Novel zirconium (IV) and hafnium (IV) phthalocyanines with dibenzoylmethane as out-of-plane ligand: Synthesis, X-ray structure and fluorescent properties

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• 作者：V.Ya. Chernii^a ; ^{mitya@ionc.kar.net} ; V.V. Bon^a ; I.N. Tretyakova^a ; O.V. Severinovskaya^b ; S.V. Volkov^a
• 关键词：Zirconium and hafnium phthalocyanines ; Synthesis ; GALDI mass spectroscopy ; UV&ndash ; vis spectroscopy ; Fluorescence ; X-ray diffraction
• 刊名：Dyes and Pigments
• 出版年：2012
• 期刊代码：31_01437208
• 类别：ms
• 出版时间：August, 2012
• 卷：94
• 期：2
• 页码：187-194
• 文件大小：1190 K

摘要

Novel phthalocyanine complexes of zirconium (IV) and hafnium (IV) containing dibenzoylmethane groups as out-of-plane ligands were synthesized and characterized by elemental analyses, GALDI mass spectrometry, IR, ¹H NMR, UV-vis and fluorescence spectroscopy. The structures of the complexes were determined by single-crystal X-Ray diffraction. The synthesized compounds are isomorphous, with their central atoms exhibiting (ZrN₄O₄ and HfN₄O₄) square-antiprism coordination geometry, which consists of four nitrogen atoms from the phthalocyanine macrocycle and four oxygen atoms from the two bidentate dibenzoylmethane ligands. GALDI mass spectrometry studies have shown that hafnium phthalocyanine forms adducts with masses higher than the mass of the molecular ion, indicating a high ability of this complex to self-associate in the gas phase. The spectral-luminescent properties of the compounds in different solvents were studied. The splitting of the Q-band observed in the absorption spectra is related to the lowering of complexes symmetry due to the incorporation of two rigid ligands to the central metal atom of the macrocycle. Study of the absorption spectra of phthalocyanines over a wide concentration range does not reveal any indications for the formation of aggregates. Fluorescence quantum yield values of the complexes were determined by a comparative method in toluene and DMSO.