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Title: Solution and Structural Investigations of Ligand Preorganization in Trivalent Lanthanide Complexes of Bicyclic Malonamides

Abstract

This report describes an investigation into the coordination chemistry of trivalentlanthanides in solution and the solid state with acyclic and preorganized bicyclic malonamide ligands. Two experimental investigations were performed: solution bindingaffinities were determined through single-phase spectrophotometric titrations and the extent of conformational change upon binding was investigated with single-crystal X-raycrystallography. Both experimental methods compare the bicyclic malonamide (BMA), which is designed to be preorganized for binding trivalent lanthanides, to an analogousacyclic malonamide. Results from the spectrophotometric titrations indicate that BMA exhibits a 10-100 times increase in binding affinity to Ln(III) over acyclic malonamide.In addition, BMA forms compounds with high ligand-metal ratios, even when competing with water and nitrate ligands for binding sites. The crystal structures exhibit nosignificant differences in the nature of the binding between Ln(III) and the BMA or acyclic malonamide. These results support the conclusion that rational ligand design canlead to compounds that enhance the binding affinities within a ligand class.

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
886712
Report Number(s):
PNNL-SA-44668
Journal ID: ISSN 0020-1669; INOCAJ; KP1302000; TRN: US200616%%1122
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry, 45(4):1498-1507; Journal Volume: 45; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; AFFINITY; CHEMISTRY; CONFORMATIONAL CHANGES; CRYSTAL STRUCTURE; CRYSTALLOGRAPHY; DESIGN; NITRATES; RARE EARTHS; WATER; bicyclic; malonamides

Citation Formats

Parks, Bevin W., Gilbertson, Robert D., Hutchison, J. E., Rather Healey, Elisabeth, Weakley, Timothy J R, Rapko, Brian M., Hay, Benjamin P., Sinkov, Sergei I., Broker, Grant A., and Rogers, Robin D. Solution and Structural Investigations of Ligand Preorganization in Trivalent Lanthanide Complexes of Bicyclic Malonamides. United States: N. p., 2006. Web. doi:10.1021/ic050437d.
Parks, Bevin W., Gilbertson, Robert D., Hutchison, J. E., Rather Healey, Elisabeth, Weakley, Timothy J R, Rapko, Brian M., Hay, Benjamin P., Sinkov, Sergei I., Broker, Grant A., & Rogers, Robin D. Solution and Structural Investigations of Ligand Preorganization in Trivalent Lanthanide Complexes of Bicyclic Malonamides. United States. doi:10.1021/ic050437d.
Parks, Bevin W., Gilbertson, Robert D., Hutchison, J. E., Rather Healey, Elisabeth, Weakley, Timothy J R, Rapko, Brian M., Hay, Benjamin P., Sinkov, Sergei I., Broker, Grant A., and Rogers, Robin D. Mon . "Solution and Structural Investigations of Ligand Preorganization in Trivalent Lanthanide Complexes of Bicyclic Malonamides". United States. doi:10.1021/ic050437d.
@article{osti_886712,
title = {Solution and Structural Investigations of Ligand Preorganization in Trivalent Lanthanide Complexes of Bicyclic Malonamides},
author = {Parks, Bevin W. and Gilbertson, Robert D. and Hutchison, J. E. and Rather Healey, Elisabeth and Weakley, Timothy J R and Rapko, Brian M. and Hay, Benjamin P. and Sinkov, Sergei I. and Broker, Grant A. and Rogers, Robin D.},
abstractNote = {This report describes an investigation into the coordination chemistry of trivalentlanthanides in solution and the solid state with acyclic and preorganized bicyclic malonamide ligands. Two experimental investigations were performed: solution bindingaffinities were determined through single-phase spectrophotometric titrations and the extent of conformational change upon binding was investigated with single-crystal X-raycrystallography. Both experimental methods compare the bicyclic malonamide (BMA), which is designed to be preorganized for binding trivalent lanthanides, to an analogousacyclic malonamide. Results from the spectrophotometric titrations indicate that BMA exhibits a 10-100 times increase in binding affinity to Ln(III) over acyclic malonamide.In addition, BMA forms compounds with high ligand-metal ratios, even when competing with water and nitrate ligands for binding sites. The crystal structures exhibit nosignificant differences in the nature of the binding between Ln(III) and the BMA or acyclic malonamide. These results support the conclusion that rational ligand design canlead to compounds that enhance the binding affinities within a ligand class.},
doi = {10.1021/ic050437d},
journal = {Inorganic Chemistry, 45(4):1498-1507},
number = 4,
volume = 45,
place = {United States},
year = {Mon Feb 20 00:00:00 EST 2006},
month = {Mon Feb 20 00:00:00 EST 2006}
}