Precise three-dimensional supramacromolecule interconversions
A process is provided for precise self-assembly and re-arrangement of a three-dimensional terpyridine-based coordination complex. A plurality of terpyridine-containing ligands are reacted with at least one metal ion, in a pre-selected molar ratio, to form a self-assembled three-dimensional terpyridine-based coordination complex having a first configuration. A triggering event, such as exposure to light or dilution, causes the coordination complex to re-arrange to form at least two smaller, substantially identical, three-dimensional terpyridine-based coordination complexes, each having a second configuration that is different from the first configuration. Upon application of a second triggering event, such as concentration, the re-arrangement is reversed.
1. A process for precise self-assembly and re-arrangement of a three-dimensional terpyridine-based coordination complex, the process comprising the steps of:
reacting a plurality of terpyridine-containing poly-ligand monomer molecules with at least one metal ion, wherein the metal is selected from the group consisting of Fe +2 , Ru +2 , Os +2 , Ir +2 , Zn +2 , Sn +2 , Cu +2 , Ni +2 , Ba +2 , Mg +2 , Mn +2 , Cu +2 , Pb +2 , Ca +2 , Cd +2 , and combinations thereof, to form a self-assembled three-dimensional terpyridine-based first coordination complex having a first configuration; and
exposing said first coordination complex to a triggering event selected from the group consisting of change in temperature, change in pressure, change in concentration, exposure to radiation, and combinations thereof, whereupon said first coordination complex re-arranges to form at least two smaller, substantially identical, three-dimensional terpyridine-based coordination complexes, each having a second configuration that is different from the first configuration.
2. The process of claim 1 , wherein the terpyridine-containing poly-ligand monomer molecules are bridged anthracene tetrakis(terpyridine) molecules.
3. The process of claim 2 , wherein the step of reacting includes the step of selecting a molar ratio of monomer molecules to metal ions, and wherein the selected molar ratio of monomer molecules to metal ions is about 1:2.
4. The process of claim 3 , wherein the first configuration is cuboctahedral.
5. The process of claim 4 , wherein the step of exposing said first coordination complex to a triggering event comprises the step of diluting said first coordination complex in a suitable solvent, by a factor of at least about 10.
6. The process of claim 5 , wherein the second configuration is octahedral.
7. The process of claim 1 , wherein the terpyridine-containing poly-ligand monomer molecules are tristerpyridine-based monomer molecules.
8. The process of claim 7 , wherein the step of reacting includes the step of selecting a molar ratio of monomer molecules to metal ions, and wherein the molar ratio is 2:3.
9. The process of claim 8 , wherein the first configuration is bis-rhombus.
10. The process of claim 9 , wherein the step of exposing said first coordination complex to a triggering event comprises the step of diluting said first coordination complex in a suitable solvent, by a factor of at least about 10.
11. The process of claim 10 , wherein the step of exposing said first coordination complex to a triggering event comprises the step of diluting said first coordination complex in a suitable solvent, by a factor of at least about 100.
12. The process of claim 11 , wherein the second configuration is tetrahedral.
13. The process of claim 1 , further comprising the step of exposing at least two of the smaller, three-dimensional terpyridine-based coordination complexes having the second configuration to a triggering event selected from the group consisting of change in temperature, change in pressure, change in concentration, exposure to radiation, and combinations thereof, whereupon said second coordination complexes re-arrange and combine to reform the first coordination complex having the first configuration, thereby reversing said first re-arrangement.