Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Department of Physics and Astronomy, University College London, Gower Street, London, WC1E 6BT, UK.
Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1561-1565. doi: 10.1002/anie.201609192. Epub 2017 Jan 10.
Metal-amine solutions provide a unique arena in which to study electrons in solution, and to tune the electron density from the extremes of electrolytic through to true metallic behavior. The existence and structure of a new class of concentrated metal-amine liquid, Li-NH -MeNH , is presented in which the mixed solvent produces a novel type of electron solvation and delocalization that is fundamentally different from either of the constituent systems. NMR, ESR, and neutron diffraction allow the environment of the solvated electron and liquid structure to be precisely interrogated. Unexpectedly it was found that the solution is truly homogeneous and metallic. Equally surprising was the observation of strong longer-range order in this mixed solvent system. This is despite the heterogeneity of the cation solvation, and it is concluded that the solvated electron itself acts as a structural template. This is a quite remarkable observation, given that the liquid is metallic.
金属-胺溶液为研究溶液中的电子提供了一个独特的平台，并可以从极端电解质调节到真正的金属行为来调节电子密度。本文介绍了一类新型的浓金属-胺液体 Li-NH-MeNH 的存在和结构，其中混合溶剂产生了一种新型的电子溶剂化和离域，与任何一种组成体系都有根本的不同。NMR、ESR 和中子衍射允许精确探测溶剂化电子和液体结构的环境。出乎意料的是，发现溶液是真正均匀的和金属的。同样令人惊讶的是，在这个混合溶剂体系中观察到了很强的长程有序。尽管阳离子溶剂化存在不均匀性，但可以得出结论，溶剂化电子本身充当了结构模板。这是一个非常显著的观察结果，因为液体是金属的。
