Probing the unpaired Fe spins across the spin crossover of a coordination polymer

Probing the unpaired Fe spins across the spin crossover of a coordination polymer
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探测配位聚合物自旋交叉上不成对的 Fe 自旋

DOI:
10.1039/d0ma00612b
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发表时间:
2021
期刊:
影响因子:
5
通讯作者:
Dowben, Peter A.
Dowben, Peter A.
中科院分区:
--
文献类型:
--
作者:
Ekanayaka, Thilini K.;Kurz, Hannah;Dale, Ashley S.;Hao, Guanhua;Mosey, Aaron;Mishra, Esha;N’Diaye, Alpha T.;Cheng, Ruihua;Weber, Birgit;Dowben, Peter A.

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对于自旋交叉配位聚合物[Fe(L1)(bipy)]n(其中L1是带有吩嗪荧光团的N2 O22 −配位席夫碱样配体,bipy = 4,4 ′-联吡啶),有令人信服的额外证据表明自旋状态转变。Fe 2 p X射线吸收和X射线芯能级光电子能谱都证实了磁力测量所观察到的自旋交叉的发生。然而,从X射线吸收和X射线芯能级光电发射推断的自旋状态的温度依赖性变化的细节,不同于磁力测量,特别是关于表观临界转变温度和一般的曲线进展的合作性质。比较实验的自旋交叉数据伊辛模型模拟,在160至175毫电子伏的区域中的过渡活化能表示,沿着与非零交换J.总体而言,这意味着可能有扰动的自旋状态的双稳态,这是测量依赖或表面不同的大部分关于自旋过渡时观察到的合作效应。
For the spin crossover coordination polymer [Fe(L1)(bipy)]n (where L1 is a N2O22− coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4′-bipyridine), there is compelling additional evidence of a spin state transition. Both Fe 2p X-ray absorption and X-ray core level photoemission spectroscopies confirm that a spin crossover takes place, as observed by magnetometry. Yet the details of the temperature dependent changes of the spin state inferred from both X-ray absorption and X-ray core level photoemission, differ from magnetometry, particularly with regard to the apparent critical transition temperatures and the cooperative nature of the curve progression in general. Comparing the experimental spin crossover data to Ising model simulations, a transition activation energy in the region of 160 to 175 meV is indicated, along with a nonzero exchange J. Overall, the implication is that there may be perturbations to the bistability of spin states, that are measurement dependent or that the surface differs from the bulk with regard to the cooperative effects observed upon spin transition.
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