1,6-Heptadiyne may be used in the preparation of free-standing polymer films of poly(1,6-heptadiyne). Polymerization of 1,6-heptadiyne using an insoluble Zeigler-Natta catalyst affords soluble polymer having six-membered ring containing polyene. Ruthenium(II)-catalyzed reaction of a substituted 1,6-heptadiyne with norbornene affords a tandem [2+ 2+ 2]/[4+2] cycloaddition product and a [2+ 2+2] cycloadduct.