Pa. Reynolds et al., METAMAGNETISM IN TETRACHLOROBIS(N-PHENYLACETAMIDINE)RHENIUM(IV), Journal of the Chemical Society. Dalton transactions, (2), 1997, pp. 263-267
Single-crystal magnetisation and polarised neutron diffraction (PND) m
easurements have been made for the complex cis-[ReCl4(NH=CMeNHPh)(2)].
At higher temperatures the magnetic behaviour is typical of such a rh
enium-(IV) complex, with three unpaired spins (mu = 3.6 mu(B)), an alm
ost isotropic g-tensor of 1.86(1) and a large zero-field splitting, 20
, of -20(2) cm(-1). At very low temperatures the magnetisation behavio
ur as a function of temperature and field strength and direction indic
ates two magnetically ordered structural phases when H parallel to b,
but only one for a and c, with T-N = 9.7(1) K. A tricritical point at
T = 5.8(2) K and H = 4.40(5) T was established on the transition line
in H vs. T space between the two phases when H parallel to b. This beh
aviour is metamagnetic. The two-dimensional form of the stronger magne
tic exchange implied, with weaker interlayer interaction, can be corre
lated with the observed structural feature of ab planes of ReCl4 units
separated by layers of phenyl rings. The PND experiment showed that a
bout half of the spin of the system is delocalised away from the Re by
covalent bonding to the Cl atoms and the amidine ligand, accompanied
by considerable effects resembling spin polarisation. The magnetic spa
ce groups are P2(1)/c at low magnetic fields and Pc2(1)n at high field
s along b, compared with the nuclear structural space group of Peen.