4.8 Article

Spin Crossover in a Cobalt Complex on Ag(111)

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 12, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202115892

Keywords

Electron Transfer; Molecular Devices; Scanning Probe Microscopy; Single-Molecule Studies; Spin Crossover

Funding

  1. European Union [766726]
  2. Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) through the Collaborative Research Centre (CRC) 1242 [278162697]
  3. Projekt DEAL
  4. [389895192]
  5. [WE 2623/17-1]

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The Co-based complex deposited on Ag(111) was investigated. Due to a bis(tridentate) coordination sphere, the molecules formed tetramers. Individual complexes in these tetramers undergo reversible transitions between two states with characteristic image contrasts when current is passed through them or one of their neighbors.
The Co-based complex [Co(H2B(pz)(pypz))(2)] (py=pyridine, pz=pyrazole) deposited on Ag(111) was investigated with scanning tunneling microscopy at approximate to 5 K. Due to a bis(tridentate) coordination sphere the molecules aggregate mainly into tetramers. Individual complexes in these tetramers undergo reversible transitions between two states with characteristic image contrasts when current is passed through them or one of their neighbors. Two molecules exhibit this bistability while the other two molecules are stable. The transition rates vary linearly with the tunneling current and exhibit an intriguing dependence on the bias voltage and its polarity. We interpret the states as being due to S=(1)/(2) and (3)/(2) spin states of the Co2+ complex. The image contrast and the orders-of-magnitude variations of the switching yields can be tentatively understood from the calculated orbital structures of the two spin states, thus providing first insights into the mechanism of electron-induced excited spin-state trapping (ELIESST).

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