Effect of the Environment on Molecular Properties: Synthesis, Structure, and Photoluminescence of Cu(I) Bis(2,9-dimethyl-1,10-phenanthroline) Nanoclusters in Eight Different Supramolecular Frameworks

By selection of different charge-balancing anionic frameworks and different host-to-guest ratios, the photosensitizer-dye cation [Cu(dmp)2]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) has been embedded in a series of three-dimensional
host structures. It occurs with variable geometry in different states of aggregation, including weakly interacting
monomers, isolated dimers, columns, and layers. A large variation in its emission lifetime is correlated with the
relative energy level spacings of the guest- and host-framework components. In a fully saturated host framework,
the lifetime exceeds values reported for a series of conventional Cu(dmp)2 salts.