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Tetratopic rctt-tetrakis(4-pyridyl)cyclobutane acts as an angular bifunctional ligand that yields a single-stranded helicate coordination polymer based on a Ln(III) ion.

In this microreview, we show how principles of coordination-driven self -assembly can be used to direct chemical reactivity in the organic solid state. We also show how products obtained from the templated solid-state reactions can be used as organic building units of metal-organic frameworks and coordination capsules. Self-assembled structures based on dinuclear Zn-II and Ag-I complexes are used to direct stereocontrolled [2+2] photodimerizations of vinylpyridines in the solid state in up to quantitative yield. The products are used as bi- and polytopic ligands of self-assembled coordination capsules and metal-organic frameworks. We also describe emerging metal-based approaches to conduct mechanochemical reactions in organic solids. In addition to the field of supramolecular coordination chemistry, these observations impact the field of green chemistry.

We show that a molecule constructed from an organic solid-state synthesis, namely, rctt-1,3-bis(2-pyridyl)-2,4-bis(4-pyridyl)cyclobutane (ht-2,4 ‘-tpcb) upon reaction with Cu(II) and Zn(II) ions gives one- (1D) and two-dimensional (2D) metal-organic frameworks (MOFs) of composition [Cu(hfac)(2)(2,4 ‘-tpcb-ht)](infinity) (where: hfac=hexafluoroacetylacetonate) (1) and [Zn(2,4 ‘-tpcb-ht)(2)(H2O)(2)](infinity)(2+), (2). Each MOF possesses uncoordinated, or free, 2-pyridyl groups that decorate the walls of each extended structure. (c) 2006 Elsevier B.V. All rights reserved.