Selective crystallization of four bis(phthalocyaninato)lanthanoid(iii) polymorphs

Abstract

Bis(phthalocyaninato)lanthanoid(III) (LnPc2) complexes have attracted significant attention for their exceptional optical, electronic and magnetic properties. Crystallization of these compounds usually requires cumbersome methods such as sublimation and electrocrystallization, which is...

Lanthanide bisphthalocyanine single-molecule magnets: A DFT survey of their geometries and electronic properties from lanthanum to lutetium

“…When using the smallest basis set DN, one can observe that most of the optimized structures are also staggered with a φ angle varying between 42.48 • and 45 • . The only exception is SmPc 2 for which a semieclipsed conformation with a φ angle of 27.20 • was found, which does not coincide with either the one reported for the δ-phase (44.97 • ), or other phases, as analyzed by Dailey and Besson [10]. Increasing the basis set to DND showed only an insignificant improvement (φ of 29.52 • ), whereas with DNP the calculations did not converge at all.…”

“…Lanthanide bisphthalocyanines are characterized by a sandwich structure and a square antiprismatic geometry, caused by the coordination of central metal(III) with the eight isoindole nitrogen atoms (N iso ) of the two macrocycles, which are staggered by an angle (φ) between 44.83 • and 45 • with respect to each other (Fig. 1; Table 1), according to the experimental data [10][11][12][13]15,21,24,61]. The variation of φ depends on the specific Ln atom, the crystalline phase, and the presence of solvent molecules in the crystalline lattice [10,15,21,61].…”

“…1; Table 1), according to the experimental data [10][11][12][13]15,21,24,61]. The variation of φ depends on the specific Ln atom, the crystalline phase, and the presence of solvent molecules in the crystalline lattice [10,15,21,61]. In the present work, we compared DFT-calculated structures to the following crystalline phases of LnPc 2 complexes (Fig.…”

“…Due to the deemed importance for future applications, as well as simply because of their very peculiar geometry, spectroscopic, electronic and magnetic properties, it is not surprising that a significant research effort has been to the synthesis and characterization of a large series of unsubstituted and substituted LnPc 2 derivatives (for just a few representative examples, see Refs. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25]), with a special emphasis put on their X-ray diffraction (XRD) structure determination [10][11][12][13]15,[17][18][19][20]23,24].…”

Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications

“…347 In the context of this result, an important study by Dailey and Besson on the selective crystallization of four possible polymorphs of M(Pc) 2 complexes should be mentioned. 371 The authors proposed reproducible and selective crystallization techniques affording pure a-, gand d-phases together with the CH 2 Cl 2 solvate of complexes depending on the solvent, applied for crystallization. Systematic crystallographic and UV-Vis characterization of complexes allowed some of the confusion over chemical composition in previously published literature associated with interconversion between neutral and ionic forms of bisphthalocyaninates to be explained.…”