Complete post-synthetic modification of a spin crossover complex

Abstract

Complete post-synthetic (PS) modification of an iron–triazole SCO complex is reported; and a full characterization is carried out for a series of PS-SCO complexes with 23%–100% modification.

Complete and Versatile Post‐Synthetic Modification on Iron‐Triazole Spin Crossover Complexes: A Relevant Material Elaboration Method

“…To the best of our knowledge, concerning this family of compounds, only formations of imine by PSM methodology were described in the literature. [46][47][48]50] When it was possible, we also prepared corresponding materials using the direct synthesis (DS) method in order to ease the characterization of the desired compound.…”

“…Very recently, Costa et al [50] published a complete PSM method resulting from a reaction between the [Fe(NH 2 trz) 3 ]X 2 (X=OTs) complex and vapors of aldehyde or ketones. Following our previous results [46] for which a complete PSM reaction was achieved on an iron-triazole SCO complex [Fe(NH 2 trz) 3 ](NO 3 ) 2 (with NH 2 trz = 4-amino-1,2,4-triazole), we are interested to study the PSM methodology on this family of compounds with a variety of substrates, in order to confirm the efficiency and show the versatility of such approach. We selected this "parent material" since it has a lot of advantages, i. e. [53] 1) well-known and interesting SCO properties (above room temperature with a hysteresis loop); 2) it can be easily synthesized in one step from commercial reactants; 3) it has a NH 2 group which is able to react with several reagents.…”

“…To the best of our knowledge, few examples using this methodology for SCO materials are described in the literature. They consist of post-functionalization of 3D Hofmann clathrate MOF, [41,42] a dinuclear iron(III) complex, [43] a Fe II [M IV (CN) 8 ] 4 À (M=Mo, Nb) cyanido-Bridged Framework, [44] 1D polymeric iron-triazole complexes [45][46][47][48][49][50] and of iron poly(pyrazolyl)borate complexes. [51,52] In 2001, Saf et al [49] published the synthesis of a spin crossover material, for which the last step of the synthesis corresponds to the polymerization of the methacrylate substituent present on the triazole ligand.…”

Covalent Post‐Assembly Modification: A Synthetic Multipurpose Tool in Supramolecular Chemistry

“…While exploring polymeric SCO materials, Bousseksou et al [53] demonstrated that covalent PAM and direct ligand synthesis produced functionalized products with different magnetic properties. Parent complex 57 is a coordination polymer featuring pendant amines that can undergo condensation reactions with aldehydes to produce imines (Scheme 17).…”

“…Preparation of imine-functionalized SCO compound 58 by PAM of complex 57 and direct synthesis from ligand 59 afforded products with differing magnetic properties. [53] (a) Molecular model (UFF optimized) of the parent SCO complex 57, which is a solid-state coordination polymer featuring pendant amine groups. Key: greycarbon, bluenitrogen, whitehydrogen, orangeiron(II).…”