Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2001
Supplementary information
Crystal structures, magnetic and spectroscopic properties of
manganese(II), cobalt(II), nickel(II) and zinc(II) dichloro complexes
bearing two 2-pyridyl-substituted imino nitroxides
Youhei Yamamoto, Takayoshi Suzuki and Sumio Kaizaki*
Contents
Figure S1 Perspective drawings of (a) (OC-6-22)-[CoCl2(IM2py)2] 2, (b)
(OC-6-22)-[NiCl2(IM2py)2] 3 and (c) (OC-6-22)-[ZnCl2(IM2py)2] 4.
Hydrogen atoms are omitted for clarity, and the thermal elipsoids are drawn
at 50% probability level.
Figure S2 Temperature-dependence of vis-NIR absorption spectrum of complex 2 in
dichloromethane: 300 K (• • • • • • •), 275 K (– • • – • • –), 250 K (— • — • —),
225 K (– – – –) and 200 K (———).
Figure S3 Temperature-dependence of vis-NIR absorption spectrum of complex 1 in
dichloromethane: 300 K (• • • • • • •), 275 K (– • • – • • –), 250 K (— • — • —),
225 K (– – – –) and 200 K (———).
Equations S1–S4
Equations used in the analyses of magnetic susceptibitily data for
complexes 4, 1, 3 and 2, respectively.
( S1 )
Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2001
(b)
(a)
N(1')
N(3')
Cl'
N(1')
N(3')
Cl'
Co
C(12)
N(3)
C(2)
Cl
Cl
N(3)
C(1)
C(12)
C(8)
C(8)
C(9)
N(1)
C(3)
C(4)
C(1) C(2)
C(10)
C(5)
N(1)
C(11)
Ni
C(4)
C(5)
C(7)
N(2)
C(7)
N(2)
C(3)
C(11)
C(6)
O
C(6)
O
C(9)
C(10)
(c)
N(3')
N(1')
C(4)
Cl'
Zn
C(5)
N(1)
C(2)
C(1)
C(3)
Cl
N(3)
C(12)
C(8)
C(7)
N(2)
C(6)
C(11)
C(9)
O
Figure S1
C(10)
Perspective drawings of (a) (OC-6-22)-[CoCl2(IM2py)2] 2, (b)
(OC-6-22)-[NiCl2(IM2py)2] 3 and (c) (OC-6-22)-[ZnCl2(IM2py)2] 4.
Hydrogen atoms are omitted for clarity, and the thermal elipsoids are
drawn at 50% probability level.
( S2 )
Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2001
3
-1
)
-1
cm
/ dm
log(
1
3
mol
2
0
8
10
12
10
Figure S2
-3
 / cm
14
16
-1
Temperature-dependence of vis-NIR absorption spectrum of complex 2 in
dichloromethane: 300 K (• • • • • • •), 275 K (– • • – • • –), 250 K (— • — •
—), 225 K (– – – –) and 200 K (———).
( S3 )
Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2001
3
-1
)
-1
cm
3
mol
/ dm
log(
2
1
15
Figure S3
10 -3  / cm-1
20
25
Temperature-dependence of vis-NIR absorption spectrum of complex 1 in
dichloromethane: 300 K (• • • • • • •), 275 K (– • • – • • –), 250 K (— • — •
—), 225 K (– – – –) and 200 K (———).
( S4 )
Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2001
Equations S1
Equation used in the analyses of magnetic susceptibitily data for
complex 4.
2N2gR(bis)2
MW(bis) N2gR(mono)2
M = ———————— • (1–) + ———— • —————— • 
kT{3 + exp(2J’/kT)}
MW(mono) 4kT
where J’ is a coupling constant between two IM2py (H = – 2J'SR1• SR2), gR(bis) and
gR(mono) are g factors of IM2py radicals in [ZnCl2(IM2py)2] and [ZnCl2(IM2py)],
respectively, MW(bis) and MW(mono) are molecular weight of [ZnCl2(IM2py)2] and
[ZnCl2(IM2py)], respectively, and  is an impurity factor of comtamination with
[ZnCl2(IM2py)]. Other symbols have their usual meanings.
Equations S2
Equation used in the analyses of magnetic susceptibitily data for
complex 1.
N2 10g12 + 35g22e5x + 84g32e12x + 35g42e7x–2x’
M = —— • ———————————————————
4kT
2 + 3e5x + 4e12x + 3e7x–2x’
where x and x' denote J/kT and J’/kT (H = – 2J SMn•(SR1 + SR2) – 2J' SR1• SR2),
respectively, and g1, g2, g3, and g4 express (7gMn – 2gR)/5, (31gMn + 4gR)/35, (5gMn +
2gR)/7, and gMn, respectively. Other symbols have their usual meanings.
( S5 )
Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2001
Equations S3
Equation used in the analyses of magnetic susceptibitily data for
complex 3.
N2
(gNi + gR)2(5 + e–4x) + 4gNi2e–2x–2x’
M = ———— • ———————————————
2k(T–)
5 + 3e–4x + e–6x + 3e–2x–2x’
where x and x' denote J/kT and J’/kT (H = – 2J SNi•(SR1 + SR2) – 2J' SR1• SR2),
respectively. The parameter  is Weiss constant, and other symbols have their usual
meanings.
Equations S4
Equation used in the analyses of magnetic susceptibitily data for
complex 2.
N2 35g12 + 10g22e–5x + g32e–8x + 10g42e–3x–2x’
M = ———— • ———————————————————
4k(T–)
3 + 2e–5x + e–8x + 2e–3x–2x’
where x and x' denote J/kT and J’/kT (H = – 2J SCo•(SR1 + SR2) – 2J' SR1• SR2),
respectively, and g1, g2, g3, and g4 express (3gCo + 2gR)/5, (11gCo + 4gR)/15, (5gCo –
2gR)/3, and gCo, respectively. Other symbols including  have their usual meanings.
( S6 )