Self-Assembly of Flexible Supramolecular Metallacyclic Ensembles: Structures and Adsorption Properties of Their Nanoporous Crystalline Frameworks

The syntheses, structures, and N2 adsorption properties of six new supramolecular metallacycles
are reported. Flexible ditopic linkers, 1−4, with systematically varied lengths and conformational degrees
of freedom were synthesized utilizing ester linkages. They were used in combination with (dppp)M(OTf)2,
where M = Pt(II) and Pd(II), and cis-(Me3P)2Pt(OTf)2 to form flexible supramolecular metallacycles 5−10
in 88−98% isolated yields. Their structures were characterized via multinuclear NMR and X-ray
crystallography. The metallacycles stack to form porous structures in the crystalline state. The pore
dimensions depend on both the phosphorus ligands attached to the metals and the flexible linkers. Adsorption
studies on the porous materials show that 5a, 6, 8, and 9 held 11.7, 16.5, 5.7, and 6.8 cm3/g STP of N2 at
77 K, respectively. A guest-exchange study with nitromethane and toluene reveals that the nanopore in 5
is flexible, a property which was transferred from the linker to the supramolecular structure in the solid
state.