Reactions of silver(I) perchlorate with the nonplanar aromatic compounds triptycene (L-1), 9,9-bifluorenylidene (L-2), (R)-(+)-1,1-bi-2-naphthol (L-3) and 2,5-norbornadiene (L-4) have isolated four novel hydrocarbon-bridged polymeric complexes: [Ag-3(L-1)(3)(ClO4)(3)]. 2C(6)H(5)Me (1), [Ag-2(L-2)(2)(ClO4)(2)]. C6H4Me2 (2), [Ag-2(L-3)(C6H6)(2)(ClO4)(2)] (3), and [Ag(L-4)(ClO4)] (4). Structural studies using single-crystal X-ray diffraction have shown that all compounds contain extended two- or three-dimensional structures based on cation-rr interactions. While complex 1 in the solid stale contains a three-dimensional architecture in which die triangular molecule triptycene exhibits an unprecedented mu-eta(2)-eta(2) or mu-eta(2)-eta(2)-eta(1) coordination mode depending on the steric requirements of the network, 3 represents the first example of pi coordination of naphthol-containing micropores in its metal complexes. Infinite chains consisting of alternating silver ions and hydrocarbon molecules observed in both 2 and 4 are linked together by perchlorates, affording 2-D frameworks. The potential use of these pi complexes for the rational control and synthesis of polymeric organometallic materials is discussed. Crystal data: 1, C74H58Ag3Cl3O12, monoclinic, Cc, a = 37.951(4) Angstrom, b = 8.047(4) Angstrom, c = 20.882(5) Angstrom, beta = 93.72(1)degrees, V= 6365(3) Angstrom(3), Z = 4; 2, C60H42Ag2Cl2O8. monoclinic, P2(1)/n, a = 12.317(4) Angstrom, b = 7.961(1) Angstrom, c = 24.741(1) Angstrom, beta = 100.015(1)degrees, V = 2389(6) Angstrom(3) , Z = 2; 3, C32H26Ag2Cl2O10, tetragonal, P4(1)2(1)2, a = 8.759(6) Angstrom, c = 39.967(8) Angstrom V= 3065(3) Angstrom(3), Z = 4; 4, C7H8-AgClO4 monoclinic, p2(1)/n, a = 9.847(4) Angstrom, b = 9.0543 Angstrom, c = 10.662(3) Angstrom, beta = 106.72(2)degrees, V= 910.3(4) Angstrom(3), Z = 4.