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• W2045349169 abstract "The synthesis, crystal structures and magnetic properties of two hexanuclear Fe6 clusters of general formula [Fe6(O)2(OH)2(O2CR)10(dipaH2)2]·xMeCN.yH2O (R = Ph, x = 5.5, y = 1 (1), R = C(Me)3, x = 2, y = 3 (2)) are reported. The presence of the flexible amino-alcohol ligand diisopropanolamine (dipaH3) induces the dimerisation of two trinuclear FeIII complexes, [Fe3O(O2CPh)6(H2O)3](NO3) and [Fe3O(O2CC(Me)3)6(H2O)3](O2CC(Me)3), to form the hexanuclear clusters 1 and 2. DC magnetic susceptibility measurements on 1 and 2 assign ground spin states of S = 5, with zero-field splitting parameters (D) of ca. 0.25 cm−1 obtained from magnetisation isotherms. AC susceptibilities showed no maxima as a function of frequency, at low temperatures, and this confirmed the lack of single-molecule magnetic behaviour. Clusters 1 and 2 are isostructural, consisting of two fused {Fe3O} trinuclear units, bridged in two positions by one μ2-OH− unit and two μ2-O2CR− bridging carboxylates (R = Ph (1), C(Me)3(2)). The two singly deprotonated dipaH2− bridging ligands span the Fe1–Fe2 edges in 1 and 2via one μ2-bridging alcohol arm and one terminal nitrogen atom while the second alcohol arm remains free. The ground spin state of S = 5 in 1 and 2 can be attributed to the presence of spin frustration within the system. 1 and 2 join a small family of spin frustrated S = 5 Fe6 systems the magnetism of which give weight to a recent report that it is the trans position of the two shortest Fe2 pair frustrated exchange pathways in these Fe6 clusters that gives rise to a ground spin state of S = 5 (trans) and not a ground spin state of S = 0 (cis). The Mössbauer spectra of 1 and 2 show two quadrupole doublets, as expected, at 295 K, but a broad asymmetric lineshape at 77 K. The synthesis and magnetic properties of {[CoII3CoIII(OH)(O2CC(Me)3)4(HO2CC(Me)3)2(dipaH)2]·2MeCN}n (3) are reported. 3 is a covalently bonded 1D polymer of tetrameric cobalt clusters. The presence of the dipaH3 ligand here not only dimerises the [CoII2(μ-H2O)(O2CC(Me)3)4(HO2CC(Me)3)4] starting complex into the tetranuclear species but also polymerises the [CoII3CoIII] clusters in 3 by acting as the propagating ligand in the 1D chain. Magnetic susceptibility measurements on 3 show each [Co4] moiety exhibits weak antiferromagnetic coupling between the three CoIIS = 3/2 metal centres and fitted J values are given. The ambiguity in assignment of the spin ground state of S = 1/2 or 3/2 is discussed." @default.
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• W2045349169 date "2005-01-01" @default.
• W2045349169 modified "2023-10-09" @default.
• W2045349169 title "The role of diisopropanolamine (dipaH3) in cluster dimerisation and polymerisation: from spin frustrated S= 5 FeIII6 clusters to the novel 1-D covalent polymer of mixed valence [CoII3CoIII] tetramers" @default.
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• W2045349169 doi "https://doi.org/10.1039/b504270d" @default.
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