ABSTRACT
Aggregation of cationic isothiouronium polythiophenes with alkoxy-spacers of different lengths at the 3-position of the thiophene ring was studied in solvents of different polarities. Hydrogen-bonding capacity was assessed by steady-state absorption and fluorescence spectroscopy, whereas the aggregation in aqueous solutions was studied by electron paramagnetic resonance spectroscopy, using paramagnetic probes of different polarities. The two polymers displayed similar features in respect to conformation, effect of cosolvents on aggregation, unstructured absorption-fluorescence spectra, Stokes shifts when aggregated, solvatochromic effect, and self-quenching concentration. However, these polymers also showed different specific interactions with water, Stokes shifts in water, effect of the solvent on the extent of dominant state of the S1 level, and also different inner cavities and hydrophobic-hydrophilic surface area in aqueous solution aggregates. Water maximized the difference between the polymers concerning the effect of specific increases in concentration, whereas the presence of 1,4-dioxane generated almost identical effects on both polymers.
ABSTRACT
Dioxotungsten(vi) complexes with tetradentate amino bisphenolates were converted into the corresponding Cs-symmetric amino bisphenolate disulphido complexes by a reaction with either Lawesson's reagent or P2S5. Further reaction with diethyl acetylenedicarboxylate leads to the formation of diamagnetic tungsten(iv) dithiolene compounds. The syntheses, crystal structures, spectroscopic and electrochemical characterization of such disulphido and dithiolene complexes are presented.
Subject(s)
Hydroxybenzoates/chemistry , Organometallic Compounds/chemistry , Sulfides/chemistry , Tungsten/chemistry , Electrochemistry , Models, Molecular , Molecular Conformation , Organometallic Compounds/chemical synthesis , Oxides/chemistryABSTRACT
The reaction of VO(acac)2 (acac(-) = acetyl acetonate) with tripodal glycine bisphenol H3L(1) under an ambient atmosphere yields a hexacoordinated vanadium(iv) complex [V(acac)(L(1))] (1). The corresponding reactions with tripodal 2-propanolamine bisphenol H3L(2) and potentially pentadentate ethoxyethanolamine bisphenol H3L(3) lead to the oxidation of the metal centre and formation of mononuclear oxovanadium(v) complexes [VO(L(2))] (2) and [VO(L(3))] (3), respectively. Alternatively, these latter two complexes can be prepared using VOSO4·5H2O or VO(OPr)3 as a precursor. The CV of 1 in an ACN solution shows a reversible one-electron process at E1/2 = +1.18 V, whereas 2 and 3 have an irreversible redox response at -1.6 V and -1.2 V, respectively. Complexes 2 and 3 show moderate activity in the epoxidation of cis-cyclooctene by tert-BuOOH at 50 °C.