Determination of the Orientation of Pendants on Rigid-Rod Polymers.

Bis-norbornene and bis-cyclobutene with different kinds of linkers have been extensively used for the synthesis of double stranded ladderphanes under ruthenium- or molybdenum-catalyzed ring opening metathesis polymerization (ROMP) conditions. The key to the success relies on the selective formation of comb-like polynorbornenes or polycycloubtenes, where pendants are all aligned towards similar direction. This minireview summarizes various methods (chemical methods, spectroscopic means, and nonlinear optical measurements) for determining the comb-like conformations of pendants on these rigid-rod polymers. The approach is based on the proximal relationship between adjacent pendants. Interactions between these adjacent pendants would enable a change in chemical reactivity.