Archer Rosanna J, Scott Hayley S, Polson Matthew I J, Mathonière Corine, Rouzières Mathieu, Clérac Rodolphe, Kruger Paul E
School of Physical and Chemical Sciences, University of Canterbury, Private Bag 4800, Christchurch, 8041, New Zealand.
MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Physical and Chemical Sciences, University of Canterbury, Private Bag 4800, Christchurch, 8041, New Zealand.
Chem Asian J. 2019 Jul 1;14(13):2225-2229. doi: 10.1002/asia.201900522. Epub 2019 Jun 11.
The synthesis and physico-chemical characterization of an Fe complex Fe(L1) ⋅CH CN⋅0.5H O, 1, incorporating a bidentate imidazolylimine-based ligand are reported. Complex 1 crystallises as the mer-isomer and the crystal lattice is replete with hydrogen bonding interactions between ClO anions, solvent molecules and imidazole N-H groups. Variable-temperature structural, magnetic, photomagnetic and optical reflectivity techniques have been deployed to fully characterise the spin-crossover (SCO) behaviour in 1 along with its desolvated phase, 1⋅desolv. Variable-temperature (1.8-300 K) magnetic-susceptibility measurements reveal a broad two-step full SCO for 1 (T =158 and 184 K) and photomagnetic experiments at 10 K under white-light irradiation revealed complete photo-induced SCO. 1⋅desolv displays considerably different magnetic behaviour with sharp single-step SCO accompanied by a thermal hysteresis (T =105 K, T =95 K) in addition to full photo-induced SCO at lower temperatures.
报道了一种铁配合物Fe(L1)₂·CH₃CN·0.5H₂O（1）的合成及其物理化学表征，该配合物含有一种基于双齿咪唑基亚胺的配体。配合物1以面式异构体形式结晶，晶格中充满了ClO₄⁻阴离子、溶剂分子和咪唑N-H基团之间的氢键相互作用。已采用变温结构、磁性、光磁和光学反射率技术对1及其去溶剂化相1·desolv中的自旋交叉（SCO）行为进行全面表征。变温（1.8 - 300 K）磁化率测量表明1呈现出宽泛的两步完全SCO（T₁/₂ = 158和184 K），并且在10 K白光照射下的光磁实验显示出完全的光致SCO。1·desolv表现出显著不同的磁行为，具有尖锐的单步SCO并伴有热滞现象（T₁ = 105 K，T₂ = 95 K），此外在较低温度下还有完全的光致SCO。
