Electron spin resonance studies of the reorientational motion of Ni(mnt)2(-).
Electron spin resonance studies of the planar bis(maleonitriledithiolato)nickel complex ion, Ni(mnt)(2)(-), have been carried out from the motional narrowing region to the glassy limit in a series of ethers: 2-methyltetrahydrofuran (MTHF), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), and tetraethylene glycol dimethyl ether (tetraglyme). Analyses of the spectra show that Ni(mnt)(2)(-) is reorienting a factor of 3 faster about its long in-plane axis in all of these solvents; i.e., axially symmetric rotational diffusion produces agreement between the experimental and calculated line widths with D(parallel)/D(perpendicular) = 3.0 +/- 0.2; D(parallel) and D(perpendicular) are the diffusion constants for reorientation about the long in-plane (parallel) and perpendicular axes, respectively. The temperature dependence of the reorientational correlation time tau(2)(0) = (6D(perpendicular))(-1) determined from the widths is in agreement with the modified Stokes-Einstein-Debye model; the results indicate that Ni(mnt)(2)(-) has relatively strong (but not associative) interactions with the ethers. The experimental values of tau(2)(0) and the solvents' viscosities, self-diffusion constants, and dielectric relaxation times are compared and found to have a common temperature dependence. The ESR data also are compared with values of tau(solv), the correlation time obtained when a fluorescent probe is excited and its emission is monitored as the nonequilibrium solvent distribution relaxes. tau(solv) and tau(2)(0) are found to have a common temperature dependence in MTHF, tetraglyme, and two other solvents (ethyl alcohol and 1-butanol) in which Ni(mnt)(2)(-) has been studied. The factors determining these transport properties are discussed.
Kowert
Bruce A
BA
Department of Chemistry, Saint Louis University, 3501 Laclede Avenue, St. Louis, Missouri 63103, USA. kowertba@slu.edu
Thurman-Keup
Eva M
EM
Stemmler
Ann Joern
AJ
Stemmler
Timothy L
TL
Fehr
Michael J
MJ
Caldwell
Cassondra V C
CV
Gentemann
Stephen J
SJ
D004578:Electron Spin Resonance Spectroscopy; D009038:Motion; D009942:Organometallic Compounds / Q000737:chemistry*; D013696:Temperature
D009942:Organometallic Compounds; C507196:bis(maleonitriledithiolato) nickelate(III)