Messages in Molecules: Ligand/Cation Coding and Self-Recognition in a Constitutionally Dynamic System of Heterometallic Double Helicates
Annie Marquis Dr.
Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard-Monge, BP 70028, 67083 Strasbourg cedex, France, Fax: (+33) 3-90-24-51-40
Search for more papers by this authorVirginia Smith Dr.
Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard-Monge, BP 70028, 67083 Strasbourg cedex, France, Fax: (+33) 3-90-24-51-40
Search for more papers by this authorJack Harrowfield Dr.
Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard-Monge, BP 70028, 67083 Strasbourg cedex, France, Fax: (+33) 3-90-24-51-40
Search for more papers by this authorJean-Marie Lehn Prof. Dr.
Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard-Monge, BP 70028, 67083 Strasbourg cedex, France, Fax: (+33) 3-90-24-51-40
Search for more papers by this authorHaiko Herschbach
Laboratoire de Spectrométrie de Masse Bio-Organique, Ecole de Chimie, Polymères et Matériaux (ECPM), Université Louis Pasteur and CNRS, 25, rue Becquerel, 67087 Strasbourg cedex 2, France
Search for more papers by this authorRossella Sanvito Dr.
Laboratoire de Spectrométrie de Masse Bio-Organique, Ecole de Chimie, Polymères et Matériaux (ECPM), Université Louis Pasteur and CNRS, 25, rue Becquerel, 67087 Strasbourg cedex 2, France
Search for more papers by this authorEmmanuelle Leize-Wagner Dr.
Laboratoire de Spectrométrie de Masse Bio-Organique, Ecole de Chimie, Polymères et Matériaux (ECPM), Université Louis Pasteur and CNRS, 25, rue Becquerel, 67087 Strasbourg cedex 2, France
Institut de Chimie LC3, Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard Monge, BP 70028, 67083 Strasbourg cedex, France
Search for more papers by this authorAlain Van Dorsselaer Dr.
Laboratoire de Spectrométrie de Masse Bio-Organique, Ecole de Chimie, Polymères et Matériaux (ECPM), Université Louis Pasteur and CNRS, 25, rue Becquerel, 67087 Strasbourg cedex 2, France
Search for more papers by this authorAnnie Marquis Dr.
Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard-Monge, BP 70028, 67083 Strasbourg cedex, France, Fax: (+33) 3-90-24-51-40
Search for more papers by this authorVirginia Smith Dr.
Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard-Monge, BP 70028, 67083 Strasbourg cedex, France, Fax: (+33) 3-90-24-51-40
Search for more papers by this authorJack Harrowfield Dr.
Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard-Monge, BP 70028, 67083 Strasbourg cedex, France, Fax: (+33) 3-90-24-51-40
Search for more papers by this authorJean-Marie Lehn Prof. Dr.
Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard-Monge, BP 70028, 67083 Strasbourg cedex, France, Fax: (+33) 3-90-24-51-40
Search for more papers by this authorHaiko Herschbach
Laboratoire de Spectrométrie de Masse Bio-Organique, Ecole de Chimie, Polymères et Matériaux (ECPM), Université Louis Pasteur and CNRS, 25, rue Becquerel, 67087 Strasbourg cedex 2, France
Search for more papers by this authorRossella Sanvito Dr.
Laboratoire de Spectrométrie de Masse Bio-Organique, Ecole de Chimie, Polymères et Matériaux (ECPM), Université Louis Pasteur and CNRS, 25, rue Becquerel, 67087 Strasbourg cedex 2, France
Search for more papers by this authorEmmanuelle Leize-Wagner Dr.
Laboratoire de Spectrométrie de Masse Bio-Organique, Ecole de Chimie, Polymères et Matériaux (ECPM), Université Louis Pasteur and CNRS, 25, rue Becquerel, 67087 Strasbourg cedex 2, France
Institut de Chimie LC3, Institut de Science et d'Ingénierie Supramoléculaires (ISIS), 8, allée Gaspard Monge, BP 70028, 67083 Strasbourg cedex, France
Search for more papers by this authorAlain Van Dorsselaer Dr.
Laboratoire de Spectrométrie de Masse Bio-Organique, Ecole de Chimie, Polymères et Matériaux (ECPM), Université Louis Pasteur and CNRS, 25, rue Becquerel, 67087 Strasbourg cedex 2, France
Search for more papers by this authorGraphical Abstract
Secret code unfolded! A set of four tritopic ligands built from two subunits (bipyridine (B) and terpyridine (T)) and four metal cations generates 11 double-stranded species (see scheme), through correct coding of metal-ion recognition by the pairs B⋅B, B⋅T, and T⋅T, directed by the coordination geometry of CuI, CuII, and ZnII ions involved.
Abstract
enDouble helicates are known to exhibit self-recognition characteristics determined by the coordination geometry of the metal involved as well as by the topicity of the ligands. Combining tridentate (terpyridine, T) or bidentate (bipyridine, B) subunits in a tritopic strand affords a set of ligands able to assemble by pairs to form double helicates, homo- or heterostranded, homo- or heterotopic, depending on the coordination properties of the metals involved. The four ligand strands, BBB, TTT, BBT, and TBT form constitutionally dynamic sets of double helicates with the metal ions CuI, CuII, and ZnII; these helicates correspond to the correct coding of the BB, BT, and TT pairs for tetra-, penta-, and hexacoordinate CuI, CuII, and ZnII cations, respectively.
Abstract
frLes métallohélicates à double brin sont connus pour manifester des propriétés d'auto-reconnaissance codées à la fois par la géométrie des métaux impliqués et par la topicité des ligands. En combinant dans un même brin trimère des sous-unités tridentées (terpyridine, T) et/ou bidentées (bipyridine, B), on génère un ensemble de ligands s’appariant en double hélices pouvant être homo- ou hétéroassemblées, homo- ou hétérotopiques, selon les propriétés de coordination des métaux impliqués. Ainsi, les quatre ligands BBB, TTT, BBT et TBT forment avec les ions CuI, CuII et ZnII une bibliothèque dynamique de double hélicates, correspondant au codage correct entre les paires BB, BT et TT et les cations tétra-, penta- et hexacoordinés CuI, CuII et ZnII respectivement.
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