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Iron in a Cage: Fixation of a Fe(II)tpy$_{2}$ Complex by Fourfold Interlinking

Brandl, Thomas; Johannsen, Sven; Häussinger, Daniel; Suryadevara, Nithin; Prescimone, Alessandro; Bernhard, Stefan; Gruber, Manuel; Ruben, Mario; Berndt, Richard; Mayor, Marcel

The coordination sphere of the Fe(II) terpyridine complex 1 is rigidified by fourfold interlinking of both terpyridine ligands. Profiting from an octa‐aldehyde precursor complex, the ideal dimensions of the interlinking structures are determined by reversible Schiff‐base formation, before irreversible Wittig olefination provided the rigidified complex. Reversed‐phase HPLC enables the isolation of the all‐trans isomer of the Fe(II) terpyridine complex 1, which is fully characterized. While temperature independent low‐spin states were recorded with superconducting quantum interference device (SQUID) measurements for both, the open precursor 8 and the interlinked complex 1, evidence of the increased rigidity of the ligand sphere in 1 was provided by proton T$_{2}$ relaxation NMR experiments. The ligand sphere fixation in the macrocyclized complex 1 even reaches a level resisting substantial deformation upon deposition on an Au(111) surface, as demonstrated by its pristine form in a low temperature ultra‐high vacuum scanning tunneling microscope experiment.

Verlagsausgabe §
DOI: 10.5445/IR/1000126302
Veröffentlicht am 08.02.2021
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsmonat/-jahr 09.2020
Sprache Englisch
Identifikator ISSN: 0044-8249, 1521-3757
KITopen-ID: 1000126302
HGF-Programm 43.21.04 (POF III, LK 01) Molecular Engineering
Erschienen in Angewandte Chemie
Verlag John Wiley and Sons
Band 132
Heft 37
Seiten 16081–16086
Vorab online veröffentlicht am 29.06.2020
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