Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X-ray Absorption Spectroscopy

被引:41
作者
Canton, Sophie E. [1 ]
Zhang, Xiaoyi [4 ]
Daku, Latevi M. Lawson [6 ]
Smeigh, Amanda L. [7 ]
Zhang, Jianxin [2 ]
Liu, Yizhu [2 ]
Wallentin, Carl-Johan [2 ]
Attenkofer, Klaus [8 ]
Jennings, Guy [4 ]
Kurtz, Charles A. [4 ]
Gosztola, David [5 ]
Warnmark, Kenneth [2 ]
Hauser, Andreas [6 ]
Sundstrom, Villy [3 ]
机构
[1] Lund Univ, Dept Synchrotron Radiat Instrumentat, S-22100 Lund, Sweden
[2] Lund Univ, Ctr Anal & Synth, Dept Chem, S-22100 Lund, Sweden
[3] Lund Univ, Dept Chem Phys, S-22100 Lund, Sweden
[4] Argonne Natl Lab, Xray Sci Div, Argonne, IL 60439 USA
[5] Argonne Natl Lab, Ctr Nanoscale Mat, Argonne, IL 60439 USA
[6] Univ Geneva, Dept Chim Phys, CH-1211 Geneva 4, Switzerland
[7] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
[8] Brookhaven Natl Lab, Photon Sci Directorate, Upton, NY 11973 USA
基金
欧洲研究理事会; 瑞典研究理事会;
关键词
FE(II) COMPLEXES; ELECTRONIC-STRUCTURE; MULTIPLE-SCATTERING; IRON(II) COMPLEXES; SCREENING MODEL; METAL-COMPLEXES; CRYSTAL-FIELD; K-EDGE; STATE; LIGHT;
D O I
10.1021/jp5003963
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
For numerous spin crossover complexes, the anisotropic distortion of the first coordination shell around the transition metal center governs the dynamics of the high-spin/low-spin interconversion. However, this structural parameter remains elusive for samples that cannot be investigated with crystallography. The present work demonstrates how picosecond X-ray absorption spectroscopy is able to capture this specific deformation in the photoinduced high-spin state of solvated [Fe(terpy)(2)](2+), a complex which belongs to the prominent family of spin crossover building blocks with nonequivalent metal-ligand bonds. The correlated changes in Fe-N-Axial, Fe-N-Distal, and bite angle N-Distal-Fe-N-Axial extracted from the measurements are in very good agreement with those predicted by DFT calculations in D-2d symmetry. The outlined methodology is generally applicable to the characterization of ultrafast nuclear rearrangements around metal centers in photoactive molecular complexes and nanomaterials, including those that do not display long-range order.
引用
收藏
页码:4536 / 4545
页数:10
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