Abstract
An isolated silver(I) ammonia monomer, a dimer, and a novel dimer containing an intercalated water molecule have been embedded as guests in supramolecular frameworks, [Ag(NH~3~)~2~][(H~2~thpe)(H~3~thpe)]⋅MeCN (1), [{Ag(NH~3~)~2~}~2~][(H~2~thpe)~2~]⋅4.25 H~2~O (2), and [{Ag(NH~3~)~2~}‐H~2~O‐{Ag(NH~3~)~2~}][(H~2~thpe)~2~]⋅benzene (3) (H~3~THPE=tris(hydroxyphenyl)ethane). The [{Ag(NH~3~)~2~}~2~]^2+^ dimer is not stable as an isolated entity, but is stabilized by hydrogen bonding in the supramolecular framework. The water‐intercalated silver(I) ammonia dimer, which constitutes a novel species, is also subject by hydrogen bonding in concentrated solutions. The destabilization energy of the dimer relative to isolated monomers is calculated to be ≈300 kJ mol^−1^ by both perturbation methods and DFT theory. For the water‐intercalated dimer it is calculated to be ≈200 kJ mol^−1^ according to the BSSE‐corrected MP2 calculation. The different aggregate states show a dramatic variation of absorption and emission properties, in accordance with the concentration dependent red‐shift observed in solutions. Natural‐bond‐orbital analysis shows that the disilver‐ammonium‐aquo “sandwich” cation in 3 is stabilized by interaction between the π lone pair orbital on the oxygen atom of the water molecule and Ag^I^N σ antibonding molecular orbital.