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Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.

ABSTRACT: Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18-c-6 produces [{K(18-c-6)}HAN], which contains the S=1/2 radical [HAN](.-) . The [HAN](.-) radical can be transferred to the cobalt(II) amide [Co{N(SiMe3 )2 }2 ], forming [K(18-c-6)][(HAN){Co(N'')2 }3 ]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt-ligand antiferromagnetic exchange and J?-290?cm(-1) (-2?J formalism). In contrast, the Co(II) centres in the unreduced analogue [(HAN){Co(N'')2 }3 ] are weakly coupled (J?-4.4?cm(-1) ). The finding that [HAN](.-) can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks.

SUBMITTER: Moilanen JO

PROVIDER: S-EPMC5071680 | biostudies-literature | 2016 Apr

REPOSITORIES: biostudies-literature

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Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.

Moilanen Jani O JO Chilton Nicholas F NF Day Benjamin M BM Pugh Thomas T Layfield Richard A RA

Angewandte Chemie (International ed. in English) 20160321 18

Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18-c-6 produces [{K(18-c-6)}HAN], which contains the S=1/2 radical [HAN](.-) . The [HAN](.-) radical can be transferred to the cobalt(II) amide [Co{N(SiMe3 )2 }2 ], forming [K(18-c-6)][(HAN){Co(N'')2 }3 ]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt-ligand antiferromagnetic exchange and J≈-290 cm(-1) (-2 J formalism). In contrast, the Co(II) centres in the unreduced analogue [(HAN){Co(N ...[more]

PMID: 26997130

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Project description:The ability of tetraazalene radical bridging ligands to mediate exceptionally strong magnetic exchange coupling across a range of transition metal complexes is demonstrated. The redox-active bridging ligand N,N',N'',N'''-tetra(2-methylphenyl)-2,5-diamino-1,4-diiminobenzoquinone (NMePhLH2) was metalated to give the series of dinuclear complexes [(TPyA)2M2(NMePhL2-)]2+ (TPyA = tris(2-pyridylmethyl)amine, M = MnII, FeII, CoII). Variable-temperature dc magnetic susceptibility data for these complexes reveal the presence of weak superexchange interactions between metal centers, and fits to the data provide coupling constants of J = -1.64(1) and -2.16(2) cm-1 for M = MnII and FeII, respectively. One-electron reduction of the complexes affords the reduced analogues [(TPyA)2M2(NMePhL3-˙)]+. Following a slightly different synthetic procedure, the related complex [(TPyA)2CrIII2(NMePhL3-˙)]3+ was obtained. X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy indicate the presence of radical NMePhL3-˙ bridging ligands in these complexes. Variable-temperature dc magnetic susceptibility data of the radical-bridged species reveal the presence of strong magnetic interactions between metal centers and ligand radicals, with simulations to data providing exchange constants of J = -626(7), -157(7), -307(9), and -396(16) cm-1 for M = CrIII, MnII, FeII, and CoII, respectively. Moreover, the strength of magnetic exchange in the radical-bridged complexes increases linearly with decreasing M-L bond distance in the oxidized analogues. Finally, ac magnetic susceptibility measurements reveal that [(TPyA)2Fe2(NMePhL3-˙)]+ behaves as a single-molecule magnet with a relaxation barrier of Ueff = 52(1) cm-1. These results highlight the ability of redox-active tetraazalene bridging ligands to enable dramatic enhancement of magnetic exchange coupling upon redox chemistry and provide a rare opportunity to examine metal-radical coupling trends across a transmetallic series of complexes.

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Dataset Information

Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.

Publications

Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.

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