Rational synthesis of polar and chiral solids for applications in nonlinear optics, asymmetric catalysis and chiral separation

Despite the great progress made in the synthesis of organic nonlinear optical (NLO) materials over the past two decades, two key issues remain and thus far prevent their practical applications. First, organizing organic chromophores into an acentric bulk is still a daunting task. Second, the tradeoff between optical nonlinearity and transparency has yet to be improved. Part one of this thesis will detail a research program on the crystal engineering of acentric coordination networks for second-order NLO applications. We have devised two general approaches based on metal-coordination directed self-assembly processes for the preparation of acentric coordination networks: interpenetrated diamondoid networks and 2-D square grids. These coordination networks are intrinsically acentric and have an improved optical nonlinearity-transparency tradeoff. Detailed synthetic strategies and second-order NLO properties of these novel polymeric materials will be described.; The past few years has witnessed tremendous progress in the design and synthesis of functional metal-organic frameworks. In particular robust porous coordination networks capable of functional group and size-selective sorption have recently been synthesized. Despite this tremendous progress, the use of homochiral metal-organic frameworks in heterogeneous asymmetric catalysis and enantioselective separation has not been extensively explored. Part two of this thesis will detail research towards the design and synthesis of homochiral porous metal-organic frameworks capable of heterogeneous asymmetric catalysis and chiral separation.