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Polynuclear Lanthanide-Hydroxo Complexes |
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Lanthanide
ions and complexes occupy a special position in developing synthetic
nucleases that function as catalysts for the hydrolytic cleavage of RNA or
DNA.
Stimulated by the serendipitous isolation of a number of lanthanide
complexes that feature the common active-site structure of dinuclear
metallo-phosphodiesterases, we have been attempting the rational design
and synthesis of polynuclear lanthanide–hydroxo species via ligand-controlled
hydrolysis of the lanthanide ions. The efforts yielded a series of highly
sophisticated yet structurally well-defined lanthanide–hydroxo
complexes. In addition to their potential applications for the study of
biomimetic catalysis of phosphate diester cleavage, these high-nuclearity
complexes may, with appropriate further development, be used as
contrast-enhancing agents in biomedical imaging procedures.
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| References
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Wang,
R.; Zheng, Z.; Jin, T.; Staples, R. “Coordination Chemistry of
Lanthanide at ‘High’ pH: Synthesis and Structure of the
Pentadecanuclear Complex of Europium(III) with Tyrosine” Angew.
Chem. Int. Ed. 1999, 38, 1813-1815.
Wang, R.; Carducci, M. D.; Zheng, Z. “Direct Hydrolytic Route to
Molecular Polyoxo Lanthanide Clusters” Inorg. Chem. 2000, 39,
1836-1837.
Zheng, Z.; Wang, R. “Assembling Lanthanide Clusters under Physiological
or Higher pH-Conditions” Comments Inorg. Chem.
2000, 22, 1-30.
Wang, R.; Zheng, Z.; Jin, T. “A New Paradigmatic Coordination Chemistry
of The Lanthanides: Design, Synthesis, and Structural Studies of
Polymetallic Lanthanide Complexes with a-Amino Acids under Physiological pH conditions” Sinica
Chim. Acta 2000, 58,
1481-1492.
Wang, R.; Liu, H.; Carducci, M. D.; Jin, T.; Zheng, C.; Zheng, Z.
“Lanthanide Coordination with a–Amino Acids under Near Physiological pH Conditions: Polymetallic
Complexes Containing the Cubane–Like [Ln4(m3–OH)4]8+
Cluster Core” Inorg. Chem. 2001,
40, 2743-2750.
Zheng, Z. “Ligand-Controlled Self-Assembly of Polynuclear Lanthanide-Oxo/Hydroxo
Complexes: from Synthetic Serendipity to Rational Supramolecular Design”
Chem. Commun. 2001,
2521-2529 (feature article, journal cover).
Wang,
R.; Selby, H. D.; Liu, H.; Carducci, M. D.; Jin, T.; Anthis, J.; Zheng,
Z.; Staples, R. J. “Halide-Templated Assembly of Polynuclear Lanthanide-Hydroxo
Complexes” Inorg. Chem. 2002, 41,
278-286 (featured on cover). |
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