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. 2008 Dec 8;64(50):11495-11503.
doi: 10.1016/j.tet.2008.08.062.

Carbon-rich supramolecular metallacycles and metallacages

Brian H Northrop  1 , Dennis Chercka, Peter J Stang
Affiliations

Carbon-rich supramolecular metallacycles and metallacages

Brian H Northrop et al. Tetrahedron. .

Abstract

Coordination-driven self-assembly via the directional-bonding approach utilizes rigid transition metal acceptors and electron-rich donors to allow for complex, nanoscale 2D polygons and 3D polyhedra to be prepared under mild conditions and in high yields. To ensure proper rigidity and directionality, many acceptor and donor precursors contain largely carbon-rich aromatic and/or acetylenic moieties. This article introduces self-assembly as an alternative means of synthesizing carbon-rich materials and discusses the development, design, synthesis, and applications of carbon-rich supramolecular metallacycles and metallacages as well as the self-assembly of new diastereomeric carbon-rich supramolecular triangles.

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Figures

Figure 1
Figure 1
The directional-bonding approach to the self-assembly of 2D metallacyclic polygons.
Figure 2
Figure 2
The directional-bonding approach to the self-assembly of select 3D metallacages.
Figure 3
Figure 3
Carbon-rich ditopic 90° metal acceptors (A) and ditopic 180° donors (B).
Figure 4
Figure 4
Carbon-rich Pt(II) acceptors with turning angles of 0°, 60°, 109°, 120°, and 180° (A) as well as non-linear ditopic donors (B).
Figure 5
Figure 5
Trigonal planar tritopic donors and acceptors.
Figure 6
Figure 6
Examples of three carbon-rich trigonal pyramidal tritopic donors.
Figure 7
Figure 7
31P NMR spectrum (121.5 MHz, CD3COCD3, 298 K) of the self-assembled carbon-rich supramolecular diastereomers. The inset shows that what appears to be a single sharp peak is actually composed of two peaks of differing intensity, indicating one diastereomer is formed preferentially.
Figure 8
Figure 8
Structures of symmetric and asymmetric diastereomers obtained from molecular modeling. Measurements of the distance between neighboring phenanthrene units partially demonstrates differences in structural strain between the diastereomers. Color scheme: C = grey, N = blue, P = purple, Pt = yellow.
Scheme 1
Scheme 1
The self-assembly of carbon-rich metallacyclic squares. In all cases the acceptor and donor are mixed in a 1:1 molar ratio. M = Pt, Pd.
Scheme 2
Scheme 2
Summary of protocols for self-assembling a variety of carbon-rich 2D polyhedra. In each case the donor and acceptor precursors are mixed in a 1:1 molar ratio. a = Pt(PMe3)2(OTf)2.
Scheme 3
Scheme 3
Use of trigonal planar tritopic donors to self-assemble carbon-rich truncated tetrahedra and trigonal prisms. a = Pt(PMe3)2(OTf)2.
Scheme 4
Scheme 4
The self-assembly of “walled” trigonal prism geometries using carbon-rich tetratopic donors and 90° metal acceptors in a 3:6 molar ratio.
Scheme 5
Scheme 5
The self-assembly of cuboctahedra from a 12 ditopic 120° precursors and 8 complementary tritopic trigonal planar precursors.
Scheme 6
Scheme 6
Self-assembly of trigonal bipyrimidal, adamantoid, and dodecahedral polygons. Component acceptor and donor precursors are mixed in 3:2, 6:4, and 30:20 molar ratios, respectively.
Scheme 7
Scheme 7
Self-assembly of “symmetric” and “asymmetric” diastereomers of a carbon-rich supramolecular triangle from achiral building blocks.
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