One-step orthogonal-bonding approach to the self-assembly of neutral rhenium-based metallacycles: synthesis, structures, photophysics, and sensing applications.

Self-assembled metallacycles offer structural diversity and interesting properties based on their unique frameworks and host-guest chemistry. As a result, the design and synthesis of these materials has attracted significant research interest. This Account describes our comprehensive investigations of an effective orthogonal-bonding approach for the self-assembly of neutral Re-based metallacycles. We discuss the various types of assemblies that can be created based on the nuclearity of the luminophore, including bimetallic materials, rectangles, cages, and calixarenes. This approach permits the preparation of a rectangular molecule, rather than two molecular squares, in excellent yields. We extended this strategy to the high yield synthesis of a series of Re-based metallacycles with different shapes. With the rich spectroscopic and luminescence properties, Re(I) metallacycles provide an excellent platform for studies of host-guest interactions. When possible, we also present potential applications of the luminescent Re-based metallosupramolecular assemblies. The orthogonal-bonding approach involves the simultaneous introduction of two ligands: a bis-chelating ligand to coordinate to two equatorial sites of two fac-(CO)(3)Re cores and a monotopic or ditopic nitrogen-donor ligand to the remaining orthogonal axial site. Furthermore, by the appropriate choice of the predesigned organic ligands with various backbones and connectivity information and fac-Re(CO)(3) metal centers, we could also design other novel functional metallacycles including rotors, gondolas, cages, triangles, and metallacalixarenes in high yields. The incorporation of flexible ligands into the Re(I) metallacycles allows us to introduce various conformation states and novel structures. As a result, these structures acquire new functions, such as adaptive recognition properties. For example, we assembled Re(I)-based metallacyclic rotors via a one-step process. These rotors, which contain a para-phenylene unit that rapidly rotates within the metallacycles, are prototypes of a neutral altitudinal rotor. Most of the metallacycles are luminescent. The ability to chemically modify the organic ligands offers opportunities to create structural diversity and to tune the photophysical properties of these Re(I) metallacycles efficiently. Several strategies for increasing emission quantum yields and excited-state lifetimes and tuning the colors in Re(I) metallacycles are available. The cyclometalated ligands in Re(I) metallacycles improve excited state lifetimes and quantum yields, and these C-H bond-activated metallacycles are considerably more emissive than their non-C-H bond-activated analogues. The introduction of crown-ether-like recognition sites into neutral gondola-shaped metallacycles that selectively recognize metal ions also enhanced emission. Rhenium-based rectangular boxes, synthesized via a simple one-step route, contain a large and tunable hydrophobic inner cavity, which selectively recognizes benzene molecules. Such structures were the best host for benzene reported to date. In addition, we designed and synthesized novel neutral metallacalixarenes with tunable size, cavity, color, and functionality. These structures are efficient hosts for the recognition of planar aromatic guests.