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Quadruple Phthalocyanines

The world's first quadruple-decker phthalocyanine sandwich complex is held together by cadmium and lutetium ions

by Stephen K. Ritter
March 22, 2010 | A version of this story appeared in Volume 88, Issue 12

Stacked complexes made by sandwiching metal ions between the carbon-nitrogen macrocyclic ligand phthalocyanine (Pc) exhibit a range of potentially useful electrochromic and magnetic properties. So far, chemists have been limited to making triple-decker versions containing two metal centers and three Pc groups. Takamitsu Fukuda, Tsuneaki Biyajima, and Nagao Kobayashi of Tohoku University, in Japan, have now upped those numbers by creating the first quadruple-decker Pc complex (J. Am. Chem. Soc., DOI: 10.1021/ja100125e). Because Pc is a dianion and lanthanides are trivalent cations, the researchers noted that the known triple-decker Lu2Pc3 can be regarded as LuPc2 coordinated by LuPc+, and that LuPc2 was a good candidate for stacking a second LuPc2 unit if the right metal ion could be found to hold them together. The Tohoku team found Cd2+ to be a match. The researchers treated LuPc2(N[(CH2)3CH3]4) with Cd(CO2CH3)2 at 400 °C to obtain the quadruple complex as a dark purple powder in low yield. They made positive identification by using ion cyclotron resonance mass spectrometry and confirmed the quadruple stacking by using NMR spectroscopy to analyze the distinct sets of hydrogen atoms on the inner and outer Pc ligands.


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