Tunable Fluorene-Based Dynamers through Constitutional Dynamic Chemistry

• Published in: Chemistry : a European journal Vol. 12; no. 6; pp. 1723 - 1735
• Main Authors: Giuseppone, Nicolas, Fuks, Gad, Lehn, Jean-Marie
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 08.02.2006; WILEY‐VCH Verlag; Wiley; Wiley-VCH Verlag
• Subjects: Chemical Sciences; Chemistry; Chemistry, Multidisciplinary; dynamic combinatorial chemistry; molecular diversity; Physical Sciences; polymers; Science & Technology; stimuli-responsive systems; tunable functional materials; POLYFLUORENE DERIVATIVES; COVALENT; VIRTUAL COMBINATORIAL LIBRARIES; molecular diversity; SELF-ORGANIZATION; ELECTROLUMINESCENCE; EVOLUTION; CONJUGATED POLYMERS; COMPONENT EXCHANGE; dynamic combinatorial chemistry; stimuli-responsive systems; DIVERSITY; polymers; tunable functional materials; SELECTION
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200501037

Dynamic covalent iminofluorene‐based oligomers and polymers have been generated. They undergo constitutional recomposition under the effect of two parameters, acidity and ZnII metal ions. As a result, marked changes in physical properties take place. The results illustrate the response of such a dynamic system to chemical effectors (H+ and ZnII), thus demonstrating the adaptive behavior of the system under the pressure of external factors. They also point to the possibility of modulating optical properties (UV‐visible absorption and fluorescence) by constitutional recomposition in response to a specific trigger. Such features allow the development of dynamic materials, the functional properties of which may respond to external stimuli. Des oligomères et des polymères réversibles de type iminofluorènes ont été générés. Ils subissent une recomposition constitutionnelle sous l'influence des paramètres: concentration en protons et en ions zinc(II). Il en résulte des modifications prononcées des propriétées optiques. Les résultats illustrent les possibilités offertes par les changements de constitution en réponse à des stimuli chimiques (H+ et ZnII), et ils démontrent l'adaptation de tels systèmes sous la pression de paramètres environnementaux. Cette modulation de la constitution permet la modulation des propriétés optiques (absorption UV‐Vis et fluorescence) en fonction des stimuli imposés. De tels systèmes présentent un intérêt particulier pour le développement de matériaux dynamiques dont les propriétés fonctionnelles se modifient en réponse à des stimulations externes. The actor builds the stage on which it can play! Reversible oligomers and polymers based on fluorene components form tunable sets of constituents that respond to external triggers, such as protons and metal ions (see scheme). In particular, zinc(II) ions lead to a constitutional reorganization that generates polyfluoreneimines, which in turn by interaction with these ions produce an optical signal revealing their very presence.