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

Abstract

<jats:title>Abstract</jats:title><jats:p> The preparation of the lanthanoid bisporphinates, bis[meso-tetra(p-tolyl)porphinato]-cerium(IV) [Ce(TTP)<jats:sub>2</jats:sub>**] and bis[meso-tetra(p-tolyl)porphinato]hydrogenpraseodymium-(III) [PrH(TTP)<jats:sub>2</jats:sub>] from Ce(acac)<jats:sub>3</jats:sub> and Pr(acac)<jats:sub>3</jats:sub> in boiling 1,2,4-trichlorobenzene is described. Ce(TTP)<jats:sub>2</jats:sub> is a diamagnetic and rather inert Ce<jats:sup>IV</jats:sup> derivative, PrH(TTP)<jats:sub>2</jats:sub> is a paramagnetic Pr<jats:sup>III</jats:sup> complex and may be deprotonated to give the anion [Pr(TTP)<jats:sub>2</jats:sub>]<jats:sup>-</jats:sup> which is characterized by conductivity measurements, electrophoresis, and isolation of its tetra(n-butyl)ammonium or tetraphenylarsonium salt. The compounds are identified by UV/VIS, IR, <jats:sup>1</jats:sup>H NMR, and mass spectra. The data are consistent with a sandwich-type square antiprismatic array of the two porphinate disks about the Ce<jats:sup>IV</jats:sup> or Pr<jats:sup>III</jats:sup> ion as found earlier in the bis-phthalocyaninates U(Pc)<jats:sub>2</jats:sub> or NdH(Pc)<jats:sub>2</jats:sub>.</jats:p>

Dimerization of a highly unsymmetrical lutetium bisphthalocyanine in solution

“…The comparison of the electronic spectrum of LuPcNc with those of LuPc 2 and LuNc 2 (Nc 2À = naphthalocyaninato) suggested an assymetry of the electron density over this unsymmetrical bismacrocyclic complex [5,6]. Similar sandwich complexes are known for porphyrins [7,8] and a lot of effort has been put into the synthesis and studies of heteroleptic complexes associating two different porphyrins [9,10], or two dissimilar phthalocyanines, or a phthalocyanine and a naphthalocyanine [11,12]. From near-infrared and Raman spectroscopies, it has been concluded that the oxidized macrocycle of a heteroleptic double-decker complex, coupling a phthalocyanine and a porphyrin, is the phthalocyanine (Pc ÅÀ ) and that the molecular orbital levels retain their P or Pc nature [11,[13][14][15].…”

Reactivity of Rare Earth Metal Porphyrins/Phthalocyanines in Acid Media

“…[93] The reaction between H 2 TPP and UO 2 (OAc) 2 in molar ratio 1:10 in a refluxing benzonitrile medium during 19 hours yields two complexes U(TPP) 2 The NMR spectrum of the double-decker complex agrees with the literature data for Th IV (TPP) 2 [88] and Ce IV (TTP) 2 (TTP -tetratolylporphyrin dianion). [94] The NMR spectrum of the triple-decker complex shows ten peaks what is in accord with ten kinds of protons: two -C 4 H 2 N (one inner and two outer macrocycles), two -p-C 6 H 5, threeo-C 6 H 5, and three -m-C 6 H 5 .…”

Heterocomponent ternary supramolecular complexes of porphyrins: A review

“…1). The first examples of homoleptic bis(porphyrinato) and heteroleptic porphyrinato and phthalocyanato complexes appeared in the 1980s [18,19]. The tetrapyrrole-based sandwich-type complexes have great potential in the preparation of different devices such as an enzyme-free electrochemical sensor for dopamine detection based on the (phthalocyaninato) (porphyrinato) europium III double-decker complex [20] and spintronic devices [21].…”