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Keywords = gadolinium bisphthalocyanine

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16 pages, 11694 KiB  
Article
Solvothermal Synthesis of Rare Earth Bisphthalocyanines
by Lina M. Bolivar-Pineda, Carlos U. Mendoza-Domínguez, Petra Rudolf, Elena V. Basiuk and Vladimir A. Basiuk
Molecules 2024, 29(11), 2690; https://doi.org/10.3390/molecules29112690 - 6 Jun 2024
Cited by 2 | Viewed by 1617
Abstract
Rare earth bisphthalocyanines (MPc2) are of particular interest because of their behavior as single-molecular magnets, which makes them suitable for applications in molecular spintronics, high-density data storage and quantum computation. Nevertheless, MPc2 are not commercially available, and the synthesis routes [...] Read more.
Rare earth bisphthalocyanines (MPc2) are of particular interest because of their behavior as single-molecular magnets, which makes them suitable for applications in molecular spintronics, high-density data storage and quantum computation. Nevertheless, MPc2 are not commercially available, and the synthesis routes are mainly focused on obtaining substituted phthalocyanines. Two preparation routes depend on the precursor: synthesis from phthalonitrile (PN) and the metalation of free or dilithium phthalocyanine (H2Pc and Li2Pc). In both options, byproducts such as free-base phthalocyanine and in the first route additional PN oligomers are generated, which influence the MPc2 yield. There are three preparation methods for these routes: heating, microwave radiation and reflux. In this research, solvothermal synthesis was applied as a new approach to prepare yttrium, lanthanum, gadolinium and terbium unsubstituted bisphthalocyanines using Li2Pc and the rare earth(III) acetylacetonates. Purification by sublimation gave high product yields compared to those reported, namely 68% for YPc2, 43% for LaPc2, 63% for GdPc2 and 62% for TbPc2, without any detectable presence of H2Pc. Characterization by infrared, Raman, ultraviolet–visible and X-ray photoelectron spectroscopy as well as elemental analysis revealed the main featuresof the four bisphthalocyanines, indicating the success of the synthesis of the complexes. Full article
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10 pages, 3091 KiB  
Article
Adsorption of Gadolinium Bisphthalocyanine on Atomically Flat Surfaces: Comparison of Graphene and Hexagonal Boron Nitride from DFT Calculations
by Vladimir A. Basiuk and Elena V. Basiuk
Surfaces 2024, 7(2), 404-413; https://doi.org/10.3390/surfaces7020025 - 1 Jun 2024
Viewed by 1073
Abstract
We studied the noncovalent interactions of gadolinium bisphthalocyanine (GdPc2) with cluster models for graphene and hexagonal boron nitride (hBN) of variable size by using the PBE functional of the generalized gradient approximation in conjunction with Grimme’s dispersion correction and [...] Read more.
We studied the noncovalent interactions of gadolinium bisphthalocyanine (GdPc2) with cluster models for graphene and hexagonal boron nitride (hBN) of variable size by using the PBE functional of the generalized gradient approximation in conjunction with Grimme’s dispersion correction and a DND double numerical basis set (that is, PBE-D2/DND). We found that in terms of the bonding strength, changes in the Gd-N bond lengths, the charge and spin of the Gd central ion, and the spin of the GdPc2 molecule, the behaviors of the graphene- and hBN-based model systems are rather similar. As expected, when increasing the size of the graphene and hBN cluster models, the strength of the interaction with GdPc2 increases, in which the bonding with the hBN models is usually stronger by a few kcal/mol. One of the main questions addressed in the present work was whether a change in the antiferromagnetic spin alignment to a ferromagnetic one, which is typical for GdPc2, is (at least theoretically) possible, as it has been observed previously for a number of graphene models when a smaller basis set DN was employed. We found that the use of a larger DND basis set dramatically reduces the occurrence of ferromagnetic adsorption complexes but does not exclude this possibility completely. Full article
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