Syntheses, Structures, and Magnetic Properties of seven-coordinate Lanthanide Porphyrinate or Phthalocyaninate Complexes with Kläui’s Tripodal Ligand

Abstract

A series of seven-coordinate mononuclear lanthanide(III) complexes of the general formula [(TPP)Ln(L(OEt))]·0.25H2O and [(Pc)Ln(L(OEt))] (Ln(3+) = Dy(3+), Tb(3+), Ho(3+), and Gd(3+); TPP = 5,10,15,20-tetraphenylporphyrinate; Pc = phthalocyaninate; L(OEt)(-) = [(η(5)-C5H5)Co(P(=O)(OEt)2)3](-)) are synthesized on the basis of the tripodal ligand L(OEt)(-) and either porphyrin or phthalocyanine ligands. All of the complexes are characterized by X-ray crystallography and by static and dynamic magnetic measurements. The Dy and Tb complexes show the field-induced slow relaxation of magnetization, and they are interesting seven-coordinate single-lanthanide-based SMMs. The magnetic relaxation properties of these double-decker sandwich complexes are influenced by the local molecular symmetry and are sensitive to subtle distortions of the coordination geometry of the paramagnetic lanthanide ions, such as metal-to-plane distances, plane center distances, and bending angles.

Lanthanide Metal–Organic Frameworks Assembled from Unexplored Imidazolylcarboxylic Acid: Structure and Field-Induced Two-Step Magnetic Relaxation

“…Such a case is derived from depopulation of the excited sublevels and/or intermolecular interaction. , The M versus H plotted curves of 1 – 3 show that all of the magnetizations are unsaturated even at 5 T, which is common in lanthanide ions (Figure S4). For 1 , the M versus H / T curves are thermally dependent (Figure , inset), supporting the presentation of large uniaxial anisotropy or a low-lying excited state. , …”

Highly near-IR emissive ytterbium(iii) complexes with unprecedented quantum yields

“…8a,19 In this work, we chose 2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin ( 1 ) as an antenna ligand to investigate the effect of C–H oscillators on porphyrinates, using 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin ( 2 ) and 2,3,7,8,12,13,17,18-octaduetero-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin ( 3 ) as controls. To assess the effects of the meso -pentafluorophenyl group in 1 , we replaced it with 2,6-difluorophenyl ( 4 ) and 4-trifluoromethylphenyl ( 5 ) groups.…”

Historic overview and new developments in synthetic methods for preparation of the rare-earth tetrapyrrolic complexes

“…Axial ligand(s) substitution reaction in rare-earth complexes of aromatic macrocycles was reported for Pors [126][127][128][129], N-confused Pors [130], and Pcs [131][132][133][134][135][136][137]. In the case of singledecker Pc derivatives similar reactions were also described for zirconium, hafnium [138,139], and indium [140][141][142] complexes.…”

“…ia i an tit tion reaction ith i's ligand can also be achieved in the case of rare-earth single-decker Pcs to form target dinuclear complexes 40 and 41 [131,132] be prepared by the reaction between ClIn(TFcP) and ferrocene lithium [144]. All five ferrocenes in the FcIn(TFcP) compound can be oxidized at different potentials and this organometallic Por can form highly ordered "channel" structures with the C 60 fullerene.…”