Aminoethylglycine-functionalized Ru(bpy)32+ with pendant bipyridines self-assemble multimetallic complexes by copper and zinc coordination

Carl P. Myers, Brian P. Gilmartin, Mary Elizabeth Williams

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Directed self-assembly using inorganic coordination chemistry is an attractive approach for making functional supramolecular structures. In this article, the synthesis and characterization of Ru(bpy)32+ compounds derivatized with aminoethylglycine (aeg) substituents containing pendant bipyridine (bpy) ligands is presented. The free bpy ligands in these complexes are available for metal chelation to form coordinative cross-links; addition of Cu2+ or Zn2+ assembles heterometallic structures containing two or three transition-metal complexes. Control over relative placement of metal complexes is accomplished using two strategies: two bipyridine-containing aeg strands tethered to Ru(bpy)32+ allow intramolecular coordination and result in a dimetallic hairpin motif. Ru(bpy)32+ modified with a single strand forms intermolecular cross-links forming the trimetallic complex. Each of these is characterized by a range of methods, and their photophysical properties are compared. These data, and comparison to an acetyl aegmodified Ru(bpy) 32+ complex, confirm that the metal ions cross-link bpy-containing aeg strands. Heterometallic complexes containing bound Cu 2+ cause a dramatic reduction in the Ru(bpy)32+ quantum yields and lifetimes. In contrast, the Ru(bpy)32+ hairpin with coordinated Zn2+ has only a slight decrease in quantum yield but no change in lifetime, which could be a result of steric impacts on structure in the dimetallic species. Analogous effects are not observed in the trimetallic Ru-Zn-Ru structures in which this constraint is absent. Each of these heterometallic structures represents a facile and reconfigurable means to construct multimetallic structures by metal-coordination-based self-assembly of modular artificial peptide units.

Original languageEnglish (US)
Pages (from-to)6738-6747
Number of pages10
JournalInorganic Chemistry
Volume47
Issue number15
DOIs
StatePublished - Aug 4 2008

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Coordination Complexes
strands
Zinc
Copper
zinc
Quantum yield
copper
Self assembly
self assembly
metals
Ligands
life (durability)
ligands
chelation
Chelation
peptides
Transition metals
Metal ions
metal ions
Metals

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

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title = "Aminoethylglycine-functionalized Ru(bpy)32+ with pendant bipyridines self-assemble multimetallic complexes by copper and zinc coordination",
abstract = "Directed self-assembly using inorganic coordination chemistry is an attractive approach for making functional supramolecular structures. In this article, the synthesis and characterization of Ru(bpy)32+ compounds derivatized with aminoethylglycine (aeg) substituents containing pendant bipyridine (bpy) ligands is presented. The free bpy ligands in these complexes are available for metal chelation to form coordinative cross-links; addition of Cu2+ or Zn2+ assembles heterometallic structures containing two or three transition-metal complexes. Control over relative placement of metal complexes is accomplished using two strategies: two bipyridine-containing aeg strands tethered to Ru(bpy)32+ allow intramolecular coordination and result in a dimetallic hairpin motif. Ru(bpy)32+ modified with a single strand forms intermolecular cross-links forming the trimetallic complex. Each of these is characterized by a range of methods, and their photophysical properties are compared. These data, and comparison to an acetyl aegmodified Ru(bpy) 32+ complex, confirm that the metal ions cross-link bpy-containing aeg strands. Heterometallic complexes containing bound Cu 2+ cause a dramatic reduction in the Ru(bpy)32+ quantum yields and lifetimes. In contrast, the Ru(bpy)32+ hairpin with coordinated Zn2+ has only a slight decrease in quantum yield but no change in lifetime, which could be a result of steric impacts on structure in the dimetallic species. Analogous effects are not observed in the trimetallic Ru-Zn-Ru structures in which this constraint is absent. Each of these heterometallic structures represents a facile and reconfigurable means to construct multimetallic structures by metal-coordination-based self-assembly of modular artificial peptide units.",
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Aminoethylglycine-functionalized Ru(bpy)32+ with pendant bipyridines self-assemble multimetallic complexes by copper and zinc coordination. / Myers, Carl P.; Gilmartin, Brian P.; Williams, Mary Elizabeth.

In: Inorganic Chemistry, Vol. 47, No. 15, 04.08.2008, p. 6738-6747.

Research output: Contribution to journalArticle

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AB - Directed self-assembly using inorganic coordination chemistry is an attractive approach for making functional supramolecular structures. In this article, the synthesis and characterization of Ru(bpy)32+ compounds derivatized with aminoethylglycine (aeg) substituents containing pendant bipyridine (bpy) ligands is presented. The free bpy ligands in these complexes are available for metal chelation to form coordinative cross-links; addition of Cu2+ or Zn2+ assembles heterometallic structures containing two or three transition-metal complexes. Control over relative placement of metal complexes is accomplished using two strategies: two bipyridine-containing aeg strands tethered to Ru(bpy)32+ allow intramolecular coordination and result in a dimetallic hairpin motif. Ru(bpy)32+ modified with a single strand forms intermolecular cross-links forming the trimetallic complex. Each of these is characterized by a range of methods, and their photophysical properties are compared. These data, and comparison to an acetyl aegmodified Ru(bpy) 32+ complex, confirm that the metal ions cross-link bpy-containing aeg strands. Heterometallic complexes containing bound Cu 2+ cause a dramatic reduction in the Ru(bpy)32+ quantum yields and lifetimes. In contrast, the Ru(bpy)32+ hairpin with coordinated Zn2+ has only a slight decrease in quantum yield but no change in lifetime, which could be a result of steric impacts on structure in the dimetallic species. Analogous effects are not observed in the trimetallic Ru-Zn-Ru structures in which this constraint is absent. Each of these heterometallic structures represents a facile and reconfigurable means to construct multimetallic structures by metal-coordination-based self-assembly of modular artificial peptide units.

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