Acid-base hydrolytic chemistry of surface anchored [Sn]-NEt2 moieties with dialkyne terminated molecules has been used to construct close packed thin films of good structural quality on Si(100)/(Si/SiO2) substrates. The surface coverage in these thin films was found to be 2-7 molecules/100 Angstrom(2). An elaboration of this methodology to a layer-by-layer deposition process using Sn(NEt2)(4) and 1,9-decadiyne or p-diethynylbenzene led to thin film structures of up to five layers. The evolution of thin films in the step-by-step fabrication was monitored by contact angle goniometry, ellipsometry, XPS, FTIR-ATR, and UV-vis absorption spectroscopy. Topochemical polymerization on a thin film of p-bis(butadiynyl)benzene was achieved by exposure to LTV-vis radiation, giving a blue film. Cobalt carbonyl could be easily adsorbed on these alkynyl thin films under room-temperature conditions.