ja8b03735_si_008.cif (41.24 MB)
Spin State Chemistry: Modulation of Ligand pKa by Spin State Switching in a [2×2] Iron(II) Grid-Type Complex
dataset
posted on 2018-06-06, 00:00 authored by Sébastien Dhers, Abhishake Mondal, David Aguilà, Juan Ramírez, Sergi Vela, Pierre Dechambenoit, Mathieu Rouzières, Jonathan R. Nitschke, Rodolphe Clérac, Jean-Marie LehnThe
iron(II) [2×2] grid complex Fe-8H has been
synthesized and characterized. It undergoes spin-crossover (SCO) upon
deprotonation of the hydrazine-based terpyridine-like ligand. The
deprotonation patterns have been determined by X-ray crystallography
and 1H NMR spectroscopy and discussed in relation to the
spin state of the iron(II) centers, which influences greatly the pKa of the ligand. The synthesis of the magnetically
silent zinc(II) analogue is also reported, and its (de)protonation
behavior has been characterized to serve as a reference for the study
of the FeII grid complexes. DFT computations have also
been performed in order to investigate how the successive deprotonation
of the bridging ligands affects the SCO behavior within the grid.
