Bipodal NЈ,NЈ,NٞNٞ-tetraalkyl-N,NЉ-phenylenedicarbonylbis(thiourea) readily 'self-assemble into' Pt 2 L 2 and Pt 3 L 3 metallamacrocyclic complexes depending on whether the S,O chelating moieties are meta or para relative to each other in the ligand. Thus treatment of PtCl 4 2with one equivalent of 3,3,3Ј,3Ј-tetra(n-butyl)-1,1Ј-terephthaloylbis(thiourea), {H 2 L 1 } 2 , leads to the exclusive formation of the cis-[Pt(L 1 -S,O)] 3 complex, while 3,3,3Ј,3Ј-tetraethyl-1,1Ј-isophthaloylbis(thiourea), {H 2 L 2 } 2 , yields only the cis-[Pt(L 2 -S,O)] 2 complex. The cis-[Pt(L 1 -S,O)] 3 complex forms extremely friable crystals, necessitating X-ray data collection in mother-liquor, the lattice of which was found to contain chloroform, water and ethanol molecules as 'guests'. By contrast, the sparingly soluble diethyl-substituted Pt 2 L 2 complex does not include solvent molecules in the crystal lattice.
The structures of the inclusion compounds of 2.2'-bis( 2.7-dichloro-9-hydroxy-9-fluorenyl) biphenyl with 1,4-dioxane and 1,3-dioxoIane, with host: guest ratios of 1 : 3.5 and 1 : 2 respectively, have been elucidated. Their kinetics of desolvation have been studied and the dioxane inclusion compound desoivates in two distinct steps, each following the first-order kinetic model. The dioxolane inclusion compound desolvates in one step and follows a contracting area model. X-Ray powder photography shows that the dioxane inclusion compound forms a stable intermediate y-phase before final desolvation to a non-porous a-phase.
Paper 4/04902K
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