Construction of Metal Sandwich Systems Derived from Assembly of Silver(I) Complexes with Polycyclic Aromatic Compounds

A new class of metal sandwich complexes of silver derived from silver(I) perchlorate and fluoranthene
(L1), benzo[ghi]perylene (L2), [2,2]paracyclophane (L3), and decacyclene (L4) was prepared. The idea behind
the use of polycyclic aromatic compounds as an alternative approach for construction of organometallic sandwich
systems is to combine the plasticity of the metal ion and planarity and coordinative diversity of the hydrocarbons.
Structural studies by single-crystal X-ray diffraction have shown that all compounds contain extended one- to
three-dimensional structures in which several metal atoms are sandwiched between two fused polycyclic systems.
While complex 1, [Ag3(L1)2(ClO4)3], exists in the solid state as a two-dimensional W-type architecture in
which AgClO4 layers are separated by two sheets of hydrocarbon, complex 2, [Ag(L2)(ClO4)]4·toluene, contains
two double-decker polymeric chains coupled via extensive aromatic π−π stackings. Pillared brick sandwiched
framework was observed in 3, [Ag(L3)(ClO4)], whereas the multidecker sandwich complex 4, [Ag2(L4)(ClO4)2(benzene)], is reminiscent of ladder. The structure of L1 has been redetermined and that of L2 reported; the
structural data are used for discussion of the silver−π interactions. The electrochemical behavior and ESR
spectra are consistent with formation of the organic radical species in the system. The present findings may
represent an alternative approach for predesigning the multilayered systems in organometallic chemistry.