Luminescence of W(CO)(4)(4-Me-phen) in photosensitive thin films: A molecular probe of acrylate polymerization

The complex W(CO)(4)(4-Me-phen) (4-Me-phen = 4-methyl-1,10-phenanthroline) has been determined to be luminescent and act as a spectroscopic probe in UV-curable trimethylol-propane triacrylate/poly(methyl methacrylate) thin films. Electronic absorption and luminescence characteristics have been measured for this complex in room-temperature solutions and low-temperature (80 K) glasses and in 10 mil thin films of the unexposed and exposed acrylate resins. In each environment dual luminescence bands were observed which are attributed to triplet-centered metal-to-ligand charge-transfer ((3)MLCT) excited states. For the unexposed photoresist these transitions were recorded at 520 and 750 nm and in the exposed material these are moved to 525 and 715 nm, respectively. The lowest energy emission band undergoes a substantial blue-shift and intensifies greatly on polymerization; this phenomenon provides a useful molecular probe of the acrylate cross-linking process. These changes in emission characteristics are associated with a rigidochromic effect imparted on the lowest lying and solvent sensitive b(2) --> b(2)(pi*) (3)MLCT electronically excited state in this complex. The complex W(CO)(5)(4-CN-py) (4-CN-py = 4-cyanopyridine) was also investigated as a spectroscopic probe in the acrylate system but appears unsuitable for this purpose as it was found to degrade significantly in the resin.