| The photophysical behavior, molecular structure, and electronic structure of pure and mixed crystals of dicyano silver (I) complexes have been studied. The pure crystals studied are {dollar}rm Tllbrack Ag(CN)sb2rbrack, Nalbrack Ag(CN)sb2rbrack, Klbrack Ag(CN)sb2rbrack, Cslbrack Ag(CN)sb2rbrack, Rblbrack Ag(CN)sb2rbrack, Calbrack Ag(CN)sb2rbrack, Srlbrack Ag(CN)sb2rbracksb2, and (n{dollar}-{dollar}rm Bu)sb4lbrack Ag(CN)sb2rbrack.{dollar} Also, mixed crystals comprised of {dollar}rmlbrack Ag(CN)sb2sp{lcub}-{rcub}rbrack{dollar} ions doped into the alkali halide crystals KCl and NaCl have been studied.; The results indicate the importance of closed-shell silver-silver interactions, called argentophilicity. These interactions have been shown to be weak in the ground state but very strong in the first excited state. All the crystals studied give rise to the formation of luminescent excimers and exciplexes as a result of excited state silver-silver interactions. These species represent a new class of metal-metal bonded exciplexes in inorganic chemistry. They are also the first reported metal-metal bonded exciplexes in the solid state.; An interesting new phenomenon in optical spectroscopy has been discovered in the mixed crystals studied in this thesis. The new phenomenon has been called exciplex tuning. It refers to the tuning of the luminescence by the formation of different exciplexes with a formula of {dollar}rmsp*lbrack Ag(CN)sb2sp{lcub}-{rcub}rbracksb {lcub}n{rcub}.{dollar} Tuning has been achieved by simple and convenient methods over a broad range in the ultraviolet and visible regions. The findings in this thesis might lead to the development of new laser and photoconducting materials. |
