Synthesis, Characterization, and Preliminary Host−Guest Binding Studies of Porphyrinic Molecular Squares Featuring fac-Tricarbonylrhenium(I) Chloro Corners

Abstract

Luminescent multiporphyrin molecular square assemblies have been synthesized in high yield from Re(CO)5Cl and a highly soluble dipyridylporphyrin ligand. Both free-base and ZnII-metalated variants of squares have been synthesized. The ZnII-containing squares are capable of strongly binding selected polyimine ligands in CH2Cl2 solution. Advantage has been taken of the effect to construct pentaporphyrin host−guest assemblies.

Arene Ruthenium Cages: Boxes Full of Surprises

“…[36] Studies involving the introduction of octahedral transition metals to assemble such systems appeared a few years later. [37] The fac-Re-(CO) 3 corner system was exploited by Hupp, [38] while Alessio used the fac-RuCl 2 (Me 2 SO) 3 (CO) complex [39] to generate multiple porphyrin-containing molecular assemblies. Similarly, arene ruthenium building blocks can be exploited to generate metalla-boxes.…”

Self‐Assembled Nanoreactors

“…110 The assembly has the shape of an open-ended box with an internal cavity of approximate dimensions 18 × 18 × 18 Å. This preorganized assembly can encapsulate Mn(III) porphyrin 44, which is a well-known catalyst for the epoxidation of olefins (Scheme 3).…”

Supramolecular Coordination Chemistry and Functional Microporous Molecular Materials

“…Comprising nearly all of this subset are molecular squares featuring cisligated Re(CO) 3 X (X ) Cl or Br) corners and rigid or semirigid difunctional azine or imine edges: compounds 2-9 shown. [28][29][30][31][32][33][34] They are typically obtained in a single step, in nearly quantitative yield, via a "coordinative self-assembly" process (Scheme 1). 31,35,36 The process makes use of Re(CO) 5 X as a simple synthon predisposed, via classical trans labilization effects, to liberate two (and only two) carbonyl ligands, exclusively from cis sites.…”

“…30,[80][81][82][83][84][85][86][87] Even fewer have focused on such behavior in the solid state. 28,31,35,38 A potentially significant advantage of a solid-state or materials approach over, for example, an approach based on a monolayer of receptor molecules, is the higher guest-uptake capacity available.…”