Dysprosium Heteroleptic Corrole-Phthalocyanine Triple-Decker Complexes: Synthesis, Crystal Structure, and Electrochemical and Magnetic Properties

Abstract

Two triple-decker dinuclear sandwich dysprosium complexes, which are represented as Dy[Pc(OCH)][Cor(FPh)] (1) and Dy[Pc(OCH)][Cor(ClPh)] (2), were synthesized and characterized by spectroscopic and electrochemical methods in nonaqueous media. Their electronic structures were also investigated on the basis of TD-DFT calculations. The sandwich triple-decker nature with the molecular conformation of [Pc(OCH)]Dy[Cor(FPh)]Dy[Pc(OCH)] for compound 1 was unambiguously revealed by single-crystal X-ray diffraction analysis and showed each dyprosium ion to be octacoordinated by the isoindole and pyrrole nitrogen atoms of an outer phthalocyanine ring and the central corrole ring, respectively. In addition, the magnetic properties of both compounds have also been characterized for exploring the functionalities of these types of triple-decker complexes.

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

“…Section 3.1), as evidenced from AC magnetic susceptibility measurements performed for dysprosium(III) complexes Dy 2 [(PentO) 8 Pc] 2 [(p-XPh) 3 Cor], X = F or Cl. 164 The presence of three protons in corroles suggests that the closed-shell form of triple-decker complexes should be anionic in nature, which makes them different from trisphthalocyaninates, where the charge of two trivalent REE ions is balanced by the charge of three dianionic ligands. Thus, to stabilize the negative charge of the (M 3+ ) 2 (Cor 3À )(Pc 2À ) 2 species a counterion is needed.…”

Construction of lanthanide complexes supported by 2,3‐dimethoxybenzoic acid and 5,5’‐dimethy‐2,2’‐bipyridine: crystal structures, thermoanalysis, magnetic and fluorescence properties

“…For photoluminescence, rare‐earth ions are usually used as luminescent centers for their high luminescence efficiency and adjustable emission color . Rare earth ions have magnetic anisotropy in magnetism, which makes them often used to make molecular‐based magnetic materials, such as single‐molecule magnets (SMMs) and single‐chain magnets (SCMs) . Not only that, rare‐earth ions are also used in other fields, such as bioassays, biological labels, light‐converting optical materials luminescent probes and light emitting diodes .…”

Construction of three types of lanthanide complexes based on 3,4‐dimethylbenzoic acid and 5,5′‐dimethyl‐2,2′‐bipyridine: Syntheses, Structures, Thermodynamic properties, Luminescence, and Bacteriostatic activities

“…The Tb1 center is eight‐coordinated, involved in a distorted square antiprism geometry and bound completely to six oxygen atoms (O1, O3, O5, O7, O9 and O10) respectively, which from one bidentate chelating and four bridging bidentate 3,4‐DMBA − ligands. The Tb2 is also eight‐coordinated with six oxygen atoms (O2, O4, O6, O8, O11 and O13) from one coordination water, one monodentate 3,4‐DMBA − ligand and four bridging bidentate 3,4‐DMBA − ligands, resulting in a distorted triangular dodecahedral geometry (Figure ). From the Table , we can see the average bond length of Tb‐O is 2.348 Å, which is shorter than that of Tb‐N bond (2.571 Å) owing to the stronger coordination ability of the oxygen atoms, which have been confirmed that the 5,5′‐DM‐2,2′‐bipy ligands are lost firstly in the thermal decomposition process.…”