Electrochemical and spectroelectrochemical properties of tetra-tert-butylphthalocyanine indium(III)

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Novel phenoxy-substituted subphthalocyanines possessing an extended π-system: synthesis and property investigation

Russian Chemical Bulletin - Novel phenoxy-substituted subnaphthalocyanine and binuclear subphthalocyanine were synthesized. Structures of the target compounds were established by 1H NMR...     

Phenoxy-substituted boron subphthalocyanine as a ionophore of ion-selective electrodes

Phenoxy-substituted boron subphthalocyanine was synthesized and studied as an ionophore of plasticized polyvinyl chloride membranes of ion-selective electrodes. The electrodes exhibit reversible response to dobutamine, demonstrating the cation function, as well as reversible response to the salicylate anion. The effects of concentration of the ionophore (0.2–5 wt %) and ionic components (sodium tetraphenylborate, TPhBNa, and tributylhexadecylphosphonium bromide, TBGDPBr), including ionic liquids (ILs), such as diphenylbutylethylphosphonium bis(triflyl)imide, diphenylbutylethylphosphonium hexafluorophosphate, and 1,3-dihexadecylimidazolium chloride, as well as plasticizers, such as ortho-nitrophenyloctyl ether and diethyl sebacate, on the electrochemical characteristics of membranes were studied. For the electrode containing 2% of the phenoxy-substituted boron subphthalocyanine in dobutamine and salicylate solutions, the slopes of the electrode function were 36 ± 1 mV/dec and–46 ± 3 mV/dec and the limits of detection (LODs) were 4 × 10^–5 M and 3 × 10^–4 M, respectively. The addition of an ionic liquid containing the diphenylbutylethylphosphonium cation and the bis(triflyl)imide and hexaflurophosphate anions to the membrane composition had no effect on the response of membrane electrodes to both dobutamine and salicylate. The use of phenoxy-substituted boron subphthalocyanine in an amount of 2% and the TPhBNa additive significantly improved sensor characteristics: the slope of the electrode function (S) for the dobutamine-selective electrode was (54 ± 1) mV/dec and LOD was 1 × 10^–5 M. Dobutamine can be determined in the presence of dopamine, adrenalin, and glucose. Electrodes based on 2% phenoxy-substituted boron subphthalocyanine and 0.5% (C₁₆H₃₃)₂ImCl, or TBGDPBr in salicylate solutions demonstrate the slope of the electrode function close to the theoretical one and a low limit of detection: S = (–59 ± 1) mV/dec, LOD = 2 × 10^–5 M and S = (–57 ± 1) mV/dec, LOD = 4 × 10^–5 M, respectively. The anti-Hofmeister selectivity of sensors was observed. The electrode based on phenoxy-substituted boron subphthalocyanine and (C₁₆H₃₃)₂ImCl was used for the assay of acetylsalicylic acid in the drug Cardiomagnyl.     

Sandwich double-decker lanthanide(III) "intracavity" complexes based on clamshell-type phthalocyanine ligands: synthesis, spectral, electrochemical, and spectroelectrochemical investigations

Phthalocyanine compounds of novel type based on a bridged bis-ligand, denoted "intracavity" complexes, have been prepared. Complexation of clamshell ligand 1,1'-[benzene-1,2-diylbis(methanediyloxy)]bis[9(10),16(17),23(24)-tri-tert-butylphthalocyanine] ((clam,tBu)Pc(2)H(4), 1) with lanthanide(III) salts [Ln(acac)(3)]?n?H(2)O (Ln = Eu, Dy, Lu; acetylacetonate) led to formation of double-deckers (clam,tBu)Pc(2)Ln (2?a-c). Formation of high molecular weight oligophthalocyanine complexes was demonstrated as well. The presence of an intramolecular covalent bridge affecting the relative arrangement of macrocycles was shown to result in specific physicochemical properties. A combination of UV/Vis/NIR and NMR spectroscopy, MALDI-TOF mass-spectrometry, cyclic voltammetry, and spectroelectrochemistry provided unambiguous characterization of the freshly prepared bis-phthalocyanines, and also revealed intrinsic peculiarities in the structure-property relationship, which were supported by theoretical calculations. Unexpected NMR activity of the paramagnetic dysprosium complex 2?b in the neutral π-radical form was observed and examined as well.