Strianese Maria, Milione Stefano, Bertolasi Valerio, Pellecchia Claudio
Dipartimento di Chimica, Università di Salerno , via Giovanni Paolo II 132, I-84084 Fisciano, Salerno, Italy.
Inorg Chem. 2013 Oct 21;52(20):11778-86. doi: 10.1021/ic401055k. Epub 2013 Sep 27.
Water-soluble iron and manganese pyridoxal-based complexes pyr2enFeCl (1) and pyr2enMnCl (2) (pyr2en = N,N'-ethylenebis(pyridoxylideneiminato) have been synthesized and characterized. Proof-of-principle results that the title complexes can be efficiently used as fluorescent probes for nitrite and nitrate detection are provided. The fluorescent complex pyr2enFeCl (1) selectively recognizes nitrate anions by fluorescent enhancement in an aqueous solution displaying high binding affinities. ESI-MS experiments clearly show the binding of these anions via the substitution of the chloride anion at the metal center. The pyridoxal-based manganese complexes of NO2(-) and NO3(-) have been isolated, and their structures have been established by single-crystal XRD. Density functional theory (DFT) calculations show that the substitution of the chloride anion at the metal center by the nitrite or nitrate anion is favored by the gain in the energies of hydration.
已合成并表征了基于水溶性铁和锰的吡哆醛配合物pyr2enFeCl（1）和pyr2enMnCl（2）（pyr2en = N，N'-亚乙基双（吡哆醛亚氨基））。提供了原理验证结果，表明标题配合物可有效地用作亚硝酸盐和硝酸盐检测的荧光探针。荧光配合物pyr2enFeCl（1）在水溶液中通过荧光增强选择性识别硝酸根阴离子，显示出高结合亲和力。电喷雾质谱（ESI-MS）实验清楚地表明这些阴离子通过金属中心的氯离子取代而结合。已分离出基于吡哆醛的NO2(-)和NO3(-)锰配合物，并通过单晶X射线衍射确定了它们的结构。密度泛函理论（DFT）计算表明，亚硝酸盐或硝酸盐阴离子取代金属中心的氯离子受水合能增加的影响。
