Synthesis,Structures, and Properties of Crystalline Salts with Radical Anions of Metal‐Containing and Metal‐Free Phthalocyanines |
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Authors: | Dr Dmitri V Konarev Dr Alexey V Kuzmin Dr Maxim A Faraonov Dr Manabu Ishikawa Dr Salavat S Khasanov Dr Yoshiaki Nakano Dr Akihiro Otsuka Prof Hideki Yamochi Prof?Dr Gunzi Saito Prof Rimma N Lyubovskaya |
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Institution: | 1. Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432 (Russia);2. Institute of Solid State Physics RAS, Chernogolovka, Moscow Region, 142432 (Russia);3. Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo‐ku, Kyoto 606‐8501 (Japan);4. Research Institute, Meijo University, 1‐501 Shiogamaguchi, Tempaku‐ku, Nagoya 468‐8502 (Japan) |
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Abstract: | Radical anion salts of metal‐containing and metal‐free phthalocyanines MPc(3?)].?, where M=CuII, NiII, H2, SnII, PbII, TiIVO, and VIVO ( 1 – 10 ) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C?Nimine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1 – 10 show new bands at 833–1041 nm in the NIR range, whereas the Q‐ and Soret bands are blue‐shifted by 0.13–0.25 eV (38‐92 nm) and 0.04–0.07 eV (4–13 nm), respectively. Radical anions with NiII, SnII, PbII, and TiIVO have S=1/2 spin state, whereas CuIIPc(3?)].? and VIVOPc(3?)].? containing paramagnetic CuII and VIVO have two S=1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal‐free phthalocyanine radical anions H2Pc(3?)].? (linewidth of 0.08–0.24 mT), broad EPR signals are manifested (linewidth of 2–70 mT) with g‐factors and linewidths that are strongly temperature‐dependent. Salt 11 containing the NaIPc(2?)]? anions as well as previously studied FeIPc(2?)]? and CoIPc(2?)]? anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of MPc(3?)].? in 1 – 10 . |
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Keywords: | complex chemistry phthalocyanine magnetic properties optical properties radical anions |
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