A Charge-Transfer-Induced Spin Transition in the Discrete Cyanide-Bridged Complex {[Co(tmphen)2]3[Fe(CN)6]2}

Berlinguette, Curtis P.; Dragulescu‐Andrasi, Alina; Sieber, Andreas; Galán‐Mascarós, José Ramón; Güdel, Hans‐Ulrich; Achim, Catalina; Dunbar, Kim R.

doi:10.1021/ja039451k

Cited by 211 publications

(151 citation statements)

References 21 publications

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“…However, introduction of ligands with weak ligand-field strengths and combinations of heterometal ions afford interesting magnetic properties such as spin crossover, [5] photoinduced magnetism, [6] and superparamagnetism. [7] Furthermore, molecules with more than one spin-crossover site can be used as multistepped molecular switches.…”

Section: Molecular Switchesmentioning

confidence: 99%

Two‐Step Spin Conversion in a Cyanide‐Bridged Ferrous Square

et al. 2005

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Molecules with many spin-crossover sites could be used as multistepped molecular switches. The CNbridged molecular square [Fe II 4 (m-CN) 4 (bpy) 4 (tpa) 4 ](PF 6 ) 4 (bpy = 2,2'-bipyridine; tpa = tris(2-pyridylmethyl)amine), a Prussian blue analogue, undergoes thermally induced, two-step spin conversion. For more information, see the Communication by H. Oshio and co-workers on the following pages.

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Section: Molecular Switchesmentioning

confidence: 99%

Two‐Step Spin Conversion in a Cyanide‐Bridged Ferrous Square

et al. 2005

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“…[4] Over the last decade, research in this area has produced coordination polymers and multinuclear clusters with diverse and interesting properties such as photoinduced magnetism, [5,6] single-molecule magnetism, [7][8][9][10][11][12][13] spin crossover, [14][15][16][17] and charge transfer induced spin transition. [18,19] With few exceptions, the cyanide containing precursor in the aforementioned chemistry is a homoleptic hexacyanometalate anion. Cyanometalates with coordination numbers other than six have been used much less frequently.…”

Section: Introductionmentioning

confidence: 99%

Variation of Heterometallic Structural Motifs Based on [W(CN)₈]³⁻ Anions and Mn^II Ions as a Function of Synthetic Conditions

Zhao

Shatruk

Prosvirin

et al. 2007

Chemistry A European J

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Reactions of [W(CN)(8)](3-/4-) anions with complexes of Mn(2+) ion with tridentate organic ligand 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) lead to a series of heterobimetallic complexes. The crystal structures of these compounds are derived from the same basic structural fragment, namely a W(2)Mn(2) square constructed of alternating cyanide-bridged W and Mn ions. In [Mn(II)(tptz)(OAc)(H(2)O)(2)](2){[Mn(II)(tptz)(MeOH)(1.58)(H(2)O)(0.42)](2)[W(V)(CN)(8)](2)}.5 MeOH.9.85 H(2)O (3), isolated molecular squares are co-crystallized with mononuclear cationic Mn(II) complexes. The structure of {[Mn(II)(tptz)(MeOH)](2)[W(IV)(CN)(8)].2 MeOH}(infinity) (4) is based on an infinite chain of vertex-sharing squares, while {[Mn(II) (2)(tptz)(2)(MeOH)(3)(OAc)][W(V)(CN)(8)].3.5 MeOH0.25 H(2)O}(infinity) (5) and {[Mn(II) (2)(tptz)(2)(MeOH)(3)W(V)(CN)(8)][Mn(II)(tptz)(MeOH)W(V)(CN)(8)].2 H(2).OMeOH}(8) (7) are derived from such an infinite chain by removing one of the W-C[triple bond]N-Mn linkages in each of the squares. The decanuclear cluster [Mn(II) (6)(tptz)(6)(MeOH)(4)(DMF)(2)W(V) (4)(CN)(32)].8.2 H(2)O.2.3 MeOH (6) is a truncated version of structure 4 and consists of three vertex-sharing W(2)Mn(2) squares. The structure of [Mn(II)(tptz)(MeOH)(NO(3))](2)[Mn(II)(tptz)(MeOH) (DMF)](2)[W(V)(CN)(8)](2).6 MeOH (8) consists of a hexanuclear cluster, in which the central W(2)Mn(2) square is extended by two Mn side-arms attached via CN(-) ligands to the W corners of the square. The magnetic behavior of these heterobimetallic complexes (except for 4) is dominated by antiferromagnetic coupling between Mn(II) and W(V) ions mediated by cyanide bridges. Compounds 3, 6, and 8 exhibit high spin ground states of S=4, 13, and 9, respectively, while 5 and 7 exhibit behavior typical of a ferrimagnetic chain with alternating spin centers. Complex 4 contains diamagnetic W(IV) centers but holds promise as a potential photomagnetic solid.

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“…(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) family associates [M(CN) 6 ] n-building-block anions (M = divalent or trivalent first-row transition metal ion) and cationic assembling units of the general formula [MЈL x -(H 2 O) m ] n+ (MЈ = divalent first row transition metal ion; L = polyamine, macrocyclic ligand, Schiff base, ...) having selected free coordination sites, instead of simple hexa-solvated complexes; [8][9][10][11] anions. [12,13] In both families, a large number of such lowsymmetry cyano-bridged assemblies display rich and fascinating structural architectures ranging from discrete polynuclear complexes [11,13] to extended 3D networks, [8][9][10]12] and in some cases exhibit interesting properties such as high n-units, most of the materials are extended bimetallic compounds having a three-or four-coordinate [MЈL x ] 2+ assembling block which constrains the number of adjacent hexacyanometalate building blocks to two and/or a limited dimensionality of two.…”

Section: Introductionmentioning

confidence: 99%

New, Multi‐Dimensional Cu(tn)‐[M(CN)₆]^n– Cyano‐Bridged, Bimetallic Coordination Materials (M = Fe^II, Co^III, Cr^III and tn = 1,3‐Diaminopropane)

et al. 2005

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International audienceReaction of the [FeIII(CN)6]3– anion with [CuII(tn)(H2O)n]2+ (tn = 1,3-diaminopropane) affords the compounds [{CuII(tn)}2{FeII(CN)6}]·KCl·5H2O (1), [{CuII(tn)}2{FeII(CN)6}]·4H2O (2), and [{CuII(tnH)2(H2O)2}{FeII(CN)6}]·2H2O (3). Each iron center in 1 and 2 is linked to six copper(II) ions by six cyanide bridges, while each copper ion is linked to three equivalent iron(II) ions. Despite these resemblances, the two compounds present large structural differences caused by two different orientations of the Cu–NC–Fe bridges: compound 1 has a 2D structure which can be described as successions of “Cu4Fe3” defective cubane units, while compound 2 displays a 3D arrangement. Compound 3, in which only two trans-CN groups are bridging, displays a 1D structure. The tn ligand is chelating in 1, as is usually observed in several parent compounds, but is unexpectedly a bridging ligand in 2 and a terminal protonated tnH+ ligand in 3. Thus, the dimension of the three compounds seems to depend on the tn coordination modes. For the three iron compounds 1–3, the synthetic processes involve the spontaneous reduction of the paramagnetic [FeIII(CN)6]3– anion into the diamagnetic [FeII(CN)6]4– anion. In order to avoid such diamagnetic building blocks, the paramagnetic [Cr(CN)6]3– anion was used instead of the iron(III) analog, leading to [{CuII(tn)}3{CrIII(CN)6}2]·3H2O (4), which is the first 2D ferromagnet containing “-Cu–NC–Cr-” linkages. A similar study was performed using the diamagnetic [Co(CN)6]3– anion, leading to [{CuII(tn)}3{CoIII(CN)6}2]·3H2O (5), which is the Co analog of 4. The magnetic properties of compounds 1–3 and 5 show the presence of isolated CuII ions with weak ferromagnetic (1) or antiferromagnetic (2, 3, and 5) interactions. Compound 4 presents a long-range ferromagnetic ordering below Tc = 9.5 K

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A Charge-Transfer-Induced Spin Transition in the Discrete Cyanide-Bridged Complex {[Co(tmphen)₂]₃[Fe(CN)₆]₂}

Cited by 211 publications

References 21 publications

Two‐Step Spin Conversion in a Cyanide‐Bridged Ferrous Square

Two‐Step Spin Conversion in a Cyanide‐Bridged Ferrous Square

Variation of Heterometallic Structural Motifs Based on [W(CN)₈]³⁻ Anions and Mn^II Ions as a Function of Synthetic Conditions

New, Multi‐Dimensional Cu(tn)‐[M(CN)₆]^n– Cyano‐Bridged, Bimetallic Coordination Materials (M = Fe^II, Co^III, Cr^III and tn = 1,3‐Diaminopropane)

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A Charge-Transfer-Induced Spin Transition in the Discrete Cyanide-Bridged Complex {[Co(tmphen)2]3[Fe(CN)6]2}

Cited by 211 publications

References 21 publications

Two‐Step Spin Conversion in a Cyanide‐Bridged Ferrous Square

Two‐Step Spin Conversion in a Cyanide‐Bridged Ferrous Square

Variation of Heterometallic Structural Motifs Based on [W(CN)8]3− Anions and MnII Ions as a Function of Synthetic Conditions

New, Multi‐Dimensional Cu(tn)‐[M(CN)6]n– Cyano‐Bridged, Bimetallic Coordination Materials (M = FeII, CoIII, CrIII and tn = 1,3‐Diaminopropane)

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A Charge-Transfer-Induced Spin Transition in the Discrete Cyanide-Bridged Complex {[Co(tmphen)₂]₃[Fe(CN)₆]₂}

Variation of Heterometallic Structural Motifs Based on [W(CN)₈]³⁻ Anions and Mn^II Ions as a Function of Synthetic Conditions

New, Multi‐Dimensional Cu(tn)‐[M(CN)₆]^n– Cyano‐Bridged, Bimetallic Coordination Materials (M = Fe^II, Co^III, Cr^III and tn = 1,3‐Diaminopropane)