Spin crossover metal-organic frameworks with inserted photoactive guests: on the quest to control the spin state by photoisomerization.

Three Hofmann-like metal-organic frameworks {Fe(bpac)[Pt(CN)4]}·G (bpac = 1,2-bis(4-pyridyl)acetylene) were synthesized with photoisomerizable guest molecules (G = trans-azobenzene, trans-stilbene or cis-stilbene) and were characterized by elemental analysis, thermogravimetry and powder X-ray diffraction. The insertion of guest molecules and their conformation were inferred from Raman and FTIR spectra and from single-crystal X-ray diffraction and confronted with computational simulation. The magnetic and photomagnetic behaviors of the framework are significantly altered by the different guest molecules and different conformations. On the other hand, photoisomerization of the guest molecules becomes strongly hindered by the framework.

Low-spin and spin-crossover iron(II) complexes with pyridyl-benzimidazole ligands: synthesis, and structural, magnetic and solution study.

Two tridentate ligands (L1 = 2,6-bis(1-(3,5-di-tert-butylbenzyl)-1H-benzimidazol-2-yl)pyridine and L2 = 2,6-bis(1-(4-tert-butylbenzyl)-1H-benzimidazol-2-yl)pyridine) and one didentate ligand (L3 = 1-(4-tert-butylbenzyl)-2-pyridine-2-yl-1H-benzimidazol) were used for the synthesis of eight mononuclear Fe(ii) compounds 1-8 containing miscellaneous counterions. Single-crystal X-ray diffraction analysis confirmed the expected molecular structures of all the reported coordination compounds and revealed the octahedral geometry of metal centres in the complex dications of 1-8. Compounds 1-6 prepared from tridentate ligands were low-spin and, therefore, diamagnetic up to 400 K. On the other hand, compounds 7 and 8, in which the Fe(ii) centre was coordinated with didentate ligand L3, exhibited temperature and light triggered spin-crossover behaviour. The theoretical calculations supported the experimental magnetic investigation and helped to explain the electronic structures of the reported complexes with respect to the occurrence of thermal and light induced spin state switching. In addition, the solution redox properties of compounds 1-8 were investigated by cyclic voltammetry.

Stereochemistry of coordination polyhedra vs. single ion magnetism in penta- and hexacoordinated Co(ii) complexes with tridentate rigid ligands.

A tridentate ligand L (2,6-bis(1-(3,5-di-tert-butylbenzyl)-1H-benzimidazol-2-yl)pyridine) was synthesized and used for the preparation of three pentacoordinated Co(ii) complexes of formula [Co(L)X2] (where X = NCS- for 1, X = Cl- for 2 and X = Br- for 3) and one ionic compound 4 ([Co(L)2]Br2·2CH3OH·H2O) containing a hexacoordinated Co(ii) centre. Static magnetic data were analysed with respect to the spin (1-3) or the Griffith-Figgis (4) Hamiltonian. Ab initio calculations enable us to identify the positive axial magnetic anisotropy parameter D accompanied by a significant degree of rhombicity in the reported complexes. Also, magneto-structural correlation was outlined for this class of compounds. Moreover, all four compounds exhibit slow relaxation of magnetisation at an applied static magnetic field with either both low- and high-frequency relaxation channels (3) or a single high-frequency relaxation process (1, 2 and 4). The interplay between the stereochemistry of coordination polyhedra, magnetic anisotropy and the relaxation processes was investigated and discussed in detail.

Impact of Substituent Variation on the Presence of Thermal Spin Crossover in a Series of Mononuclear Iron(III) Schiff Base Complexes with Terminal Pseudohalido Co-ligands.

A series of novel iron(III) complexes of the general formula [Fe(L)X] (where L is a dianion of pentadentate Schiff base ligand N,N'-bis({2-hydroxy-3,5-dimethylphenyl}phenyl)methylidene-1,6-diamino-3-azapentane=H2 L1 for 1 and 2; N,N'-bis({2-hydroxy-3-ethoxyphenyl}methylidene)-1,6-diamino-3-azapentane=H2 L2 for 3 and 3⋅C3 H6 O) and X is terminal pseudohalido ligand (X=N3 for 1, X=NCS for 2, and X=NCSe for 3 and 3⋅C3 H6 O) were synthesized and thoroughly characterized. Magnetic measurements revealed the above room temperature spin crossover for isomorphic complexes 1 and 2 (T1/2 =441 K and T1/2 =435 K, respectively), whereas the solvent-free complex 3 showed a half complete spin crossover (T1/2 =250 K), which was detected by variable temperature crystallography as well. On the other hand, solvated complex 3⋅C3 H6 O exhibited permanent high spin state behaviour and either recrystallization or in situ thermal desolvation converts 3⋅C3 H6 O to solvent-free and spin-crossover-active form 3. Magnetic properties of all the reported complexes were also supported by EPR spectroscopy experiments and in addition, DFT and ab initio calculations were employed for the evaluation of the g-factor and zero field splitting parameters.