2015
DOI: 10.1021/jacs.5b09378
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Abstract: The syntheses, structures, and magnetic properties of four new complex salts, (PPN){[Mn(III)(salphen)(MeOH)]2[M(III)(CN)6]}·7MeOH (Mn2M·7MeOH) (M = Fe, Ru, Os and Co; PPN(+) = bis(triphenylphosphoranylidene)ammonium cation; H2salphen = N,N'-bis(salicylidene)-1,2-diaminobenzene), and a mixed metal Co/Os analogue (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)0.92Os(III)0.08(CN)6]}·7MeOH were undertaken. It was found that all compounds exhibit switchable single-molecule magnet (SMM) and exchange-bias behavior depending … Show more

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Cited by 123 publications
(76 citation statements)
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“…We have tried to prepare the LD assemblies involving [Re(CN) 7 ] 3− using the same cation metathesis employed in Ref. [34], where bis(triphenyl-phosphoranylidene)ammonium (PPN) cation was used to obtain trinuclear SMMs, PPN [(Mn III salphenMeOH) 2 [37,38].…”
Section: Synthetic Approachesmentioning
confidence: 99%
“…We have tried to prepare the LD assemblies involving [Re(CN) 7 ] 3− using the same cation metathesis employed in Ref. [34], where bis(triphenyl-phosphoranylidene)ammonium (PPN) cation was used to obtain trinuclear SMMs, PPN [(Mn III salphenMeOH) 2 [37,38].…”
Section: Synthetic Approachesmentioning
confidence: 99%
“…Paramagnetic orbitally degenerate hexacyanometalates of Ru and Os possessing high magnetic anisotropy are already known and have been used in the design of a few low‐dimensional magnetic materials displaying slow relaxation of magnetization (SMM and SCM) on the basis of the heterometallic unit [Mn III –NC–{Os/Ru} III –CN–Mn III ]. As demonstrated in recent studies,20,23,26,27 the magnetic properties of cyanometalate‐based molecular nanomagntes largely depend on mutual separation of the paramagnetic molecules and the bending angle in the heterometallic Mn III –NC–M pair that can be tuned by employing different counterions and/or solvent molecules of various sizes and shapes. For this reason, the availability of a great variety of precursors is essential.…”
Section: Introductionmentioning
confidence: 98%
“…In this respect, the heavier counterparts of hexacyanoferrate(III), for example, [Ru III (CN) 6 ] 3– and [Os III (CN) 6 ] 3– , are more attractive anisotropic constituents than [Fe III (CN) 6 ] 3– owing to much stronger spin–orbit coupling energy (which generally favors unquenched orbital momentum) and more diffuse magnetic orbitals (which results in larger magnetic spin coupling J ) 14. There are only a few examples of materials based on [Ru III (CN) 6 ] 3– and [Os III (CN) 6 ] 3– building blocks,17–25 including two trigonal bipyramidal clusters [M II (tmphen) 2 ] 3 [Os III (CN) 6 ] · solvent (M = Fe, Ni; tmphen = 3,4,7,8‐tetramethyl‐1,10‐phenanthroline),17,18 two Prussian blue analogues M II 3 [Os III (CN) 6 ] 2 · n H 2 O (M = Co, Ni),18,19 four SMMs involving Mn III complexes,2024 and only one SCM25 of the type (Ph 4 P) 2 [Mn(acacen)][Os(CN) 6 ] [acacen = N , N′ ‐bis(acetylacetone)ethylenediaminato]. It was recently shown that incorporation of [Ru III (CN) 6 ] 3– or [Os III (CN) 6 ] 3– complexes in Mn III –NC–M III –CN–Mn III trinuclear complexes considerably increases the SMM spin‐reversal barrier U eff relative to that of the Mn III –NC–Fe III –CN–Mn III SMM cluster 23,20.…”
Section: Introductionmentioning
confidence: 99%
“…Further, the possibility of incorporating two different benzylidene moieties and diamine backbones [3] provides access to a large variety of salen/salophen ligands that, after deprotonation of both phenolic oxygens, can form rather stable complexes with many transition and main group metals, with different oxidation states, coordination numbers and geometries that have shown interesting applications in many fields [4][5][6][7][8][9]. Recently also an extensive use of metal complexes with salen and salophen ligands has been reported in the design of new magnetic materials [10,11]. The metal, i.e., Manganese, coordinated to Schiff base can transmit chiral information inducing subtle conformational effects, while high-stereoselectivity can be achieved during the reaction by controlling the direction of the substrate approach ( Figure 2).…”
Section: Introductionmentioning
confidence: 99%