Silver(I) Complex Assemblies with Nonplanar Aromatic Compounds

Reactions of silver(I) perchlorate with the nonplanar aromatic compounds triptycene (L1), 9,9-bifluorenylidene
(L2), (R)-(+)-1,1‘-bi-2-naphthol (L3), and 2,5-norbornadiene (L4) have isolated four novel hydrocarbon-bridged
polymeric complexes:  [Ag3(L1)3(ClO4)3]·2C6H5Me (1), [Ag2(L2)2(ClO4)2]·C6H4Me2 (2), [Ag2(L3)(C6H6)2(ClO4)2]
(3), and [Ag(L4)(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−π interactions. While complex 1 in the
solid state contains a three-dimensional architecture in which the triangular molecule triptycene exhibits an
unprecedented μ-η2-η2 or μ-η2-η2-η1 coordination mode depending on the steric requirements of the network, 3
represents the first example of π 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 π complexes for the rational control and
synthesis of polymeric organometallic materials is discussed. Crystal data:  1, C74H58Ag3Cl3O12, monoclinic, Cc,
a = 37.951(4) Å, b = 8.047(4) Å, c = 20.882(5) Å, β = 93.72(1)°, V = 6363(3) Å3, Z = 4; 2, C60H42Ag2Cl2O8,
monoclinic, P21/n, a = 12.317(4) Å, b = 7.961(1) Å, c = 24.741(1) Å, β = 100.015(1)°, V = 2389(6) Å3, Z =
2; 3, C32H26Ag2Cl2O10, tetragonal, P41212, a = 8.759(6) Å, c = 39.967(8) Å, V = 3065(3) Å3, Z = 4; 4, C7H8AgClO4, monoclinic, P21/n, a = 9.847(4) Å, b = 9.054(3) Å, c = 10.662(3) Å, β = 106.72(2)°, V = 910.3(4)
Å3, Z = 4.