Molecular motions of 1,4-dihalonaphthalenes and their binary solid solutions are studied by Raman spectroscopy to understand the effect of chemical perturbation of the lattice stability. In the 1,4dihalonaphthalene series, 1,4-dichloronaphthalene and I-bromo-4-chloronaphthalene are isomorphous but the additional chemical perturbation by another bromine atom creates a lattice instability which results in a different crystal structure for 1,4-dibromonaphthalene. Not only is the binary organic alloy (solid solution) of 1,4-dichloronaphthalene with l-bromo-4-chloronaphthalene stable for all composition, but 1bromo-4-chloronaphthalene shows large solubility with 1,4-dibromonaphthalene as well. In both alloys, all phonons are amalgamated and so are some internal vibrations which are predominantly non halogen modes. In the l-bromo-4-chloronaphthalene alloy with 1,4-dibromonaphthalene, the lattice is unstable in the critical concentration region with mole fraction of 1,4-dibromonaphthalene between 0.24 and 0.44. In this region, the lattice can be driven from the l-bromo-4-chloronaphthalene crystal form to that of 1,4dibromonaphthalene by additional chemical perturbation. Certain features of the phonon motions and exciton splittings are retained across this critical concentration region, indicating that the lattice instability encountered is not along all molecular degrees of freedom and that certain intermolecular interactions do not change in going from l-bromo-4-chloronaphthalene crystal form to that of 1,4dibromonaphthalene. A close inspection of their crystal structures shows that in each case the molecules stack to form linear chains and that some of the relationships between two stacks remain unchanged. The structural similarity suggests that the one dimensional triplet exciton transport found in 1,4dibromonaphthalene may also be present in the other two compounds.5802
To understand the effect of chemical perturbation (created by a change of substituent or by a chemical impurity) on crystal structure, the crystal structures of 1,4-dichloronaphthalene (DCN, C i0H6CI2) and 1,4-dibromonaphthalene (DBN, C~0H6Brz) have been determined from three-dimensional X-ray diffraction measurements. Crystals of DCN are found to be monoclinic with cell dimensions a = 13-386 (3) (7), c = 4.048 (2) ,~ and fl = 91-95 (2) °. Previous Raman results show that some dynamic interaction topology is preserved through the structure change. The X-ray analysis shows that the topology preserved is the molecular stacks parallel to the shortest axis in both structures and the retention of the DCN screw axis as a non-crystallographic screw axis in the DBN structure at x = 0.1216,y = 0.3000 and parallel to the c axis.
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