Water molecule induced reversible single-crystal-to-single-crystal transformation between two trinuclear Fe(ii) complexes with different spin crossover behaviour

Author(s): Wen-Bin Chen ¹ ^, ² ^, ³ ^, ⁴ ^, ⁵ , Yan-Cong Chen ⁶ ^, ⁷ ^, ⁸ ^, ⁵ , Meng Yang ¹ ^, ² ^, ³ ^, ⁴ ^, ⁵ , Ming-Liang Tong ⁶ ^, ⁷ ^, ⁸ ^, ⁵ , Wen Dong ¹ ^, ² ^, ³ ^, ⁴ ^, ⁵

Publication date (Electronic): 2018

Journal: Dalton Transactions

Publisher: Royal Society of Chemistry (RSC)

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Abstract

Water molecule induced reversible single-crystal-to-single-crystal transformation between two trinuclear Fe( ii) complexes with different spin crossover behaviour.

Abstract

A 4-amino-1,2,4-triazole (NH ₂-trz) based linear trinuclear Fe( ii) complex of [Fe ₃(NH ₂-trz) ₆(SCN) ₄(H ₂O) ₂](SCN) ₂·H ₂O ( 1) has been hydrothermally synthesized by the reaction of a NH ₂-trz ligand with FeSO ₄. A single crystal of complex 1 is able to extrude one lattice water and one coordinated water, leading to another single crystal of complex 1a with a formula [Fe ₃(NH ₂-trz) ₆(SCN) ₅(H ₂O)](SCN) by heating. Complex 1a can be reversed to 1 upon the reabsorption of water. Single-crystal X-ray diffraction analysis reveals that these two complexes consist of a linear trinuclear core where a central Fe1 ion is coordinated to six nitrogen atoms from six bridged NH ₂-trz ligands and one of the terminal Fe2 ions is coordinated to five nitrogen atoms and one oxygen atom. The terminal Fe3 ion in 1 coordinates to five nitrogen atoms and one oxygen atom; however, the terminal Fe3 ion in 1a coordinates to six nitrogen atoms. Magnetic susceptibility measurements demonstrate that they exhibited gradual spin crossover (SCO) for the central Fe( ii) ion; however, different spin transition temperatures were displayed for complexes 1 and 1a ( T _1/2 = 202 K for 1 and 160 K for 1a). These different spin transition temperatures arise from the different intermolecular hydrogen bonding interactions in the two complexes.

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Azzedine Bousseksou, Gabor Molnar, Lionel Salmon … (2011)

Recently we assisted a strong renewed interest in the fascinating field of molecular spin crossover complexes by (1) the emergence of nanosized spin crossover materials through direct synthesis of coordination nanoparticles and nanopatterned thin films as well as by (2) the use of novel sophisticated high spatial and temporal resolution experimental techniques and theoretical approaches for the study of spatiotemporal phenomena in cooperative spin crossover systems. Besides generating new fundamental knowledge on size-reduction effects and the dynamics of the spin crossover phenomenon, this research aims also at the development of practical applications such as sensor, display, information storage and nanophotonic devices. In this critical review, we discuss recent work in the field of molecule-based spin crossover materials with a special focus on these emerging issues, including chemical synthesis, physical properties and theoretical aspects as well (223 references).