Solution Spin Crossover Versus Speciation Effects: A Cautionary Tale

Sriram Sundaresan; Sally Brooker

doi:10.1021/acs.inorgchem.3c00186

Solution Spin Crossover Versus Speciation Effects: A Cautionary Tale

Inorg Chem. 2023 Aug 7;62(31):12192-12202. doi: 10.1021/acs.inorgchem.3c00186. Epub 2023 Jul 23.

Authors

Sriram Sundaresan¹, Sally Brooker¹

Affiliation

¹ Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand.

PMID: 37482662
DOI: 10.1021/acs.inorgchem.3c00186

Abstract

Two acyclic tetradentate Schiff base ligands, HL^X-OH (X = H and Br), were synthesised by 2:1 condensation of either 2-pyridinecarboxaldehyde or 5-bromo-2-pyridinecarboxaldehyde and 1,3-diamino-2-propanol and then used to prepare six mononuclear complexes, [Fe^II(HL^X-OH)(NCE)₂], with three different NCE co-ligands (E = BH₃, Se, and S). The apparent solution spin crossover switching temperature, T_1/2, of these 6 complexes, determined by Evans method NMR studies, is tuned by several factors: (a) substituent X present at the 5 position of the pyridine ring of the ligand, (b) E present in the NCE co-ligand, (c) solvent employed (P'), and (d) potentially also by speciation effects. In CD₃CN, for the pair of NCE = NCBH₃ complexes, when X = H, the complex is practically LS (extrapolated T_1/2 ∼624 K), whereas when X = Br, it is far lower (373 K), which implies a higher field strength when X = H than when it is Br. The same trend, X = H results in a higher apparent T_1/2 than X = Br, is seen for the other two pairs of complexes, with E = Se (429 > 351 K, ΔT_1/2 = 78 K) or S (361 > 342 K, ΔT_1/2 = 19 K). For the family of three X = Br complexes, the change of E from BH₃ (373 K) to Se (351 K) to S (342 K) leads to an overall ΔT_1/2(apparent) = 31 K, whereas the decreases are far more pronounced in the X = H family (BH₃ ∼624 > Se 429 > S 361 K). Changing the solvent used from CD₃CN to (CD₃)₂CO and CD₃NO₂, for [Fe^II(HL^Br-OH)(NCE)₂] with either E = BH₃ or S, revealed excellent, and very similar, positive linear correlations (R² = 0.99) of increasing solvent polarity index P' (from 5 to 7) with increasing apparent T_1/2 of the complex (E = BH₃ gave T_1/2 300 < 373 < 451 K , ΔT_1/2 = 151 K; E = S gave T_1/2 288 < 342 < 427 K, ΔT_1/2 = 147 K). Several other solvent parameters were also correlated with the apparent T_1/2 of these complexes (R² = 0.74-0.96). Excellent linear correlations (R² = 0.99) are also obtained with the coordination ability (a^TM) of the three NCE co-ligands with the apparent T_1/2 in both families of compounds, [Fe^II(HL^X-OH)(NCE)₂] where X = H or Br. The ¹⁵N NMR chemical shifts of the nitrogen atom in the three NCE co-ligands (direct measurement) show modest correlations (R² = 0.74 for L^H-OH family and 0.80 for L^Br-OH family) with the apparent T_1/2 values of the corresponding complexes.