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Additional info for Metallobiochemistry [Part D] [No cover or index]
100, 3617 (1978). 46 PROBES OF METAL ION ENVIRONMENTS  Second, the various lanthanide ions and their complexes should have very similar chemical properties. Although their coordination numbers are high (most commonly 8 and 9), their radii exhibit the well-known lanthanide ion contraction. Consequently, there is variation along the series of hydration numbers of the lanthanide aqueous ions and coordination numbers, as well as in the thermodynamic and kinetic properties of their complexes. 20 Third, the replacement of the naturally occurring ion by the probe should be isomorphic.
The lanthanide complex may contain a 3-fold or higher s y m m e t r y axis in solution, or there can be effective axial s y m m e t r y resulting from either rapid internal rotation about the lanthanide-ligand bond 45 or rapid interconversion of the geometrical isomers of the complex. 46 Such fluxional behavior has been proposed for many systems whose solid-state structures indicate nonaxial symmetry, although the paramagnetic shifts appear to possess axial s y m m e t r y in solution. It has been argued that the validity of using the axial symmetry assumption can be tested by examining shifts for different lanthanide complexes.
The relaxation rates at each site are then given by l/Tiobs L = 1/TiL + 1 / r L 1/Tiobs M = 1~TiM + 1 / r M (8) (9) f o r / = 1,2. Chemical Shifts The chemical shift of the lanthanide complex (lanthanide-induced shift, LIS) is given by the sum of three contributions4°-43: A M = Acf + A d + A c (10) where Acf is the diamagnetic complex formation shift, Ad is the dipolar shift, and Ac is the contact shift. The value of Acf, which arises from electrostatic interactions or metal ion-induced ligand conformational changes, is usually estimated from the effects of La(III) and Lu(III) binding to the ligand and are assumed to be constant through the lanthanide series.