Garau Alessandra, Blake Alexander J, Aragoni Maria Carla, Arca Massimiliano, Caltagirone Claudia, Demartin Francesco, Lippolis Vito, Picci Giacomo, Podda Enrico
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, Italy.
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Molecules. 2024 Dec 31;30(1):130. doi: 10.3390/molecules30010130.
2,8-Dithia-5-aza-2,6-pyridinophane () has been used as a receptor unit in the construction of the conjugated redox chemosensor 5-ferrocenylmethyl-2,8-dithia-5-aza-2,6-pyridinophane (). In order to further explore the coordination chemistry of , and comparatively, that of its structural analogue 2,11-dithia-5,8-diaza-2,6-pyridinophane (), featuring two secondary nitrogen atoms in the macrocyclic unit, the crystal structures of the new synthesised complexes [Pb()(ClO)]·½CHCN, Cu()·CHCN and [Cd()(NO)]NO were determined by X-ray diffraction analysis. The electrochemical response of towards the metal ions Cu, Zn, Cd, Hg, and Pb was investigated by cyclic voltammetry (CV) in CHCl/CHCN 0.25:1 (/) mixture. Upon addition to of increasing amounts of the aforementioned metal cations, the wave corresponding to the Fc/Fc redox couple of the un-complexed was gradually replaced by a new reversible wave at more positive potentials and corresponding to the Fc/Fc redox couple of the complexed ligand. The maximum anodic shift of the ferrocene oxidation wave is observed in the presence of Pb (230 mV), to which corresponds a reaction coupling efficiency (RCE) value as large as 7.9 × 10. The response selectivity of is discussed in reference to the optical selectivity observed for conjugated chemosensors featuring as receptor unit and different fluorogenic fragments as signalling units.
2,8-二硫杂-5-氮杂-2,6-吡啶环番（ ）已被用作构建共轭氧化还原化学传感器5-二茂铁基甲基-2,8-二硫杂-5-氮杂-2,6-吡啶环番（ ）的受体单元。为了进一步探究 的配位化学，并与之相比较，探究其结构类似物2,11-二硫杂-5,8-二氮杂-2,6-吡啶环番（ ）（其大环单元中有两个仲氮原子）的配位化学，通过X射线衍射分析测定了新合成配合物[Pb( )(ClO )]·½CH CN、Cu( )·CH CN和[Cd( )(NO )]NO 的晶体结构。通过循环伏安法（CV）在CHCl /CH CN 0.25:1（v/v）混合物中研究了 对金属离子Cu 、Zn 、Cd 、Hg 和Pb 的电化学响应。向 中加入越来越多上述金属阳离子后，未络合的 的Fc/Fc 氧化还原对对应的波逐渐被更正电位下对应于络合配体的Fc/Fc 氧化还原对的新可逆波所取代。在Pb 存在下观察到二茂铁氧化波的最大阳极位移为230 mV，与之对应的反应耦合效率（RCE）值高达7.9×10 。参照以 为受体单元、不同荧光片段为信号单元的共轭化学传感器所观察到的光学选择性，讨论了 的响应选择性。
