Preparation and properties of some rare-earth phthalocyanines

Abstract

The preparations and magnetic and spectral properties of one ytterbium and two gadolinium phthalocyanines are described and comparisons made with previous studies. The susceptibility of all three compounds followed a Curie-Weiss law, with � small, and the magnetic moments were typical for trivalent rare-earth compounds with little or no coupling between the metal ions. The e.p.r. signals observed were due to the metal ions. Structures proposed are Cl(pc)YbCl,2H2O (where pc = C32H16N8) for ytterbium, and (pc)Gd(pc)H and an associated anionic form for gadolinium. Both gadolinium materials are stable under certain solution conditions, although the anionic material tends to decompose and is difficult to obtain from solution. A polymeric form of phthalonitrile (m.p. 306�C) was isolated during purification. A simple acid-base equilibrium is proposed for the gadolinium compounds but it is complicated by the separation procedures and by the nature and purity of the solvent.

Metallkomplexe mit Tetrapyrrol-Liganden, XXXI [1]. Neutrale und anionoide Bisporphinate des Gers und Praseodyms / Metal Complexes with Tetrapyrrole Ligands, XXXI [1]. Neutral and Anionoid Bisporphinates of Cerium and Praeseodymium

“…die symmetrischen Derivate mit den vier wertigen Zentralmetallen Thorium und Uran, Th(Pc)2 [3] und U(Pc)2 [4], sowie die unsymmetrischen Derivate mit dreiwertigen Zentralmetallen, etwa NdH(Pc)2 [5] und GdH(Pc)2 [6], die zum Ladungsausgleich noch ein acides H-Atom tragen. Sowohl in U(Pc)2 [4] als auch in NdH(Pc)2 [7] liegen achtfach koordinierte Zentral-Ionen vor.…”

“…Seltenerdmetall-Porphinate [2 b] wurden erst zugänglich, als Horrocks (Jr.) [10a-f] und dann Srivastava [11] unsere Erfahrungen in der Verwendung von Metallacetylacetonaten zum Einbau von Sc 111 , Zr IV und Hf IV in Porphyrine [12] Wie schon früher an LuH(Pc)2 und GdH(Pc)2 beobachtet [6,8], kann man 2 gemäß Gl. (3) deprotonieren, wobei ein Sandwich-Anion entsteht.…”

Reactivity of Rare Earth Metal Porphyrins/Phthalocyanines in Acid Media

“…The average twist angle of distorted square antiprisms is equal to 43°. 13 C NMR spectrum shows more than 4 signals of carbon, [78] i.e. there are macrocycles of two types in the sample (one central and two equal each other external macrocycles) (Figure 11).…”

“…[12,13] The results of works [14][15][16][17][18] prove a molecular structure of both double-decker and triple-decker rare earth metal phthalocyanines. X-Rray crystallography data for triple-decker complexes are not numerous [19,20] whereas double-decker complexes including mixed (phthalocyaninato)(porphyrinato) complexes have been studied intensively.…”

Lanthanide diphthalocyanines. Electrochemistry and display applications

“…Further purification by liquid chromatography yields the diphthalocyanine. which my appear in both blue and green forms not yet fully distinguished from one another (Mackay et al, 1974). The chromatographic step can be eliminated by vacuum subliming the diphthalocyanine from the washed powder.…”