Siegfried Knecht

Synthesis and properties of soluble phthalocyaninatomanganese(III) complexes

(Acetato)-1,8,15,22-tetra-n-heptylphthalocyaninatomanganese(III) (C7H15)4PcMn-(OAc) (+structural isomers) (1) and the octa-n-heptyl-substituted (acetato)phthalocyaninatomanganese(III) complexes 1,4,8,11,15,18,22,25-(C7H15)8PcMn(OAc) (2) and 2,3,9,10,16,17,23,24-(C7H15)8PcMn(OAc) (3) have been synthesized and characterized by IR and UV-vis spectroscopy and elemental analysis. Electrochemical investigations of complexes 1 and 2 (CV, SEC) show similar electrochemical behaviour as the literature known compound (chloro)-2,9,16,23-tetra-tert-butylphthalocyaninatomanganese(III) (t-bu)4PcMnCl (+structural isomers) (4).

Substituent effects in soluble phthalocyaninatoiron(II) complexes

The synthesis and characterization of 1,4- and 2,3-octa- and tetra-substituted bis(tert-butylisocyanide)phthalocyaninatoiron(II) complexes with linear (n-heptyl, n-octyloxy) and branched (2-ethylhexyloxy) chains are reported. Analytical, spectroscopic and electrochemical studies have been carried out to obtain an insight into the substituent effects of these compounds. 1H NMR spectroscopy shows a smaller upfield shift of the axial ligand protons for the 1,4-substituted systems than for the 2,3-substituted systems. In the UV–VIS spectra bathochromic shifts are observed for the systems with their side chains in 1,4-positions in comparison with the 2,3-substituted analogues. Cyclic voltammetric measurements were carried out in dichloromethane and pyridine to determine the redox potentials of these complexes. A decrease of the oxidation and an increase of the reduction potentials were found by introducing substituents in the 1,4-positions of the macrocycle. 1,4-Substitution perturbs the electronic structure of phthalocyanine ring systems to a larger extent than 2,3-substitution.

Synthesis of 1-alkynyl(phthalocyaninato)iron(II) and -ruthenium(II) complexes

Abstract The preparation of dilithium[trans-bis(3,3-dimethyl-1-butynyl)phthalocyaninato]iron(II) (IIIb) is described. For comparison dilithium[trans-bis(phenylethynyl)phthalocyaninato]iron(II) (IIIa) was also made. Several 1-alkynyl(phthalocyaninato)ruthenium(II) compounds (IVa,b), of the first such species are reported. The products were obtained in high yields and characterized spectroscopically. The frequencies of the IR absorptions due to the stretching vibration of the CC bond are discussed.

Synthesis and properties of soluble metallophthalocyanines

Abstract Peripheral substitution with bulky or long-chain groups is the most efficient way to overcome the problem of low solubility of the phthalocyanine ring systems in organic solvents. In the present work the synthesis of alkoxy substituted metallophthalocyanines with iron(III), palladium(II) and platinum(II) as central metal atom, respectively, is describe. The iron compounds were used to prepare bisaxially coordinated complexes and oligomers with, e.g., 2,3,5,6-tetramethyldiisocyanobenzene (me 4 dib) as bridging ligand. Furthermore a new method to prepare bisaxially complexes of [tetra(t-butyl)phthalocyaninato]ruthenium(II), (t-Bu) 4 PcRuL 2 , which are considered as precursors of pure (t-Bu) 4 PcRu is reported.

Soluble Octasubstituted (Phthalocyaninato) Metal Complexes

Abstract Long chain substituted phthalocyanines are increasingly of interest because of their high solubility in common organic solvents and their liquid crystalline properties. 2,3,9,10,16,17,23,24-Octakis(decyloxy)phthalocyaninatonickel(II) (1), -palladium(II) (2) and -platinum(II) (3) were synthesized by reacting 1,2-dicyano-4,5-bis(decyloxy)benzene with the corresponding metal(II) salts and their liquid crystalline properties were investigated. Similarly, 1,4,8,11,15,18,22,25- (4) and 2,3,9,10,16,17,23,24-octakis(heptyl)phthalocyaninatonickel(II) (5) were prepared and their properties were compared. Compound 4 was investigated in detail with respect to its electrochemical properties.

Synthesis and properties of bridged phthalocyaninatoiron(II) complexes with bidentate aliphatic isocyanides

Phthalocyaninatoiron(II) (PcFe) was reacted with several aliphatic 5, 10–13, alicyclic 14, and aromatic isocyanides 3, 4 to form monomeric 15–17 and bridged oligomeric complexes 18–22. The syntheses of the isocyanides from the corresponding amines are described. All the products were characterized by spectroscopic methods. The coordination behaviour of the isocyanides based on their spectroscopic properties is discussed. The oligomers 18–22 show conductivities in the low semiconducting region, but by doping with iodine conductivities between 10−5 and 10−2 S/cm were obtained.

Axially 1,4-diisocyanobenzene bridged substituted iron (II) phthalocyanines and 2,3-naphthalocyanines

Abstract Several tetraalkyl substituted dimeric μ-oxo iron phthalocyanines have been prepared. Electric conductivities were measured for the 1,4-diisocyanobenzene bridged oligomers obtained from substituted iron phthalocyanines and 2,3-naphthalocyanines. All compounds were characterized by UV-Vis and Moβbauer spectroscopy,

Synthesis of Oligomeric Axially Bridged Ruthenium Phthalocyanines and 2,3-Naphthalocyanines

Bridged 2,3-naphthalocyaninatoruthenium oligomers {[MacRu(L)] n } were synthesized and characterized using solid-state methods. For comparison, soluble t-butyl substituted phthalocyaninatoruthenium oligomers were prepared and their chain length examined by H NMR spectroscopy. The powder conductivities of all bridged compounds ([MacRu(L)] n ) were measured and the dependence of the conductivities on the bridging ligands is discussed.

Polymeric 2,3-naphthalocyaninatoiron(II) complexes with bidentate isocyanides as intrinsic semiconductors

Abstract 2,3-Naphthalocyaninatoiron(II) was reacted with monodentate and bidentate isocyanides to form monomeric and bridged polymeric complexes, respectively. The products were characterized by physical and spectrochemical methods. The bridged complexes show electrical conductivities in the range of 10−3–10−6 S/cm without additional doping.