Isomorphism and disorder in o-chlorohalobenzenes studied by NQR

SILVINA C. PÉREZ; ALBERTO E. WOLFENSON; MARIANO ZURIAGA

SOLID STATE NUCLEAR MAGNETIC RESONANCE

ACADEMIC PRESS INC ELSEVIER SCIENCE

Lugar: Amsterdam; Año: 2014 vol. 57 p. 39 - 45

0926-2040

In this work we present experimental results that allow to characterize different solid modifications found in o-chlorohalobenzenes. Three disordered phases have been found in o-chlorobromobenzene. The stable phase at high temperature (phase I) is also obtained by quenching the sample at 77 K. Slow cooling allow to obtain the low temperature phase III which, on heating, transforms to phase II at 183 K and this, in turns, transforms to phase I at T210 K. The disorder evidenced through the Nuclear Quadrupole Resonance spectra, is attributed to a random occupation of chlorine and bromine sites. In all phases there is evidence of molecular reorientations out of the benzene ring plane around the pseudosymmetry axis between the atoms of Cl and Br. In o-chlorofluorobenzene two phases have been found depending on the cooling rate. One phase is disordered due to the random exchange of the occupation of Cl and F sites. In this case, there is also evidence of molecular reorientations out of the benzene ring plane, but in this case the reorientation is around the pseudo-symmetry axis that pass through the C?Cl bonds. Comparisons with the behavior of o-dichlorobenzene are also made.