optimization of a tetramer complex of europium with 181 atoms. Sparkle/RM1 may be used for the prediction of geometries of large complexes, metal-organic frameworks, etc., to useful accuracy.

The Role of the Ligand‐to‐Metal Charge‐Transfer State in the Dipivaloylmethanate‐Lanthanide Intramolecular Energy Transfer Process

“…[45][46][47] From the optimized structures, singlet and triplet excited states of ligands and theoretical UV/Vis absorption spectra of the monomeric (1 and 2) and dimeric (3 and 4) complexes were calculated by using the ZINDO/S technique, wherein the Ln III ion was represented as a point charge of +3e. [45][46][47] From the optimized structures, singlet and triplet excited states of ligands and theoretical UV/Vis absorption spectra of the monomeric (1 and 2) and dimeric (3 and 4) complexes were calculated by using the ZINDO/S technique, wherein the Ln III ion was represented as a point charge of +3e.…”

In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids

“…While such models are lacking in rigor as compared to ab initio and density functional theory methods, they gain in the ability to tackle systems consisting of 10 2 -10 3 atoms and have been extensively tested for a large variety of lanthanide complexes and solid compounds. 56,57 We first consider isolated chains, ribbons, and sheets; the crystal structures will be further examined in section 4. The dimers, which are the tentative precursors of CPs (section 1), can be classified according to the number of the O-P-O bridges between the Ln 3+ ions (see Table 1 and Figure 5S), which can be two (the 1 2 -2-1 2 motif), three (the 1-3-1 2 motif), or four (the 1-4-1 motifs).…”

The Influence of Different Ammonium Cations on the Optical Properties of Tetrakis GdIII and EuIII Complexes

“…In this particular case the distance Eu-Eu may also be a factor in the deactivation; however, we were not able to quantify this effect. The ground state geometry of the complexes was determined using the Sparkle/RM1 44 and Sparkle/PM6 45 methods implemented in the Mopac2012 software 47 ( Figures 5 and 6, and Figures S3 and S4, SI section). The average Eu−O distance bond obtained by X-ray diffraction for [Eu(b-dik) 4 ]complexes is 2.3878 Å, 55,[57][58][59][60][61][62] while using the Sparkle/RM1 and Sparkle/PM6 we obtained 2.4589 (2.98% error) and 2.4306 Å (1.79% error), respectively.…”

“…Sparkle/RM1 44 and Sparkle/PM6 45 models were used to determine the complexes ground state geometries. In this model the lanthanide ion is replaced by a +3e point charge.…”