This review focuses on the gas phase photochemical fragmentation processes of coordination compounds that are precursors for the laser driven synthesis of solid-state materials such as thin films and nanoclusters from the gas phase. Specific emphasis is placed on the identification of photofragments by luminescence spectroscopy during the deposition process. In several cases, results from mass spectroscopy and from photofragmentation under the collision-free conditions of a molecular beam are included to clarify the identifications and mechanisms. Detailed experimental measurements have been made on metal diketonates, metal amides, metal xanthates and metal thiocarbamates. These compounds are useful as molecular precursors for the synthesis of thin films and nanoparticles of metals, binary and ternary materials, and semiconductor films.