Carbon-rich supramolecular metallacycles and metallacages

Northrop, Brian H.; Chercka, Dennis; Stang, Peter J.

doi:10.1016/j.tet.2008.08.062

Cited by 62 publications

(27 citation statements)

References 105 publications

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“…Substitution of the β positions of one of the pyridyl groups with chlorine atoms places these substituents too far from the Pt-N coordination site to effect self-organization. NMR spectroscopic analysis of a 1:1 mixture of 26 and 28 in CD 3 NO 2 indicated that isomer 29a was the most dominant species in solution. Isomers 29b and 29c were also formed as minor products while no evidence of isomer 29d could be observed.…”

Section: Non-absolute Self-organizationmentioning

confidence: 99%

Self-Organization in Coordination-Driven Self-Assembly

et al. 2009

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ConspectusSelf-assembly allows for the preparation of highly complex molecular and supramolecular systems from relatively simple starting materials. Typically, self-assembled supramolecules are constructed by combining complementary pairs of two highly symmetric molecular components, thus limiting the chances of forming unwanted side products. Combining asymmetric molecular components or multiple complementary sets of molecules in one complex mixture can produce myriad different ordered and disordered supramolecular assemblies. Alternatively, spontaneous self-organization phenomena can promote the formation of specific product(s) out of a collection of multiple possibilities. Self-organization processes are common throughout much of nature and are especially common in biological systems. Recently, researchers have studied self-organized self-assembly in purely synthetic systems.This Account describes our investigations of self-organization in the coordination-driven selfassembly of platinum(II)-based metallosupramolecules. The modularity of the coordination-driven approach to self-assembly has allowed us to systematically study a wide variety of different factors that can control the extent of supramolecular self-organization. In particular, we have evaluated the effects of the symmetry and polarity of ambidentate donor subunits, differences in geometrical parameters (e.g. the size, angularity, and dimensionality) of Pt(II)-based acceptors and organic donors, the influence of temperature and solvent, and the effects of intermolecular steric interactions and hydrophobic interactions on self-organization.Our studies have shown that the extent of self-organization in the coordination-driven self-assembly of both 2D polygons and 3D polyhedra ranges from no organization (a statistical mixture of multiple products), to amplified organization (wherein a particular product or products are favored over others), and all the way to the absolute self-organization of discrete supramolecular assemblies. In many cases, inputs such as dipolar interactions, steric interactions, and differences in the geometric parameters of subunits-used either alone or as multiple factors simultaneously-can achieve absolute self-organization of discrete supramolecules. We have also observed instances where selforganization is not absolute and varies in its deviation from statistical results. Steric interactions are particularly useful control factors for driving such amplified self-organization because they can be subtly tuned through small structural variations.Having the ability to fully understand and control the self-organization of complex mixtures into specific synthetic supramolecules can provide a better understanding of analogous processes in biological systems. Furthermore, self-organization may allow for the facile synthesis of complex multifunctional, multicomponent systems from simply mixing a collection of much simpler, judiciously designed individual molecular components.stang@chem.utah.edu. NIH Public Access IntroductionChemist...

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Section: Non-absolute Self-organizationmentioning

confidence: 99%

Self-Organization in Coordination-Driven Self-Assembly

et al. 2009

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“… 1 , 2 The directional bonding approach is perhaps the most intuitive design strategy. 1g , 3 This approach entails the combination of donor (ligand) and acceptor (metal complex) units, the geometries of which determine the structure of the assembly formed. A fundamental requirement of this strategy is that these building blocks are shape-persistent; possessing conformational rigidity and well-defined coordinate vectors.…”

Section: Introductionmentioning

confidence: 99%

Large, heterometallic coordination cages based on ditopic metallo-ligands with 3-pyridyl donor groups

et al. 2015

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“…The use of transition metal centres and coordination bonds has been proved to be an efficient method to obtain a great variety of discrete molecular architectures with different shapes and sizes that depends on the wide range of the species involved in the assembly process [1][2][3][4][5][6][7][8][9][10][11][12].…”

Section: Introductionmentioning

confidence: 99%