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A Two‐in‐one Pincer Ligand and its Diiron(II) Complex Showing Spin State Switching in Solution through Reversible Ligand Exchange
Author(s) -
Samanta Subhas,
Demesko Serhiy,
Dechert Sebastian,
Meyer Franc
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201408966
Subject(s) - trifluoromethanesulfonate , chemistry , ligand (biochemistry) , pincer movement , spin states , bridging ligand , octahedron , crystallography , pincer ligand , spin (aerodynamics) , photochemistry , inorganic chemistry , catalysis , crystal structure , organic chemistry , physics , thermodynamics , biochemistry , receptor
A novel pyrazolate‐bridged ligand providing two {PNN} pincer‐type compartments has been synthesized. Its diiron(II) complex LFe 2 (OTf) 3 (CH 3 CN) ( 1 ; Tf=triflate) features, in solid state, two bridging triflate ligands, with a terminal triflate and a MeCN ligand completing the octahedral coordination spheres of the two high‐spin metal ions. In MeCN solution, 1 is shown to undergo a sequential, reversible, and complete spin transition to the low‐spin state upon cooling. Detailed UV/Vis and 19 F NMR spectroscopic studies as well as magnetic measurements have unraveled that spin state switching correlates with a rapid multistep triflate/MeCN ligand exchange equilibrium. The spin transition temperature can be continuously tuned by varying the triflate concentration in solution.