2D cluster-based Coordination Polymer

1. 2D cluster-based Coordination Polymer +

2. Design and Self-Assembly of Cluster-Based Materials Abdessadek Lachgar, Wake Forest University DMR-0446763 • Supramolecular chemistry “chemistry beyond the molecule” focuses on rational design and preparation of supramolecular structures through self-assembly processes in which building units are linked through non-covalent forces such as hydrogen bonding, coordination bonds, electrostatic and charge-transfer attractions, and aromatic π-stacking interactions.[i], [ii] It is fundamentally related to the field of crystal engineering which focuses on organizing molecular or ionic building units into functional crystalline materials with desired structures and properties.[iii] Here we focus on developing synthesis strategies that will ultimately lead us to making materials by design through the bottom-up approach. We use two molecular building blocks to achieve control over the dimension and the properties of the products obtained: 1) an octahedral metal cluster with the general chemical formula [M6L12]2+ that can be considered as a nanosize metal ion 2) a metal complex with specific coordination requirements to direct the assemblies of the metal clusters into supramolecular assemblies with sizes that range between 1.7 nm and 2.7 nm (Figure 1), and hybrid inorganic-organic materials with one-, two, or three-dimensional open frameworks (Figure 2). The “nanomolecules” obtained can be functionalized in many different ways by changing the ligands of the metal complex. • [i] a) Lehn, J.M. Science1993, 260, 1762; b) Lehn, J.M. “Supramolecular Chemistry: Concepts and Perspectives” (VCH, Weinheim, 1995); c) Rebek, J., Jr.Angew. Chem. Int. Ed. Engl.1990, 29, 245; d) Vögtle, F. “Suparmolecular Chemistry” (John Wiley & Sons: New York, 1991); e) Amabilino, D.B.; Stoddart, J. F. Chem. Rev.1995, 95, 2715; f) Fyfe, M. C. T.; Stoddart, J. F. Acc. Chem. Res.1997, 30, 393; g) Harada, A.; Li, J.; Kamachi, M. Nature 1992, 356, 325; h) Harada, A.; Li, K.; Kamachi, M. Nature1994, 370, 126. • [ii] a) Rebek, J., Jr. Angew. Chem. Int. Ed. Engl.1990, 29, 245; b) Vögtle, F. Suparmolecular Chemistry; John Wiley & Sons: New York, 1991; c) Amabilino, D. B.; Stoddart, J. F. Chem. Rev.1995, 95, 2715; d) Fyfe, M. C. T.; Stoddart, J. F. Acc. Chem. Res.1997, 30, 393; e) Harada, A.; Li, J.; Kamachi, M. Nature 1992, 356, 325; f) Harada, A.; Li, K.; Kamachi, M. Nature1994, 370, 126. • [iii] a) Schmidt, G. M. J. “Photodimerization in the solid-state”, Pure Appl. Chem.1971, 27, 647; b) Desiraju, G. R. “Crystal Engineering. The Design of Organic Solids”, Elsevier: Amsterdam, 1989; (c) Etter, M. C. Acc. Chem. Res.1990, 23, 120; d) Desiraju, G. R. Nature2000, 408, 181.