Phthalocyanine triple decker complexes

Phthalocyanine triple decker complexes have been used by N. Ishikawa et al. in 2002 to detect f-f interactions in a series of homodimetallic PcLnPcLnPc compounds, where Pc denotes a phthalocyanine octa-substituted by butoxy groups. The temperature dependence of the magnetic susceptibility of these triple deckers has been compared to the same data... 

Lanthanides form phthalocyanines PcMX, sandwich-like complexes of the type Pc2M, and triple-decker complexes of the type Pc3M2. 

Bocian, Lindsey and co-workers studied sandwich complex nanocapacitors comprised of porphyrin and phthalocyanine ligands separated by lanthanide metals [133]. A triple-decker sandwich of phthalocyanine-Eu-phthalocyanine-Eu-porphy-rin, with two phenylethynyl linker wires from the porphyrin, potentially has up to nine accessible oxidation states (—4 to +4). SAMs of monomers, dimers, trimers, and oligomers of this sandwich, anchored at one or both ends by thioacetyl groups, gave charge densities up to 10 10 mol cm-2, electron-transfer rates up to 105 electrons s-1, and charge-dissipation half-lives in the 10-50 s range. 

The lanthanide phthalocyanine complexes, obtained by conventional methods starting from metal salts at 170-290°C and phthalonitrile (Example 26), contain one or two macrocycles for each metal atom [5,6,8,63,82,84-98]. Thus, according to Refs. 6,63, and 85, the complexes having compositions LnPc2H, XLnPc (X- is halide anion), and Ln2Pc3 (a super-complex ) were prepared from phthalonitrile as a precursor the ratio of the reaction products depends on the synthesis conditions and the metal nature. The ionic structure Nd(Pc)+Nd(Pc)2 was suggested [85] and refuted [63] for the neodymium super-complex Nd2Pc3 the covalent character of the donor-acceptor bonds in this compound and other lanthanide triple-decker phthalocyanines was proved by the study of dissociation conditions of these compounds [63]. 

The iodine-doped, paramagnetic compound [Pc2ln](13)2/3 can be synthesized directly from In T1 alloy and 1,2-dicyanobenzene under a stream of iodine. " The solid-state structure features onedimensional stacks of [Pc2ln] columns and I3 chains. A triple-decker indium(III) phthalocyanine complex [Pc3ln2], which is diamagnetic, has been obtained by reacting In-Sn alloy with 1,2-dicyanobenzene at 210 Indium atoms are six-coordinate, and are located between the... 

Ishikawa, N. (2001). Electronic structures and spectral properties of double- and triple-decker phthalocyanine complexes in a localized molecular orbital view J. Porphyrins Phthalocyanines, 5, 87-101. 

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