Lix(C5H5N)yFe2–zSe2: A Defect-Resilient Expanded-Lattice High-Temperature Superconductor

Two-dimensional iron chalcogenide intercalates display a remarkable correlation of the interlayer spacing with enhancement of the superconducting critical temperature (T_c). In this work, synchrotron X-ray absorption (XAS; at the Fe and Se K-edges) and emission (XES; at the Fe Κβ) spectroscopies allow one to discuss how the important rise of T_c (∼44 K) in the molecule-intercalated Li_x(C₅H₅N)_yFe_2-zSe₂ relates to the electronic and local structural changes felt by the inorganic host upon doping (x). XES shows that widely separated layers of edge-sharing FeSe₄ tetrahedra carry low-spin moieties, with a local Fe magnetic moment slightly reduced compared to the parent β-Fe_2-zSe₂. Pre-edge XAS expresses the progressively reduced mixing of metal 3d-4p states upon lithiation. Doping-mediated local lattice modifications, probed by conventional T_c optimization measures (cf. the anion height and FeSe₄ tetrahedra regularity), become less relevant when layers are spaced far away. On the basis of extended X-ray absorption fine structure, such distortions are compensated by a softer Fe network that relates to Fe-site vacancies, alleviating electron-lattice correlations and superconductivity. Density functional theory (DFT) guided modification of the isolated Fe_2-zSe₂ (z, vacant sites) planes, resembling the host layers, identify that Fe-site deficiency occurs at low energy cost, giving rise to stretched Fe sheets, in accordance with experiments. The robust high-T_c in Li_x(C₅H₅N)_yFe_2-zSe₂, arises from the interplay of electron-donating spacers and the iron selenide layer's tolerance to defect chemistry, a tool to favorably tune its Fermi surface properties.