Polymers containing the pendant propargyl groups can be effectively crosslinked upon UV irradiation in the presence of a small amount of W(CO)(6). The alkyne-tungsten carbonyl complex was formed initially as evident by IR spectroscopy, which was involved in the subsequent crosslinking reaction. Analyses by UV, IR, and C-13 NMR CP/MAS spectroscopic methods confirmed the polymer crosslinking as a result of the conversion of the acetylenic units to the polyene and diacetylene moieties in the crosslinked system. (C) 2003 Elsevier Ltd. All rights reserved.