(Porphyrinato)bis(phthalocyaninato)dilanthanide(III) complexes presenting a sandwich triple-decker-like structure
Bis(phthalocyaninato)lanthanide(III) derivatives presenting a sandwich-type structure have been known for many years. These complexes are still intensively studied due to their semi-conductor and electrochromic properties. The synthesis and properties of bis(porphyrinato) and tris(porphyrinato)lanthanide(III) derivatives have also been reported. X-ray structural studies have shown that bis(porphyrinato) complexes have geometries that are similar to those displayed by the LnPc/sub 2/ complexes (Ln = lanthanide; Pc = phthalocyanine) whereas the tris(porphyrinato) derivatives present structures in which two lanthanide(III) metal cations are sandwiched between three macrocyclic rings in triple-decker-like geometry. Structural, magnetic, and spectroscopic properties of the green form of lutetium(III) bis(phthalocyanate) have shown that this complex is in a nonprotonated, one-electron-oxidized ligand form, Ln (Pc/sup 2 -/) (Pc..pi..). In such a molecule, the unpaired spin could be either located on one phthalocyanine ring or delocalized over both rings. In order to force the localization of the unpaired spin on one ring, the authors have tried to synthesize a dissymmetric mixed-ligand, porphyrin (Por) phthalocyanine (Pc), lanthanide sandwich Ln(Por)(Pc). However, under the conditions used, the authors obtained dilanthanide sandwich-triple-decker-like complexes. (Por(Ln)Pc(Ln)Pc) in which the two metal cations are sandwiched between three macrocyclic rings. They report the synthesis and spectral properties of such derivatives obtained with Ln = Nd(III), Eu(III), and Gd(III) and with meso-tetrakis(4-methoxyphenyl) porphyrin (H/sub 2/T(4-OCH/sub 3/)PP) and phthalocyanine (H/sub 2/Pc). The X-ray structure of the neodymim complex is also reported.
- Research Organization:
- Universite Louis Pasteur, Strasbourg, France
- OSTI ID:
- 5658802
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:13; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400400 -- Electrochemistry
ABSORPTION SPECTROSCOPY
CARBOXYLIC ACIDS
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
EUROPIUM COMPLEXES
EXPERIMENTAL DATA
GADOLINIUM COMPLEXES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NEODYMIUM COMPLEXES
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PORPHYRINS
RARE EARTH COMPLEXES
SCATTERING
SPECTRA
SPECTROSCOPY
SYNTHESIS
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
X-RAY DIFFRACTION