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char = .;code = 46
result sql = Axial ligand orientations in a distorted porphyrin macrocycle: synthesis, structure, and properties of low-spin bis(imidazole)iron(III) and iron(II) porphyrinates.
Axial ligand orientations in a distorted porphyrin macrocycle: synthesis, structure, and properties of low-spin bis(imidazole)iron(III) and iron(II) porphyrinates.
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char = f;code = 102
char = u;code = 117
char = n;code = 110
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = o;code = 111
char = r;code = 114
char = y;code = 121
char = ;code = 32
char = (;code = 40
char = D;code = 68
char = F;code = 70
char = T;code = 84
char = );code = 41
char = ,;code = 44
char = ;code = 32
char = w;code = 119
char = h;code = 104
char = i;code = 105
char = c;code = 99
char = h;code = 104
char = ;code = 32
char = s;code = 115
char = h;code = 104
char = o;code = 111
char = w;code = 119
char = s;code = 115
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = t;code = 116
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = l;code = 108
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = v;code = 118
char = e;code = 101
char = ;code = 32
char = p;code = 112
char = a;code = 97
char = r;code = 114
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = e;code = 101
char = l;code = 108
char = ;code = 32
char = o;code = 111
char = r;code = 114
char = i;code = 105
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = t;code = 116
char = w;code = 119
char = o;code = 111
char = ;code = 32
char = 1;code = 49
char = -;code = 45
char = M;code = 77
char = e;code = 101
char = I;code = 73
char = m;code = 109
char = ;code = 32
char = a;code = 97
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = m;code = 109
char = o;code = 111
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = s;code = 115
char = t;code = 116
char = a;code = 97
char = b;code = 98
char = l;code = 108
char = e;code = 101
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = n;code = 110
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = p;code = 112
char = e;code = 101
char = r;code = 114
char = p;code = 112
char = e;code = 101
char = n;code = 110
char = d;code = 100
char = i;code = 105
char = c;code = 99
char = u;code = 117
char = l;code = 108
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = o;code = 111
char = r;code = 114
char = i;code = 105
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = s;code = 115
char = .;code = 46
char = ;code = 32
char = X;code = 88
char = -;code = 45
char = r;code = 114
char = a;code = 97
char = y;code = 121
char = ;code = 32
char = s;code = 115
char = t;code = 116
char = r;code = 114
char = u;code = 117
char = c;code = 99
char = t;code = 116
char = u;code = 117
char = r;code = 114
char = e;code = 101
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = F;code = 70
char = e;code = 101
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = );code = 41
char = (;code = 40
char = t;code = 116
char = n;code = 110
char = -;code = 45
char = O;code = 79
char = E;code = 69
char = P;code = 80
char = );code = 41
char = (;code = 40
char = 1;code = 49
char = -;code = 45
char = M;code = 77
char = e;code = 101
char = I;code = 73
char = m;code = 109
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = F;code = 70
char = e;code = 101
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = );code = 41
char = (;code = 40
char = t;code = 116
char = n;code = 110
char = -;code = 45
char = O;code = 79
char = E;code = 69
char = P;code = 80
char = );code = 41
char = (;code = 40
char = 1;code = 49
char = -;code = 45
char = M;code = 77
char = e;code = 101
char = I;code = 73
char = m;code = 109
char = );code = 41
char = (;code = 40
char = 2;code = 50
char = );code = 41
char = .;code = 46
char = T;code = 84
char = H;code = 72
char = F;code = 70
char = ;code = 32
char = a;code = 97
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = p;code = 112
char = o;code = 111
char = r;code = 114
char = t;code = 116
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = t;code = 116
char = ;code = 32
char = d;code = 100
char = e;code = 101
char = m;code = 109
char = o;code = 111
char = n;code = 110
char = s;code = 115
char = t;code = 116
char = r;code = 114
char = a;code = 97
char = t;code = 116
char = e;code = 101
char = ,;code = 44
char = ;code = 32
char = f;code = 102
char = o;code = 111
char = r;code = 114
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = f;code = 102
char = i;code = 105
char = r;code = 114
char = s;code = 115
char = t;code = 116
char = ;code = 32
char = t;code = 116
char = i;code = 105
char = m;code = 109
char = e;code = 101
char = ,;code = 44
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = n;code = 110
char = e;code = 101
char = a;code = 97
char = r;code = 114
char = -;code = 45
char = p;code = 112
char = e;code = 101
char = r;code = 114
char = p;code = 112
char = e;code = 101
char = n;code = 110
char = d;code = 100
char = i;code = 105
char = c;code = 99
char = u;code = 117
char = l;code = 108
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = a;code = 97
char = x;code = 120
char = i;code = 105
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = o;code = 111
char = r;code = 114
char = i;code = 105
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = (;code = 40
char = 8;code = 56
char = 0;code = 48
char = .;code = 46
char = 9;code = 57
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = 8;code = 56
char = 9;code = 57
char = .;code = 46
char = 8;code = 56
char = ;code = 32
char = d;code = 100
char = e;code = 101
char = g;code = 103
char = r;code = 114
char = e;code = 101
char = e;code = 101
char = s;code = 115
char = ,;code = 44
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = s;code = 115
char = p;code = 112
char = e;code = 101
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = v;code = 118
char = e;code = 101
char = l;code = 108
char = y;code = 121
char = );code = 41
char = ;code = 32
char = f;code = 102
char = o;code = 111
char = r;code = 114
char = ;code = 32
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = (;code = 40
char = I;code = 73
char = I;code = 73
char = );code = 41
char = ;code = 32
char = p;code = 112
char = o;code = 111
char = r;code = 114
char = p;code = 112
char = h;code = 104
char = y;code = 121
char = r;code = 114
char = i;code = 105
char = n;code = 110
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = s;code = 115
char = t;code = 116
char = o;code = 111
char = r;code = 114
char = t;code = 116
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = m;code = 109
char = a;code = 97
char = c;code = 99
char = r;code = 114
char = o;code = 111
char = c;code = 99
char = y;code = 121
char = c;code = 99
char = l;code = 108
char = i;code = 105
char = c;code = 99
char = ;code = 32
char = e;code = 101
char = n;code = 110
char = v;code = 118
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = .;code = 46
char = ;code = 32
char = E;code = 69
char = v;code = 118
char = e;code = 101
char = n;code = 110
char = ;code = 32
char = s;code = 115
char = t;code = 116
char = a;code = 97
char = r;code = 114
char = t;code = 116
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = f;code = 102
char = r;code = 114
char = o;code = 111
char = m;code = 109
char = ;code = 32
char = p;code = 112
char = a;code = 97
char = r;code = 114
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = e;code = 101
char = l;code = 108
char = ;code = 32
char = a;code = 97
char = x;code = 120
char = i;code = 105
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = o;code = 111
char = r;code = 114
char = i;code = 105
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = s;code = 115
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = 1;code = 49
char = -;code = 45
char = M;code = 77
char = e;code = 101
char = I;code = 73
char = m;code = 109
char = ,;code = 44
char = ;code = 32
char = g;code = 103
char = e;code = 101
char = o;code = 111
char = m;code = 109
char = e;code = 101
char = t;code = 116
char = r;code = 114
char = y;code = 121
char = ;code = 32
char = o;code = 111
char = p;code = 112
char = t;code = 116
char = i;code = 105
char = m;code = 109
char = i;code = 105
char = z;code = 122
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = u;code = 117
char = s;code = 115
char = i;code = 105
char = n;code = 110
char = g;code = 103
char = ;code = 32
char = D;code = 68
char = F;code = 70
char = T;code = 84
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = n;code = 110
char = v;code = 118
char = e;code = 101
char = r;code = 114
char = g;code = 103
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = w;code = 119
char = e;code = 101
char = l;code = 108
char = l;code = 108
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = p;code = 112
char = e;code = 101
char = r;code = 114
char = p;code = 112
char = e;code = 101
char = n;code = 110
char = d;code = 100
char = i;code = 105
char = c;code = 99
char = u;code = 117
char = l;code = 108
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = a;code = 97
char = x;code = 120
char = i;code = 105
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = a;code = 97
char = l;code = 108
char = i;code = 105
char = g;code = 103
char = n;code = 110
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = 8;code = 56
char = 2;code = 50
char = .;code = 46
char = 5;code = 53
char = 4;code = 52
char = ;code = 32
char = d;code = 100
char = e;code = 101
char = g;code = 103
char = r;code = 114
char = e;code = 101
char = e;code = 101
char = ;code = 32
char = d;code = 100
char = i;code = 105
char = h;code = 104
char = e;code = 101
char = d;code = 100
char = r;code = 114
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = a;code = 97
char = n;code = 110
char = g;code = 103
char = l;code = 108
char = e;code = 101
char = ,;code = 44
char = ;code = 32
char = w;code = 119
char = h;code = 104
char = i;code = 105
char = c;code = 99
char = h;code = 104
char = ;code = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = c;code = 99
char = l;code = 108
char = o;code = 111
char = s;code = 115
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = g;code = 103
char = r;code = 114
char = e;code = 101
char = e;code = 101
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = ;code = 32
char = e;code = 101
char = x;code = 120
char = p;code = 112
char = e;code = 101
char = r;code = 114
char = i;code = 105
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = .;code = 46
char = ;code = 32
char = T;code = 84
char = h;code = 104
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = s;code = 115
char = h;code = 104
char = a;code = 97
char = r;code = 114
char = p;code = 112
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = n;code = 110
char = t;code = 116
char = r;code = 114
char = a;code = 97
char = s;code = 115
char = t;code = 116
char = ;code = 32
char = t;code = 116
char = o;code = 111
char = ;code = 32
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = ;code = 32
char = e;code = 101
char = a;code = 97
char = r;code = 114
char = l;code = 108
char = i;code = 105
char = e;code = 101
char = r;code = 114
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = p;code = 112
char = o;code = 111
char = r;code = 114
char = t;code = 116
char = s;code = 115
char = ,;code = 44
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = w;code = 119
char = h;code = 104
char = i;code = 105
char = c;code = 99
char = h;code = 104
char = ;code = 32
char = s;code = 115
char = t;code = 116
char = e;code = 101
char = r;code = 114
char = i;code = 105
char = c;code = 99
char = a;code = 97
char = l;code = 108
char = l;code = 108
char = y;code = 121
char = ;code = 32
char = c;code = 99
char = r;code = 114
char = o;code = 111
char = w;code = 119
char = d;code = 100
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = i;code = 105
char = m;code = 109
char = i;code = 105
char = d;code = 100
char = a;code = 97
char = z;code = 122
char = o;code = 111
char = l;code = 108
char = e;code = 101
char = ;code = 32
char = (;code = 40
char = s;code = 115
char = u;code = 117
char = c;code = 99
char = h;code = 104
char = ;code = 32
char = a;code = 97
char = s;code = 115
char = ;code = 32
char = 2;code = 50
char = -;code = 45
char = M;code = 77
char = e;code = 101
char = I;code = 73
char = m;code = 109
char = );code = 41
char = ;code = 32
char = o;code = 111
char = r;code = 114
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = n;code = 110
char = e;code = 101
char = a;code = 97
char = r;code = 114
char = l;code = 108
char = y;code = 121
char = ;code = 32
char = p;code = 112
char = l;code = 108
char = a;code = 97
char = n;code = 110
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = p;code = 112
char = o;code = 111
char = r;code = 114
char = p;code = 112
char = h;code = 104
char = y;code = 121
char = r;code = 114
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = r;code = 114
char = e;code = 101
char = ;code = 32
char = w;code = 119
char = i;code = 105
char = t;code = 116
char = h;code = 104
char = ;code = 32
char = a;code = 97
char = ;code = 32
char = ";code = 34
char = p;code = 112
char = i;code = 105
char = c;code = 99
char = k;code = 107
char = e;code = 101
char = t;code = 116
char = ;code = 32
char = f;code = 102
char = e;code = 101
char = n;code = 110
char = c;code = 99
char = e;code = 101
char = ";code = 34
char = ;code = 32
char = e;code = 101
char = n;code = 110
char = v;code = 118
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = m;code = 109
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = a;code = 97
char = t;code = 116
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = s;code = 115
char = t;code = 116
char = r;code = 114
char = i;code = 105
char = c;code = 99
char = t;code = 116
char = s;code = 115
char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = r;code = 114
char = o;code = 111
char = t;code = 116
char = a;code = 97
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 = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
char = a;code = 97
char = x;code = 120
char = i;code = 105
char = a;code = 97
char = l;code = 108
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = s;code = 115
char = ;code = 32
char = i;code = 105
char = s;code = 115
char = ;code = 32
char = r;code = 114
char = e;code = 101
char = q;code = 113
char = u;code = 117
char = i;code = 105
char = r;code = 114
char = e;code = 101
char = d;code = 100
char = ;code = 32
char = f;code = 102
char = o;code = 111
char = r;code = 114
char = ;code = 32
char = p;code = 112
char = e;code = 101
char = r;code = 114
char = p;code = 112
char = e;code = 101
char = n;code = 110
char = d;code = 100
char = i;code = 105
char = c;code = 99
char = u;code = 117
char = l;code = 108
char = a;code = 97
char = r;code = 114
char = ;code = 32
char = o;code = 111
char = r;code = 114
char = i;code = 105
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = .;code = 46
char = ;code = 32
char = E;code = 69
char = l;code = 108
char = e;code = 101
char = c;code = 99
char = t;code = 116
char = r;code = 114
char = o;code = 111
char = c;code = 99
char = h;code = 104
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result sql = We have reported here, for the first time, the parallel and perpendicular orientation preferences of two planar and unhindered imidazoles as axial ligands (L) while coordinated toward iron(III) and iron(II) porphyrins, respectively, in a nonplanar porphyrinic environment. The synthesis and characterization of low-spin Fe(III)(tn-OEP)(L)(2) x ClO(4) and Fe(II)(tn-OEP)(L)(2) are reported. Fe(III)(tn-OEP)(L)(2) x ClO(4) shows rhombic electron paramagnetic resonance (EPR) spectra (at 77 K) in both solid and solution phases that are very characteristic for low-spin (S = 1/2) iron porphyrins with two axial imidazole ligands aligned parallel to each other. Single-point energy calculation is also performed on Fe(III)(tn-OEP)(1-MeIm)(2)(+) using density functional theory (DFT), which shows that the relative parallel orientations of two 1-MeIm are more stable than the perpendicular orientations. X-ray structures of Fe(II)(tn-OEP)(1-MeIm)(2) and Fe(II)(tn-OEP)(1-MeIm)(2).THF are reported that demonstrate, for the first time, the near-perpendicular axial ligand orientation (80.9 and 89.8 degrees, respectively) for iron(II) porphyrins in a distorted macrocyclic environment. Even starting from parallel axial orientations of 1-MeIm, geometry optimization using DFT converged well to the perpendicular axial alignment with a 82.54 degree dihedral angle, which is in close agreement with experiment. This is in sharp contrast to all earlier reports, in which sterically crowded imidazole (such as 2-MeIm) or a nearly planar porphyrin core with a "picket fence" environment that restricts the rotation of the axial ligands is required for perpendicular orientation. Electrochemical data obtained from a cyclic voltammetric study for Fe(II)(tn-OEP)(L)(2) reveal one-electron oxidation at very high positive potential, which readily explains why the complexes are so stable in air. Bulk oxidation of Fe(II)(tn-OEP)(1-MeIm)(2) at a constant potential of 0.69 V in dichloromethane with 0.1 M tetrabutylammonium perchlorate as the supporting electrolyte generates Fe(III)(tn-OEP)(1-MeIm)(2) x ClO(4), which has the same EPR spectrum and which upon reduction at 0.29 V regenerates Fe(II)(tn-OEP)(1-MeIm)(2) again. Thus, we have demonstrated here, for the first time, that iron(II) and iron(III) porphyrinates with two planar and unhindered axial imidazoles have different orientation preferences in a nonplanar porphyrinic environment.

Publication: Inorg Chem 2010 Mar 1 ;49(5)::2057-67. :doi: 10.1021/ic9016504.
Publication Date: 2010 Mar 1
Study Author(s): Patra, Ranjan;Chaudhary, Arvind;Ghosh, Sudip Kumar;Rath, Sankar Prasad;
Institution: Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
Shortcut link to this study:
We have reported here, for the first time, the parallel and perpendicular orientation preferences of two planar and unhindered imidazoles as axial ligands (L) while coordinated toward iron(III) and iron(II) porphyrins, respectively, in a nonplanar porphyrinic environment. The synthesis and characterization of low-spin Fe(III)(tn-OEP)(L)(2) x ClO(4) and Fe(II)(tn-OEP)(L)(2) are reported. Fe(III)(tn-OEP)(L)(2) x ClO(4) shows rhombic electron paramagnetic resonance (EPR) spectra (at 77 K) in both solid and solution phases that are very characteristic for low-spin (S = 1/2) iron porphyrins with two axial imidazole ligands aligned parallel to each other. Single-point energy calculation is also performed on Fe(III)(tn-OEP)(1-MeIm)(2)(+) using density functional theory (DFT), which shows that the relative parallel orientations of two 1-MeIm are more stable than the perpendicular orientations. X-ray structures of Fe(II)(tn-OEP)(1-MeIm)(2) and Fe(II)(tn-OEP)(1-MeIm)(2).THF are reported that demonstrate, for the first time, the near-perpendicular axial ligand orientation (80.9 and 89.8 degrees, respectively) for iron(II) porphyrins in a distorted macrocyclic environment. Even starting from parallel axial orientations of 1-MeIm, geometry optimization using DFT converged well to the perpendicular axial alignment with a 82.54 degree dihedral angle, which is in close agreement with experiment. This is in sharp contrast to all earlier reports, in which sterically crowded imidazole (such as 2-MeIm) or a nearly planar porphyrin core with a "picket fence" environment that restricts the rotation of the axial ligands is required for perpendicular orientation. Electrochemical data obtained from a cyclic voltammetric study for Fe(II)(tn-OEP)(L)(2) reveal one-electron oxidation at very high positive potential, which readily explains why the complexes are so stable in air. Bulk oxidation of Fe(II)(tn-OEP)(1-MeIm)(2) at a constant potential of 0.69 V in dichloromethane with 0.1 M tetrabutylammonium perchlorate as the supporting electrolyte generates Fe(III)(tn-OEP)(1-MeIm)(2) x ClO(4), which has the same EPR spectrum and which upon reduction at 0.29 V regenerates Fe(II)(tn-OEP)(1-MeIm)(2) again. Thus, we have demonstrated here, for the first time, that iron(II) and iron(III) porphyrinates with two planar and unhindered axial imidazoles have different orientation preferences in a nonplanar porphyrinic environment.
PMID: 20128598

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