Ten novel cation-induced complexes, {(BIQPT)2[Ag2I6]} (1), {[(BIQBT)CuI3]} (2), {(BIQHX)2[Cu4I8]·DMF} (3), {(BIQBT)1.5[MoOS3Cu3I4]·DMF} (4), {(BIQHX)[Ag4Br6]}n (5), {[(BIQHX)Ag4I6]}n (6), {(BIQHX)[Cu2(SCN)4]}n (7), {(BIQBT)[Cu2(SCN)4]}n (8), {(BIQPP)[Cu2(SCN)4]}n (9), {(BIQEH)[Cu2(SCN)4]}n (10) {BIQPT = 1,5-bis(isoquinoline)pentane, BIQBT = 1,4-bis(isoquinoline)butane, BIQHX = 1,6-bis(isoquinoline)hexane, BIQPP = 1,3-bis(isoquinoline)propane, BIQEH = 1,2-bis(isoquinoline)ethane} have been constructed via anion exchange reaction of bis(isoquinoline) ionic liquids. In these ten compounds, the anion structures ranged from mononuclear (2), dimer (1), tetranuclear oligomer (3 and 4), to 1D chain (5, 6,7 and 8) and 2D polymeric architectures (9 and 10). These results indicated that anion exchange reaction is an efficient approach for the preparation of cluster-functionalized ILs or IL-functionalized MOFs.