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Published on: March 2, 2016
Spectral investigation of phthalocyanine complexes of high-valence silver and their aggregates
Hiroaki Isago1, Harumi Fujita1, Suzuko Nakai2
1National Institute for Materials Science (NIMS), 1-2-1, Sengen, Tsukuba, Ibaraki 305-0047, Japan.
Abstract:
Several novel silver(II) complexes ligating a tetra-substituted phthalocyaninate, [Ag(tbpc)] (where tbpc denotes tetra-tert-butylphthalocyaninate), [Ag(tppc)] (tppc = tetrakis(2,6-dimethylphenoxy)phthalocyaninate), [Ag(tObpc)] (tObpc = tetra-n-butoxyphthalocyaninate), and [Ag(tpySpc)] (tpySpc = tetrakis(4-pyridylthio)phthalocyaninate) have been synthesized and characterized by elemental analyses, MALDI-TOF MS, optical absorption, and magnetic circular dichroism (MCD) spectroscopy. Although all the compounds are well soluble in common organic solvents, concentration studies on their optical spectra in solutions have found that they are prone to strongly aggregate in a cofacial manner (i.e., H-aggregate). Silver(II) complexes, which are essentially non-fluorescent, are readily demetallated in the presence of appropriate reductant (e.g., I- or BH4-) to liberate the corresponding macrocyclic ligand, which emits intense red fluorescence. Chemical oxidation by using NOBF4 generates the corresponding silver(III) species.
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