Sciortino Natasha F, Zenere Katrina A, Corrigan Maggie E, Halder Gregory J, Chastanet Guillaume, Létard Jean-François, Kepert Cameron J, Neville Suzanne M
School of Chemistry , The University of Sydney , NSW 2006 , Australia . Email:
X-ray Science Division , Advanced Photon Source , Argonne National Laboratory , IL 60439 , USA.
Chem Sci. 2017 Jan 1;8(1):701-707. doi: 10.1039/c6sc03114e. Epub 2016 Sep 12.
A four-stepped cascade of Fe(ii) high spin (HS) to low spin (LS) states is demonstrated in a family of 2-D Hofmann materials, [Fe(saltrz)(M(CN))]·8(HO) (M = Pd ( ), Pt ( ); saltrz = ()-2-(((4-1,2,4-triazol-4-yl)imino)methyl)phenol). Alongside the fully HS and LS Fe(ii) states, fractional spin state stabilization occurs at HS/LS values of 5/6, 2/3, and 1/6. This unconventional spin state periodicity is driven by the presence of multiple spin crossover (SCO) active Fe(ii) sites which are in subtly distinct environments driven by a network of antagonistic host-host and host-guest interactions. Alternating long- and short-range magnetostructural ordering is achieved over the five distinct spin state ratios HSLS, HSLS, HSLS, HSLS, and HSLS owing to the flexibility of this 2-D interdigitated lattice topology interconnected by intermolecular interactions. A distinct wave-like spin state patterning is structurally evidenced for each intermediate phase.
在二维霍夫曼材料家族[Fe(saltrz)(M(CN))]·8(H₂O)（M = Pd ( )，Pt ( )；saltrz = ( )-2-(((4-1,2,4-三唑-4-基)亚氨基)甲基)苯酚）中，展示了Fe(ii)高自旋（HS）到低自旋（LS）态的四步级联。除了完全的HS和LS Fe(ii)态外，在HS/LS值为5/6、2/3和1/6时出现了分数自旋态稳定化。这种非常规的自旋态周期性是由多个自旋交叉（SCO）活性Fe(ii)位点的存在驱动的，这些位点处于由拮抗的主-主和主-客体相互作用网络驱动的微妙不同的环境中。由于这种通过分子间相互作用相互连接的二维叉指晶格拓扑结构的灵活性，在五个不同的自旋态比率HSLS、HSLS、HSLS、HSLS和HSLS上实现了交替的长程和短程磁结构有序。每个中间相在结构上都有独特的波状自旋态图案。
