Login / Signup

Lattice solvent- and substituent-dependent spin-crossover in isomeric iron(II) complexes.

Kuppusamy Senthil KumarAsato MizunoLea SpiekerSoma SalamonBenoît HeinrichCorinne BaillyIvan ŠalitrošHeiko WendeMario Ruben
Published in: Dalton transactions (Cambridge, England : 2003) (2024)
Spin-state switching in iron(II) complexes composed of ligands featuring moderate ligand-field strength-for example, 2,6-bi(1 H -pyrazol-1-yl)pyridine (BPP)-is dependent on many factors. Herein, we show that spin-state switching in isomeric iron(II) complexes composed of BPP-based ligands-ethyl 2,6-bis(1 H -pyrazol-1-yl)isonicotinate (BPP-COOEt, L1) and (2,6-di(1 H -pyrazol-1-yl)pyridin-4-yl)methylacetate (BPP-CH 2 OCOMe, L2)-is dependent on the nature of the substituent at the BPP skeleton. Bi-stable spin-state switching-with a thermal hysteresis width (Δ T 1/2 ) of 44 K and switching temperature ( T 1/2 ) = 298 K in the first cycle-is observed for complex 1·CH 3 CN composed of L1 and BF 4 - counter anions. Conversely, the solvent-free isomeric counterpart of 1·CH 3 CN-complex 2a, composed of L2 and BF 4 - counter anions-was trapped in the high-spin (HS) state. For one of the polymorphs of complex 2b·CH 3 CN-2b·CH 3 CN-Y, Y denotes yellow colour of the crystals-composed of L2 and ClO 4 - counter anions, a gradual and non-hysteretic SCO is observed with T 1/2 = 234 K. Complexes 1·CH 3 CN and 2b·CH 3 CN-Y also underwent light-induced spin-state switching at 5 K due to the light-induced excited spin-state trapping (LIESST) effect. Structures of the low-spin (LS) and HS forms of complex 1·CH 3 CN revealed that spin-state switching goes hand-in-hand with pronounced distortion of the trans-N {pyridyl}-Fe-N{pyridyl} angle ( ϕ ), whereas such distortion is not observed for 2b·CH 3 CN-Y. This observation points that distortion is one of the factors making the spin-state switching of 1·CH 3 CN hysteretic in the solid state. The observation of bi-stable spin-state switching with T 1/2 centred at room temperature for 1·CH 3 CN indicates that technologically relevant spin-state switching profiles based on mononuclear iron(II) complexes can be obtained.
Keyphrases
  • room temperature
  • ionic liquid
  • lymph node metastasis
  • squamous cell carcinoma
  • density functional theory
  • clinical trial
  • escherichia coli
  • single cell
  • peripheral blood
  • iron deficiency