Use of a substituted digermylene oxide as a ligand has been demonstrated through the isolation of a series of group 11 metal (I) iodide complexes. Accordingly, the reactions of digermylene oxide [{(i-Bu)(2)ATIGe}(2)O] (ATI = aminotroponiminate) (1) with CuI under different conditions afforded [({(i-Bu)(2)ATIGe}(2)O)(2)(Cu4I4)] (2) with a Cu4I4 octahedral core, [({(i-Bu)(2)ATIGe}(2)O)(2)(Cu3I3)] (3) with a Cu3I3 core, and [{(i-Bu)(2)ATIGe}(2)O(Cu2I2)(C5H5N)(2)] (4) with a butterfly-type Cu2I2 core. The reactions of compound 1 with AgI and AuI produced [({(i-Bu)(2)ATIGe}(2)O)(2)(Ag4I4)] (5) with a Ag4I4 octahedral core and [{(i-Bu)(2)ATIGe}(2)O(Au2I2)] (6) with a Au2I2 core, respectively. The presence of metallophilic interactions in these compounds is shown through the single-crystal X-ray diffraction and atom-in-molecule (AIM) studies. Preliminary photophysical studies on compound 6 are also carried out.