Yuchi Akio, Hiramatsu Hiroaki, Ohara Miyuki, Ohata Nayumi
Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555, Japan.
Anal Sci. 2003 Aug;19(8):1177-81. doi: 10.2116/analsci.19.1177.
An X-ray crystallographic study demonstrated that the tris complex of Al3+ with 2-methyl-8-quinolinol (Hmq), [Al(mq)3], had a discrete octahedral geometry in a meridional configuration with respect to mq-; the Al-N bonds were appreciably elongated. In organic solvents, the complex reacted with water to give a lower species of a mu-oxo dimer, [Al2O(mq)4], and a protonated ligand, depending on the concentrations of water and of excess ligand. None of Cl-, Br-, I-, ClO4-, and CH3COO- showed any reactions with [Al(mq)3]. The anions having high affinities to Al3+, such as H2PO4- and F-, replaced all the ligand. The anion having a lower affinity, HSO4-, exclusively formed a mixed-ligand complex of [Al(mq)2HSO4], which had a more intense fluorescence than the others. In contrast, the corresponding 8-quinolinol (Hq) complex, [Alq3], showed no reactions with any anions.
X射线晶体学研究表明，Al3+与2-甲基-8-喹啉醇（Hmq）形成的三配合物[Al(mq)3]，相对于mq-呈经式构型，具有离散的八面体几何结构；Al-N键明显拉长。在有机溶剂中，该配合物与水反应，根据水和过量配体的浓度，生成较低级的μ-氧代二聚体[Al2O(mq)4]和质子化配体。Cl-、Br-、I-、ClO4-和CH3COO-均未与[Al(mq)3]发生任何反应。对Al3+具有高亲和力的阴离子，如H2PO4-和F-，会取代所有配体。亲和力较低的阴离子HSO4-仅形成[Al(mq)2HSO4]混合配体配合物，其荧光比其他配合物更强。相比之下，相应的8-喹啉醇（Hq）配合物[Alq3]与任何阴离子均无反应。
