作为阴离子分子探针的空前 1,3-二氮杂[3]费罗芬烷骨架。

Unprecedented 1,3-diaza[3]ferrocenophane scaffold as molecular probe for anions.

机构信息

Departamento de Química Orgánica, Facultad de Química, Campus de Espinardo, Universidad de Murcia, E-30100 Murcia, Spain.

出版信息

Inorg Chem. 2011 May 2;50(9):4212-20. doi: 10.1021/ic102314r. Epub 2011 Feb 14.

DOI:10.1021/ic102314r

PMID:21319783

Abstract

The guanidine unit in the guise of 2-aminoimidazole in the new structural motif 2-arylamino-1,3-diaza[3]ferrocenophane 4 acts as a binding site for anions. The electrochemical behavior of this compound has been studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) and was found to exhibit a quasi reversible oxidation peak, associated to the Fe(II)/Fe(III) redox couple (Ep = 440 mV), and a non-reversible oxidation wave (Ep = 817 mV), probably associated to the oxidation of the C═N unit present in the guanidine bridge. Recognition of AcO(-), PhCO(2)(-), F(-), Cl(-), and Br(-) anions by the free receptor and the less basic anions Br(-), Cl(-), and NO(3)(-) by its monoprotonated form takes place by unusual redox-ratiometric measurements and spectroscopic ((1)H NMR and UV-vis) changes.

摘要

新结构 motif 2-芳基氨基-1,3-二氮杂[3]费罗芬 4 中的胍基单元伪装成 2-氨基咪唑，充当阴离子的结合位点。该化合物的电化学行为已通过循环伏安法 (CV) 和差分脉冲伏安法 (DPV) 进行了研究，结果表明它表现出准可逆氧化峰，与 Fe(II)/Fe(III) 氧化还原对相关 (Ep = 440 mV)，以及不可逆氧化波 (Ep = 817 mV)，可能与胍桥中存在的 C ═ N 单元的氧化有关。游离受体对 AcO(-)、PhCO(2)(-)、F(-)、Cl(-)和 Br(-)阴离子的识别以及其单质子化形式对较不碱性的 Br(-)、Cl(-)和 NO(3)(-)阴离子的识别是通过不寻常的氧化还原比色测量和光谱 ((1)H NMR 和 UV-vis) 变化来实现的。