Terpy(Pt–salphen)2 Switchable Luminescent Molecular Tweezers |
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Authors: | Benjamin Doistau Arnaud Tron Dr. Sergey A. Denisov Dr. Gediminas Jonusauskas Dr. Nathan D. McClenaghan Geoffrey Gontard Dr. Valérie Marvaud Prof. Dr. Bernold Hasenknopf Dr. Guillaume Vives |
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Affiliation: | 1. Sorbonne Universités, UPMC Univ Paris 06, UMR 8232, Institut Parisien de Chimie Moléculaire, 4 place Jussieu, 75005, Paris (France), Fax: (+33)?1‐44‐27‐38‐41;2. CNRS, UMR 8232, Institut Parisien de Chimie Moléculaire, 4 place Jussieu, 75005, Paris (France);3. Univ. Bordeaux, ISM (CNRS UMR 5255) & LOMA (CNRS UMR 5798), 33400 Talence (France) |
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Abstract: | The design and synthesis of switchable molecular tweezers based on a luminescent terpy(Pt‐salphen)2 ( 1 ; terpy=terpyridine) complex is reported. Upon metal coordination, the tweezers can switch from an open “W”‐shaped conformation to a closed “U”‐shaped form that is adapted for selective recognition of cations. Closing of the tweezers by metal coordination (M=Zn2+, Cu2+, Pb2+, Fe2+, Hg2+) was monitored by 1H NMR and/or UV/Vis titrations. During the titration, exclusive formation of the 1:1 complex [M( 1 )] was observed, without appearance of an intermediate 1:2 complex [M( 1 )2]. The crystallographic structure of the 1:1 complex was obtained with Pb2+ and showed a distorted helical structure. Selective intercalation of Hg2+ cations by the closed “U” form was observed. The tweezers were reopened by selective metal decoordination of the terpyridine ligand by using tris(2‐aminoethyl)amine (tren) as a competitive ligand without modification of the Pt–salphen complex. Detailed photophysical studies were performed on the open and closed tweezers. Structured emission was observed in the open form from the Pt–salphen moieties, with a high quantum yield and a long lifetime. The emission is slightly modified upon closing with 1 equivalent of Zn2+ or Hg2+, whereas a dramatic quenching was obtained upon intercalation of additional Hg2+. |
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Keywords: | cooperativity molecular tweezers phosphorescence platinum salphen |
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