Optical limiting properties, structure and simplified TD-DFT calculations of scandium tetra-15-crown-5 phthalocyaninates

Abstract

The optical limiting properties of crown-ether-substituted scandium(III) phthalocyaninate complexes, bis-tetra-15-crown-5-phthalocyaninates Sc[(15C5)4Pc][Formula: see text] (I) and Sc[(15C5)4Pc][Formula: see text] (Ia), together with monophthalocyaninate [(15C5)4Pc]Sc(OAc) (II) were measured by using the Z-scan technique (532 nm laser and pulse rate of 10 ns). It was revealed that expansion of the [Formula: see text]-system on moving from the monomeric Sc complex II to sandwich compound I and changing the electronic state of the sandwich compound from the anionic Ia species to the neutral radical I improves the optical limiting properties. The Im[[Formula: see text]] values obtained lie in the 10[Formula: see text]–10[Formula: see text] esu range that is consistent with those reported previously for other organic chromophores. The crystal structure of sandwich Sc(III) complex I was elucidated by means of single-crystal X-ray diffraction analysis and was used to guide a series of theoretical calculations. It was demonstrated that the application of simplified time-dependent density functional theory (sTD-DFT) calculations can provide reasonably accurate predictions for compounds of this type when the geometries of the complexes are clearly defined.

Heteroleptic Crown-Substituted Tris(phthalocyaninates) as Dynamic Supramolecular Scaffolds with Switchable Rotational States and Tunable Magnetic Properties

“…Dispersion correction D3BJ was included. It has been previously found to be particularly important to reproduce the deformations of macrocyclic ligands in sandwich Pc complexes. , The observed consistency between the X-ray and DFT data suggests that an increase in the distance between the substituted Pc ligands occurs because of the repulsion rather than the intercalation of K ions.…”

“…It has been previously found to be particularly important to reproduce the deformations of macrocyclic ligands in sandwich Pc complexes. 33,34 The observed consistency between the X-ray and DFT data suggests that an increase in the distance between the substituted Pc ligands occurs because of the repulsion rather than the intercalation of K ions. Such an analysis became possible because of the correlation between the predominantly dipolar lanthanide-induced shift [LIS; Δδ p , eq 1] and the structure of the complexes: this…”

Redox-Triggered Switching of Conformational State in Triple-Decker Lanthanide Phthalocyaninates

“…In the absence of this correction, geometrical optimization of sandwich phthalocyaninates lead to structures with severely concaved Pc ligands which clearly contradicts X-ray data [ 47 ]. On the other hand, it has already been reported that the applied D3BJ correction overestimates the stabilisation of the g -conformations of alkoxy-substituted sandwiches even in cases where such conformation can be excluded on the basis of experimental data [ 48 ].…”

Interface Asymmetry Induced and Surface Pressure Controlled Valence Tautomerism in Monolayers of bis-Phthalocyaninates of Lanthanides

“…While the N (290 nm), Soret or B (300-400 nm) and Q (670-680 nm) bands are typical for phthalocyanines in general, the additional absorbances at 480-490 (blue valence bands, BV), 910-920 (red valence bands, RV) and 1400-1600 nm (intervalence bands, IV) are characteristics of double-decker complexes containing one unpaired electron [28,35,36]. The positions of all bands in the spectra of series of complexes gradually shift following the decrease in lanthanide ions radius causing the increase in intramolecular π-π interaction [37].…”