Charles N. Moorefield

Square-planar Pd(II), Pt(II), and Au(III) terpyridine complexes: their syntheses, physical properties, supramolecular constructs, and biomedical activities.

5.1.2. Viscosity and Thermal Denaturation 1874 5.1.3. Induced Circular Dichroism 1875 5.1.4. Competitive Fluorescence Spectroscopy 1875 5.1.5. Closed Circular DNA 1876 5.1.6. Stereochemical Changes in DNA 1876 5.1.7. Site-Specific Intercalation 1877 5.1.8. Other Mononuclear Intercalators 1877 5.1.9. Multinuclear Intercalators 1878 5.2. Covalent Binding to Biomolecules 1881 5.3. Labeling Biomolecules 1882 5.4. Cytotoxicity 1885 5.4.1. Chemotherapeutic Agents 1886 5.4.2. Radiotherapeutic Agents 1892 6. Conclusion 1892 7. Acknowledgments 1892 8. References 1893

Nanoassembly of a Fractal Polymer: A Molecular Sierpinski "Hexagonal Gasket"

Mathematics and art converge in the fractal forms that also abound in nature. We used molecular self-assembly to create a synthetic, nanometer-scale, Sierpinski hexagonal gasket. This nondendritic, perfectly self-similar fractal macromolecule is composed of bis-terpyridine building blocks that are bound together by coordination to 36 Ru and 6 Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.

Recent progress and applications for metallodendrimers

Progress in metallodendritic architectures is discussed as it relates to catalysis, luminescence, sensors, and molecular switches. It is intended that the reader will gain an appreciation for the different roles that metals can play in dendritic connectivity as well as their vast potential for application-oriented nanoscale device construction.

Stoichiometric Self-Assembly of Shape-Persistent 2D Complexes: A Facile Route to a Symmetric Supramacromolecular Spoked Wheel

An approach to multicomponent coordination-driven self-assembly of the first terpyridine-based, shape-persistent, giant two-dimensional D(6h) supramacromolecular spoked wheel is reported. Mixing core T6, rim T3, and Zn(II) or Cd(II) ions in a stoichiometric ratio (1:6:12) permitted the selective generation of a highly symmetric spoked wheel in 94% isolated yield via geometric and thermodynamic control. The products were characterized by a combination of traveling-wave ion mobility mass spectrometry and NMR techniques together with TEM imaging, which agreed with computational simulations.

Self- and Directed Assembly of Hexaruthenium Macrocycles

Rigid terpyridine-based building blocks allow easy access to large polymetallomacrocycles (see picture) through a self-assembly process. Such routes are envisioned to provide one-step methods to higher order motifs and facilitate the creation of precisely organized, metal-based networks for new energy storage devices.

Hexagonal terpyridine--ruthenium and -iron macrocyclic complexes by stepwise and self-assembly procedures.

Methods for the self-assembly, as well as directed construction, of hexaruthenium metallomacrocycles employing bisterpyridine building blocks are described. Self-assembly is effected by a combination of equimolar mixtures of bismetalated and nonmetalated bis(terpyridinyl) monomers each possessing the requisite planar, 60 degrees, terpyridine-metal-terpyridine connectivity. Stepwise synthesis of the identical hexamer is also discussed and used to aid in verification of the self-assembled product. Preparation and analysis of the related FeII metallomacrocycle are detailed and its TEM image confirms the hexameric structure. Characterization of the metalated products includes cyclic voltammetry along with the routine analytical techniques.

Stoichiometric Self-Assembly of Isomeric, Shape-Persistent, Supramacromolecular Bowtie and Butterfly Structures

Two novel macromolecular constitutional isomers have been self-assembled from previously unreported terpyridine ligands in a three-component system. The terpyridine ligands were synthesized in high yields via a key Suzuki coupling. Restrictions of the possible outcomes for self-assembly ultimately provided optimum conditions for isolation of either a molecular bowtie or its isomeric butterfly motif. These isomers have been characterized by ESI-MS, TWIM-MS, (1)H NMR, and (13)C NMR. Notably, these structural isomers have remarkably different drift times in ion mobility separation, corresponding to different sizes and shapes at high charge states.

Metallomicellanols: incorporation of ruthenium(II)–2,2′: 6′,2″-terpyridine triads into cascade polymers

Facile alkoxylation of 4′-chloro-2,2′ :6′,2″-terpyridine with the mono- and tri-hydroxylic cascade (dendritic) building blocks, 4-(3-hydroxypropyl)-4-(3-benzyloxypropyl)-1,7-bis(benzyloxy)heptane 4 and 4-amino-4-(3-hydroxypropyl)heptane-1,7-diol 3, has allowed the synthesis of a dodecaruthenium macromolecule 11 employing ligand–metal–ligand connectivity.

Supramolecular chemistry of flexible, dendritic-based structures employing molecular recognition

Molecular recognition of glutarimide using 2,6-diamidopyridine units incorporated into dendritic building blocks is examined.

Self-Assembly of a Supramolecular, Three-Dimensional, Spoked, Bicycle-like Wheel†

Where theres a wheel, theres a way: The terpyridine-based title system has been synthesized through a facile self-assembly process. Two tris(terpyridine) ligands possessing angles of either 120° or 60° between adjacent tpy units were mixed with a stoichiometric amount of Zn(2+) (2:6:12) to generate the desired coordination-driven bicycle-like wheel (90 % yield).