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Spectroscopy
applied to species having one or more unpaired
electrons : free radicals, biradicals, other triplet
states, transition metal compounds
species having one unpaired electron has two
electron spin energy levels:
E = g BBoMs
selection rule
==>
Ms = 1
E = g BBo
g: proportionality constant,
2.00232 for free electron
1.99 2.01 for radicals
1.4 3.0 for transition metal compounds
in isotropic systems (gas, liquid or solution
of low viscosity, solid sites with spherical
or cubic environment) , g is independent of
field direction
B: Bohr magneton
9.274 x 10-24 J T-1 for electron
MS: electron spin quantum number
1
+1/2 or 1/2
Ex. 1
Ex. 2
Ex. 3
BH4- + C(CH3)3
[BH3]- + HC(CH3)3
Ex. 4
S(=NBut)2 + Me2SiCl2
S
g = 2.005
NBut
+
SiMe
NBut
A(N) =
0.45 mT
Ex. 5 S(=NBut)2 -
Ex. 6
g = 2.0071
A(N) = 0.515 mT
(MeO)3PBH2
Ex. 7
CrIII(porphyrin)Cl
zero-field splitting
in the absence of magnetic field, 2S + 1
energy states split depends on the structure of
sample, spin-orbit coupling
anisotropic systems
solids, frozen solutions, radicals prepared by
irradiation of crystalline materials, radical
trapped in host matrices, paramagnetic
point defect in single crystals
for systems with spherical or cubic symmetry
g factors
for systems with lower symmetry,
g ==> g and g ==> gxx, gyy, gzz
ESR absorption line shapes show distinctive
envelope
system with an axis of symmetry
no symmetry
10
Ex. 9
A(55Mn) = 6.5 mT
A(55Mn) = 3.5 mT
A(83Kr) = 0.4 mT
11
12
trans-[Cr(pyridine)4Cl2]+
(b) in trans[Rh(pyridine)4Cl2]Cl6H2O
powder
Ex. 11
low-spin
d6 system
diamagnetic
Oh
tetragonal
high-spin 5D 5T2 5B2
short relaxation times
==> broad resonances
large zero-field splittings
==> no resonance observed
13
Ex. 12
d9 system
14
multiple resonance
ENDOR (electron-nuclear double resonance)
Ex. 13 [Ti(C8H8)(C5H5)] in toluene (frozen
solution)
15
16
17