Luminescent silver(I) coordination polymers having a {Ag-2(mu-X)(2)} rhombic core (X = I, Br) were prepared using pyrazine (pyz), methylpyrazine (Mepyz), and aminopyrazine (ampyz) as bridging ligands. Photophysical measurements show that the complexes were strongly luminescent in the solid state at room temperature; further, the emissive excited state of the pyz and Mepyz complexes was a triplet charge-transfer ((CT)-C-3) excited state, similar to that of their copper(I) congeners, whereas that of the ampyz complex was a intraligand ((IL)-I-3) excited state. The energy of the (CT)-C-3 excited state of a silver halogenido complex was revealed to be ca. 5000 cm(-1) higher than that of the corresponding copper complex.