journal article·2020-03-19Open access

Revealing Hot and Long-Lived Metastable Spin States in the Photoinduced Switching of Solvated Metallogrid Complexes with Femtosecond Optical and X-ray Spectroscopies

Maria A. Naumova, Aleksandr Kalinko, Joanne W. L. Wong, Mohamed Abdellah, Huifang Geng, Edoardo Domenichini, Jie Meng, Sol Alvarez Gutierrez, Pierre-Adrien Mante, Weihua Lin, Peter Zalden, Andreas Galler, Frederico Lima, Katharina Kubicek, Mykola Biednov, Alexander Britz, Stefano Checchia, Victoria Kabanova, Michael Wulff, Jennifer Zimara, Dirk Schwarzer, Serhiy Demeshko, Vadim Murzin, David Gosztola, Martin Jarenmark, Jianxin Zhang, Matthias Bauer, Max Latevi Lawson Daku, Wojciech Gawelda, Dmitry Khakhulin, Christian Bressler, Franc Meyer, Kaibo Zheng, Sophie E. Canton

Abstract

An atomistic understanding of the photoinduced spin-state switching (PSS) within polynuclear systems of d4-d7 transition metal ion complexes is required for their rational integration into light-driven reactions of chemical and biological interest. However, in contrast to mononuclear systems, the multidimensional dynamics of the PSS in solvated molecular arrays have not yet been elucidated due to the expected complications associated with the connectivity between the metal centers and the strong interactions with the surroundings. In this work, the PSS in a solvated triiron(II) metallogrid complex is characterized using transient optical absorption and X-ray emission spectroscopies on the femtosecond time scale. The complementary measurements reveal the photoinduced creation of energy-rich (hot) and long-lived quintet states, whose dynamics differ critically from their mononuclear congeners. This finding opens major prospects for developing novel schemes in solution-phase spin chemistry that are driven by the dynamic PSS process in compact oligometallic arrays.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Magnetism in coordination complexes · Porphyrin and Phthalocyanine Chemistry · Electron Spin Resonance Studies

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Deutsches Elektronen Synchrotron (DESY), Notkestrasse 85, D-22607 Hamburg, Germany

Department Chemie and Center for Sustainable Systems Design (CSSD), University of Paderborn, Warburger Straße 100, D-33098 Paderborn, Germany

Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077 Göttingen, Germany

Chemical Physics and NanoLund, Lund University, Box 124, 22100 Lund, Sweden

Department of Chemistry, Qena Faculty of Science, South Valley University, 83523 Qena, Egypt

ELI-ALPS, ELI-HU Non-Profit Ltd., Dugonics ter 13, Szeged 6720, Hungary

Université de Strasbourg, CNRS, IPCMS, F-67000 Strasbourg, France

Department of Chemistry, Technical University of Denmark, DK-2800 Kongens Lyngby, Denmark

Department of Applied Physics, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong

European XFEL, Holzkoppel 4, 22869 Schenefeld, Germany

MAX IV Laboratory, Lund University, 22100 Lund, Sweden

European Synchrotron Radiation Facility (ESRF), 38000 Grenoble Cedex 9, France

Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, 37077 Göttingen, Germany

Bergische Universität Wuppertal, Gaußstraße 20, 42119 Wuppertal, Germany

Center for Nanoscale Materials, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States

Department of Geology, Lund University, 223 62 Lund, Sweden

State Key Laboratory of Hollow Fiber Membrane Materials and Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China

Département de Chimie Physique, Université de Genève, Quai E. Ansermet 30, CH-1211 Genève 4, Switzerland

Faculty of Physics, Adam Mickiewicz University, ul. Uniwersytetu Poznańskiego 2, 61-614 Poznań, Poland

The Hamburg Centre for Ultrafast Imaging, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany

References (60)

Show source-provided references
1. Shores, M. P.; Klug, C. M.; Fielder, R. S. In Spin Crossover Materials: Properties and Applications; Halcrow, M. A., Ed. Wiley: Chichester, U.K., 2013; pp 281–301.10.1002/9781118519301.ch10 ↗
2. 10.1126/science.107594810.1126/science.1075948 ↗
3. 10.1002/anie.20030063610.1002/anie.200300636 ↗
4. 10.1002/anie.20035293710.1002/anie.200352937 ↗
5. 10.1002/ange.20080452910.1002/ange.200804529 ↗
6. 10.1002/adma.20120302010.1002/adma.201203020 ↗
7. 10.1021/jacs.6b1246510.1021/jacs.6b12465 ↗
8. 10.1002/anie.20140896610.1002/anie.201408966 ↗
9. 10.1002/anie.20140306810.1002/anie.201403068 ↗
10. 10.1002/1521-3773(20000717)39:14<2504::AID-ANIE2504>3.0.CO;2-B10.1002/1521-3773(20000717)39:14<2504::AID-ANIE2504>3.0.CO;2-B ↗
11. 10.1002/anie.20100153610.1002/anie.201001536 ↗
12. 10.1021/ic402183810.1021/ic4021838 ↗
13. 10.1039/B701085K10.1039/B701085K ↗
14. 10.1039/c1cs15046d10.1039/c1cs15046d ↗
15. 10.1021/jacs.8b0373510.1021/jacs.8b03735 ↗
16. 10.1021/cs501721y10.1021/cs501721y ↗
17. 10.1039/B303922F10.1039/B303922F ↗
18. 10.1021/ar960201110.1021/ar9602011 ↗
19. 10.1021/cr960132410.1021/cr9601324 ↗
20. 10.1038/nature1325210.1038/nature13252 ↗
21. 10.1039/C8SC04023K10.1039/C8SC04023K ↗
22. 10.1039/C7CP07838B10.1039/C7CP07838B ↗
23. 10.1021/ic701951a10.1021/ic701951a ↗
24. 10.1016/j.ccr.2004.04.01110.1016/j.ccr.2004.04.011 ↗
25. 10.1016/j.ccr.2017.03.02410.1016/j.ccr.2017.03.024 ↗
26. 10.1107/S160057751900664710.1107/S1600577519006647 ↗
27. 10.1017/hpl.2015.1710.1017/hpl.2015.17 ↗
28. 10.3390/app706059210.3390/app7060592 ↗
29. 10.1038/ncomms735910.1038/ncomms7359 ↗
30. 10.1364/OL.44.00165010.1364/OL.44.001650 ↗
31. 10.1038/nchem.230510.1038/nchem.2305 ↗
32. 10.1002/anie.20090272810.1002/anie.200902728 ↗
33. 10.1038/ncomms1534210.1038/ncomms15342 ↗
34. 10.1039/c3cc43833c10.1039/c3cc43833c ↗
35. 10.1039/C9CP03483H10.1039/C9CP03483H ↗
36. 10.1021/ja00175a01210.1021/ja00175a012 ↗
37. 10.1021/ja00043a04910.1021/ja00043a049 ↗
38. 10.1021/ja00054a04310.1021/ja00054a043 ↗
39. 10.1039/b802607f10.1039/b802607f ↗
40. 10.1021/ic000656t10.1021/ic000656t ↗
41. 10.1063/1.294013010.1063/1.2940130 ↗
42. 10.1021/j100048a00410.1021/j100048a004 ↗
43. 10.1039/C6SC05624E10.1039/C6SC05624E ↗
44. 10.1002/chem.20170474610.1002/chem.201704746 ↗
45. 10.1063/1.512750710.1063/1.5127507 ↗
46. 10.1002/ejic.20170065710.1002/ejic.201700657 ↗
47. 10.1002/chem.20160037410.1002/chem.201600374 ↗
48. 10.1002/chem.20120378410.1002/chem.201203784 ↗
49. 10.3390/inorganics503006010.3390/inorganics5030060 ↗
50. 10.1021/acs.inorgchem.6b0023810.1021/acs.inorgchem.6b00238 ↗
51. 10.1021/ja00058a02610.1021/ja00058a026 ↗
52. 10.1021/jp500396310.1021/jp5003963 ↗
53. 10.1063/1.46125510.1063/1.461255 ↗
54. 10.1007/b9541610.1007/b95416 ↗
55. 10.1007/b1352810.1007/b13528 ↗
56. 10.1016/j.ccr.2005.12.00610.1016/j.ccr.2005.12.006 ↗
57. 10.1021/jacs.7b0929710.1021/jacs.7b09297 ↗
58. 10.1021/jp511718910.1021/jp5117189 ↗
59. 10.1021/acs.inorgchem.5b0276210.1021/acs.inorgchem.5b02762 ↗
60. 10.1038/nmat460610.1038/nmat4606 ↗