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result sql = Synthesis and characterization of homo- and heterodinuclear M(II)-M'(III) (M(II) = Mn or Fe, M'(III) = Fe or Co) mixed-valence supramolecular pseudo-dimers. The effect of hydrogen bonding on spin state selection of M(II).
Synthesis and characterization of homo- and heterodinuclear M(II)-M'(III) (M(II) = Mn or Fe, M'(III) = Fe or Co) mixed-valence supramolecular pseudo-dimers. The effect of hydrogen bonding on spin state selection of M(II).
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char = e;code = 101
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = p;code = 112
char = r;code = 114
char = e;code = 101
char = p;code = 112
char = a;code = 97
char = r;code = 114
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = b;code = 98
char = y;code = 121
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char = t;code = 116
char = h;code = 104
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char = ;code = 32
char = a;code = 97
char = e;code = 101
char = r;code = 114
char = o;code = 111
char = b;code = 98
char = i;code = 105
char = c;code = 99
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char = r;code = 114
char = e;code = 101
char = a;code = 97
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
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char = o;code = 111
char = f;code = 102
char = ;code = 32
char = [;code = 91
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char = e;code = 101
char = H;code = 72
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char = 3;code = 51
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char = L;code = 76
char = (;code = 40
char = 1;code = 49
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char = ];code = 93
char = (;code = 40
char = B;code = 66
char = F;code = 70
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ;code = 32
char = w;code = 119
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char = t;code = 116
char = h;code = 104
char = ;code = 32
char = 1;code = 49
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char = e;code = 101
char = q;code = 113
char = u;code = 117
char = i;code = 105
char = v;code = 118
char = a;code = 97
char = l;code = 108
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = s;code = 115
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char = o;code = 111
char = f;code = 102
char = ;code = 32
char = p;code = 112
char = o;code = 111
char = t;code = 116
char = a;code = 97
char = s;code = 115
char = s;code = 115
char = i;code = 105
char = u;code = 117
char = m;code = 109
char = ;code = 32
char = h;code = 104
char = y;code = 121
char = d;code = 100
char = r;code = 114
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char = x;code = 120
char = i;code = 105
char = d;code = 100
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = o;code = 111
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char = g;code = 103
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char = e;code = 101
char = ;code = 32
char = {;code = 123
char = [;code = 91
char = F;code = 70
char = e;code = 101
char = H;code = 72
char = (;code = 40
char = 1;code = 49
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char = L;code = 76
char = (;code = 40
char = 1;code = 49
char = );code = 41
char = ];code = 93
char = (;code = 40
char = B;code = 66
char = F;code = 70
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = );code = 41
char = };code = 125
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ;code = 32
char = o;code = 111
char = r;code = 114
char = ;code = 32
char = b;code = 98
char = y;code = 121
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = m;code = 109
char = e;code = 101
char = t;code = 116
char = a;code = 97
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = s;code = 115
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = a;code = 97
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = [;code = 91
char = F;code = 70
char = e;code = 101
char = H;code = 72
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = L;code = 76
char = (;code = 40
char = 1;code = 49
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char = ];code = 93
char = [;code = 91
char = F;code = 70
char = e;code = 101
char = H;code = 72
char = L;code = 76
char = (;code = 40
char = 1;code = 49
char = );code = 41
char = ];code = 93
char = (;code = 40
char = C;code = 67
char = l;code = 108
char = O;code = 79
char = (;code = 40
char = 4;code = 52
char = );code = 41
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ;code = 32
char = w;code = 119
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char = t;code = 116
char = h;code = 104
char = ;code = 32
char = s;code = 115
char = o;code = 111
char = d;code = 100
char = i;code = 105
char = u;code = 117
char = m;code = 109
char = ;code = 32
char = h;code = 104
char = e;code = 101
char = x;code = 120
char = a;code = 97
char = f;code = 102
char = l;code = 108
char = u;code = 117
char = o;code = 111
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char = o;code = 111
char = p;code = 112
char = h;code = 104
char = o;code = 111
char = s;code = 115
char = p;code = 112
char = h;code = 104
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = g;code = 103
char = i;code = 105
char = v;code = 118
char = e;code = 101
char = ;code = 32
char = [;code = 91
char = F;code = 70
char = e;code = 101
char = H;code = 72
char = (;code = 40
char = 3;code = 51
char = );code = 41
char = L;code = 76
char = (;code = 40
char = 1;code = 49
char = );code = 41
char = ];code = 93
char = [;code = 91
char = F;code = 70
char = e;code = 101
char = L;code = 76
char = (;code = 40
char = 1;code = 49
char = );code = 41
char = ];code = 93
char = (;code = 40
char = P;code = 80
char = F;code = 70
char = (;code = 40
char = 6;code = 54
char = );code = 41
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = c;code = 99
char = o;code = 111
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char = p;code = 112
char = l;code = 108
char = e;code = 101
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char = e;code = 101
char = s;code = 115
char = ;code = 32
char = w;code = 119
char = e;code = 101
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = c;code = 99
char = h;code = 104
char = a;code = 97
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char = a;code = 97
char = c;code = 99
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char = e;code = 101
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char = i;code = 105
char = z;code = 122
char = e;code = 101
char = d;code = 100
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char = b;code = 98
char = y;code = 121
char = ;code = 32
char = E;code = 69
char = A;code = 65
char = ,;code = 44
char = ;code = 32
char = I;code = 73
char = R;code = 82
char = ,;code = 44
char = ;code = 32
char = E;code = 69
char = S;code = 83
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char = -;code = 45
char = M;code = 77
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char = ,;code = 44
char = ;code = 32
char = v;code = 118
char = a;code = 97
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char = i;code = 105
char = a;code = 97
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char = l;code = 108
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char = e;code = 101
char = m;code = 109
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char = e;code = 101
char = r;code = 114
char = a;code = 97
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char = u;code = 117
char = r;code = 114
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char = ;code = 32
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char = n;code = 110
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char = l;code = 108
char = e;code = 101
char = ;code = 32
char = c;code = 99
char = r;code = 114
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char = s;code = 115
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char = a;code = 97
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char = -;code = 45
char = r;code = 114
char = a;code = 97
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char = ;code = 32
char = d;code = 100
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char = f;code = 102
char = f;code = 102
char = r;code = 114
char = a;code = 97
char = c;code = 99
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char = o;code = 111
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char = ;code = 32
char = a;code = 97
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char = M;code = 77
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char = 2;code = 50
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char = s;code = 115
char = b;code = 98
char = a;code = 97
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char = e;code = 101
char = r;code = 114
char = ;code = 32
char = s;code = 115
char = p;code = 112
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char = c;code = 99
char = o;code = 111
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char = T;code = 84
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char = a;code = 97
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char = s;code = 115
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char = a;code = 97
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char = a;code = 97
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char = [;code = 91
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char = 1;code = 49
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char = C;code = 67
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char = );code = 41
char = );code = 41
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char = X;code = 88
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char = M;code = 77
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char = I;code = 73
char = I;code = 73
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result sql = Reaction of H(3)L(1), the Schiff base condensate of tris(2-aminoethyl)amine with three equivalents of 5-methyl-1H-pyrazole-3-carboxaldehyde, with manganese(II)perchlorate or iron(II)tetrafluoroborate results in the isolation of [MH(3)L(1)]X(2) (M = Mn and X = ClO(4) and M = Fe and X = BF(4)). These complexes are high spin d(5) and d(6), respectively, as inferred from the long M-N bond distances obtained by single crystal X-ray diffraction for both and variable temperature magnetic susceptibility and Mössbauer spectroscopy for the iron complex. Aerobic treatment of a solution of [CoH(3)L(1)](2+) with three equivalents of potassium hydroxide produced [CoL(1)]. Homonuclear pseudo-dimers were prepared by the aerobic reaction of [FeH(3)L(1)](BF(4))(2) with 1.5 equivalents of potassium hydroxide to give {[FeH(1.5)L(1)](BF(4))}(2) or by the metathesis reaction of [FeH(2)L(1)][FeHL(1)](ClO(4))(2) with sodium hexafluorophosphate to give [FeH(3)L(1)][FeL(1)](PF(6))(2). The complexes were characterized by EA, IR, ESI-MS, variable temperature single crystal x-ray diffraction and Mössbauer spectroscopy. The iron(III) atom is low spin while the iron(II) atom is spin crossover. Heteronuclear pseudo-dimers were prepared by the 1:1 reaction of [FeH(3)L(1)](BF(4))(2) or [MnH(3)L(1)](ClO(4))(2) with [CoL(1)]. [MH(3)L(1)][CoL(1)](X)(2) (M = Fe and X = BF(4) or M = Mn and X = ClO(4)), were characterized by IR, EA, variable temperature single crystal X-ray diffraction and Mössbauer spectroscopy in the iron case. The data support a spin crossover and high spin assignment for the iron(II) and manganese(II), respectively. DFT calculations demonstrate that the spin state of the iron(II) atom in {[FeH(3)L(1)][FeL(1)]}(2+) changes from high spin to low spin as the iron(II)-iron(III) distance decreases. This is supported by experimental results and is a result of hydrogen bonding interactions which cause a significant compression of the M(II)-N(pyrazole) bond distances.

Publication: Dalton Trans 2011 Jan 7 ;40(1)::181-94. :doi: 10.1039/c0dt01098g.
Publication Date: 2011 Jan 7
Study Author(s): Brewer, Cynthia T;Brewer, Greg;Butcher, Ray J;Carpenter, Everett E;Schmiedekamp, Ann M;Schmiedekamp, Carl;Straka, Alison;Viragh, Carol;Yuzefpolskiy, Yevgeniy;Zavalij, Peter;
Institution: The Catholic University, Washington, DC 20064, USA.
Shortcut link to this study:
Reaction of H(3)L(1), the Schiff base condensate of tris(2-aminoethyl)amine with three equivalents of 5-methyl-1H-pyrazole-3-carboxaldehyde, with manganese(II)perchlorate or iron(II)tetrafluoroborate results in the isolation of [MH(3)L(1)]X(2) (M = Mn and X = ClO(4) and M = Fe and X = BF(4)). These complexes are high spin d(5) and d(6), respectively, as inferred from the long M-N bond distances obtained by single crystal X-ray diffraction for both and variable temperature magnetic susceptibility and Mössbauer spectroscopy for the iron complex. Aerobic treatment of a solution of [CoH(3)L(1)](2+) with three equivalents of potassium hydroxide produced [CoL(1)]. Homonuclear pseudo-dimers were prepared by the aerobic reaction of [FeH(3)L(1)](BF(4))(2) with 1.5 equivalents of potassium hydroxide to give {[FeH(1.5)L(1)](BF(4))}(2) or by the metathesis reaction of [FeH(2)L(1)][FeHL(1)](ClO(4))(2) with sodium hexafluorophosphate to give [FeH(3)L(1)][FeL(1)](PF(6))(2). The complexes were characterized by EA, IR, ESI-MS, variable temperature single crystal x-ray diffraction and Mössbauer spectroscopy. The iron(III) atom is low spin while the iron(II) atom is spin crossover. Heteronuclear pseudo-dimers were prepared by the 1:1 reaction of [FeH(3)L(1)](BF(4))(2) or [MnH(3)L(1)](ClO(4))(2) with [CoL(1)]. [MH(3)L(1)][CoL(1)](X)(2) (M = Fe and X = BF(4) or M = Mn and X = ClO(4)), were characterized by IR, EA, variable temperature single crystal X-ray diffraction and Mössbauer spectroscopy in the iron case. The data support a spin crossover and high spin assignment for the iron(II) and manganese(II), respectively. DFT calculations demonstrate that the spin state of the iron(II) atom in {[FeH(3)L(1)][FeL(1)]}(2+) changes from high spin to low spin as the iron(II)-iron(III) distance decreases. This is supported by experimental results and is a result of hydrogen bonding interactions which cause a significant compression of the M(II)-N(pyrazole) bond distances.
PMID: 21103467

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