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Lösliche (Tetraethylphthalocyaninato)eisen(II)‐ und ‐cobalt(II)‐Verbindungen
Author(s) -
Beck Anton,
Mangold KlausMichael,
Hanack Michael
Publication year - 1991
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19911241026
Subject(s) - chemistry , cobalt , chloroform , toluene , proton nmr , medicinal chemistry , redox , cyclic voltammetry , stereochemistry , electrochemistry , inorganic chemistry , organic chemistry , electrode
Soluble (Tetraethylphthalocyaninato)iron(II) and ‐cobalt(II) Compounds The (tetraethylphthalocyaninato)iron and ‐cobalt compounds Et 4 PcFe (9), Et 4 PcCo ( 8 ), and Et 4 PcH 2 ( 7 ) have been synthesized starting from 3,4‐dibromoacetophenone ( 1 ) via the corresponding dinitrile 5 or isoindolenine 6 , respectively. Et 4 PcFe ( 9 ) reacts with t BuNC, p ‐diisocyanobenzene (dib), and me 4 dib to form the bisaxially coordinated compound Et 4 PcFe( t BuNc) 2 ( 10 ) and the oligomers [Et 4 PcFe(dib)] n ( 11 ) and [Et 4 PcFe‐ (me 4 dib)] n ( 12 ). All of the synthesized compounds, except the oligomers with a chain length of more than 8 – 14 units, are soluble in organic solvents such as chloroform or toluene. The new compounds were characterized by 1 H‐, 13 C‐NMR, 13 C‐CP/NMR, UV/Vis, and IR spectra. In addition the redox properties of Et 4 PcCo ( 8 ) were studied by cyclic voltammetry and spectroelectrochemical methods. The Mößbauer spectra of the (phthalocyaninato)iron compounds 9, 11 , and 12 demonstrate the bridged structure of [Et 4 PcFe(L)] n (L = dib, me 4 dib) ( 11 , 12 ). The powder conductivity of [Et 4 PcFe(dib)] n ( 11 ) (σ RT = 5·10 ‐6 S/cm) is ca. 10 6 times higher than that of Et 4 PcFe ( 9 ) (σ RT = 9·10 ‐12 S/cm). After doping with iodine the oligomers 11 and 12 show an increase in conductivity of 10 5 and 10 4 , respectively (σ RT ≈ 10 ‐2 S/cm for [Et 4 PcFe(dib)I 0.85 ] n ).