Silver(I) Complex Assemblies with Nonplanar Aromatic Compounds

Abstract

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 (ClO 4 ) 3 ]·2C 6 H 5 Me ( 1 ), [Ag 2 (L 2 ) 2 (ClO 4 ) 2 ]·C 6 H 4 Me 2 ( 2 ), [Ag 2 (L 3 )(C 6 H 6 ) 2 (ClO 4 ) 2 ] ( 3 ), and [Ag(L 4 )(ClO 4 )] ( 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-η 2 -η 2 or μ-η 2 -η 2 -η 1 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, C 74 H 58 Ag 3 Cl 3 O 12, monoclinic, Cc, a = 37.951(4) Å, b = 8.047(4) Å, c = 20.882(5) Å, β = 93.72(1)°, V = 6363(3) Å 3, Z = 4; 2, C 60 H 42 Ag 2 Cl 2 O 8, monoclinic, P 2 1 / n, a = 12.317(4) Å, b = 7.961(1) Å, c = 24.741(1) Å, β = 100.015(1)°, V = 2389(6) Å 3, Z = 2; 3, C 32 H 26 Ag 2 Cl 2 O 10, tetragonal, P 4 1 2 1 2, a = 8.759(6) Å, c = 39.967(8) Å, V = 3065(3) Å 3, Z = 4; 4, C 7 H 8 AgClO 4, monoclinic, P 2 1 / n, a = 9.847(4) Å, b = 9.054(3) Å, c = 10.662(3) Å, β = 106.72(2)°, V = 910.3(4) Å 3, Z = 4.