Spin switching via targeted structural distortion

C.J. Milios; A. Prescimone; P.A. Wood; S. Parsons; E.K. Brechin; A. Vinslava; W. Wernsdorfer; G. Christou; S.P. Perlepes

doi:10.1021/ja070411g

Spin switching via targeted structural distortion

C.J. Milios, A. Prescimone, P.A. Wood, S. Parsons, E.K. Brechin, A. Vinslava, W. Wernsdorfer, G. Christou, S.P. Perlepes

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Abstract / Description of output

The deliberate "stepwise" structural distortion of the [Mn O(sao)(OCR) L] (S = 4, U = 28 K) family of SMMs (where sao is the dianion of salicylaldoxime or 2-hydroxybenzaldeyhyde oxime and L = MeOH, EtOH) via the use of derivatized oxime ligands and bulky carboxylates leads to a family of single-molecule magnets with larger spin ground states and enhanced blocking temperatures. Replacing sao and HCO in the molecule [MnO (sao)(OCH)(MeOH)] (1), with Et-sao (Et-saoH = 2-hydroxypropiophenone oxime) and MeCCO (pivalate), produces the complex [MnO(Et-sao)(O -CCMe)(EtOH)] (2) that displays an S = 7 ground state with U = 30 K. Replacing Me CCO with PhCO produces the complex [MnO(Et-sao)(O CPh)(EtOH)(HO)] (3) that displays an S = 12 ground state with U = 53 K. The ligand substitution invokes a subtle structural distortion to the core of the molecule evidenced by an increased "twisting" of the oxime moiety (Mn-N-O-Mn) and a change in carboxylate ligation, which, in turn, invokes a dramatic change in the observed magnetic properties by switching weak antiferromagnetic exchange to weak ferromagnetic exchange.

Original language	English
Pages (from-to)	6547-6561
Number of pages	15
Journal	Journal of the American Chemical Society
Volume	129
Issue number	20
DOIs	https://doi.org/10.1021/ja070411g
Publication status	Published - 23 May 2007

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title = "Spin switching via targeted structural distortion",

abstract = "The deliberate {"}stepwise{"} structural distortion of the [Mn O(sao)(OCR) L] (S = 4, U = 28 K) family of SMMs (where sao is the dianion of salicylaldoxime or 2-hydroxybenzaldeyhyde oxime and L = MeOH, EtOH) via the use of derivatized oxime ligands and bulky carboxylates leads to a family of single-molecule magnets with larger spin ground states and enhanced blocking temperatures. Replacing sao and HCO in the molecule [MnO (sao)(OCH)(MeOH)] (1), with Et-sao (Et-saoH = 2-hydroxypropiophenone oxime) and MeCCO (pivalate), produces the complex [MnO(Et-sao)(O -CCMe)(EtOH)] (2) that displays an S = 7 ground state with U = 30 K. Replacing Me CCO with PhCO produces the complex [MnO(Et-sao)(O CPh)(EtOH)(HO)] (3) that displays an S = 12 ground state with U = 53 K. The ligand substitution invokes a subtle structural distortion to the core of the molecule evidenced by an increased {"}twisting{"} of the oxime moiety (Mn-N-O-Mn) and a change in carboxylate ligation, which, in turn, invokes a dramatic change in the observed magnetic properties by switching weak antiferromagnetic exchange to weak ferromagnetic exchange.",

author = "C.J. Milios and A. Prescimone and P.A. Wood and S. Parsons and E.K. Brechin and A. Vinslava and W. Wernsdorfer and G. Christou and S.P. Perlepes",

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AU - Milios, C.J.

AU - Prescimone, A.

AU - Wood, P.A.

AU - Parsons, S.

AU - Brechin, E.K.

AU - Vinslava, A.

AU - Wernsdorfer, W.

AU - Christou, G.

AU - Perlepes, S.P.

PY - 2007/5/23

Y1 - 2007/5/23

N2 - The deliberate "stepwise" structural distortion of the [Mn O(sao)(OCR) L] (S = 4, U = 28 K) family of SMMs (where sao is the dianion of salicylaldoxime or 2-hydroxybenzaldeyhyde oxime and L = MeOH, EtOH) via the use of derivatized oxime ligands and bulky carboxylates leads to a family of single-molecule magnets with larger spin ground states and enhanced blocking temperatures. Replacing sao and HCO in the molecule [MnO (sao)(OCH)(MeOH)] (1), with Et-sao (Et-saoH = 2-hydroxypropiophenone oxime) and MeCCO (pivalate), produces the complex [MnO(Et-sao)(O -CCMe)(EtOH)] (2) that displays an S = 7 ground state with U = 30 K. Replacing Me CCO with PhCO produces the complex [MnO(Et-sao)(O CPh)(EtOH)(HO)] (3) that displays an S = 12 ground state with U = 53 K. The ligand substitution invokes a subtle structural distortion to the core of the molecule evidenced by an increased "twisting" of the oxime moiety (Mn-N-O-Mn) and a change in carboxylate ligation, which, in turn, invokes a dramatic change in the observed magnetic properties by switching weak antiferromagnetic exchange to weak ferromagnetic exchange.

AB - The deliberate "stepwise" structural distortion of the [Mn O(sao)(OCR) L] (S = 4, U = 28 K) family of SMMs (where sao is the dianion of salicylaldoxime or 2-hydroxybenzaldeyhyde oxime and L = MeOH, EtOH) via the use of derivatized oxime ligands and bulky carboxylates leads to a family of single-molecule magnets with larger spin ground states and enhanced blocking temperatures. Replacing sao and HCO in the molecule [MnO (sao)(OCH)(MeOH)] (1), with Et-sao (Et-saoH = 2-hydroxypropiophenone oxime) and MeCCO (pivalate), produces the complex [MnO(Et-sao)(O -CCMe)(EtOH)] (2) that displays an S = 7 ground state with U = 30 K. Replacing Me CCO with PhCO produces the complex [MnO(Et-sao)(O CPh)(EtOH)(HO)] (3) that displays an S = 12 ground state with U = 53 K. The ligand substitution invokes a subtle structural distortion to the core of the molecule evidenced by an increased "twisting" of the oxime moiety (Mn-N-O-Mn) and a change in carboxylate ligation, which, in turn, invokes a dramatic change in the observed magnetic properties by switching weak antiferromagnetic exchange to weak ferromagnetic exchange.

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Spin switching via targeted structural distortion

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