Synthesis and Optoelectronic Properties of Hexahydroxylated 10‐O‐R‐Substituted Anthracenes via a New Modification of the Friedel–Crafts Reaction Using O‐Protected ortho‐Acetal Diarylmethanols |
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Authors: | Dr Agnieszka Bodzioch Dr Bernard Marciniak Dr Ewa Ró?ycka‐Soko?owska Prof Jeremiasz K Jeszka Dr Pawe? Uznański Dr Sylwester Kania Janusz Kuliński Prof Piotr Ba?czewski |
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Institution: | 1. Department of Heteroorganic Chemistry, Department of Polymer Physics, Department of Engineering of Polymer Materials, Center of Molecular and Macromolecular Studies, Polish Academy of Science, Sienkiewicza 112, 90‐363 ?ód? (Poland), Fax: (+48)?426847126;2. Department of Structural and Material Chemistry, Institute of Chemistry, Environmental Protection and Biotechnology, Jan D?ugosz University, Armii Krajowej 13/15, 42‐200 Cz?stochowa (Poland);3. Department of Man‐Made Fibres, Technical University of ?ód? ul. ?eromskiego 116, 90‐543 ?ód? (Poland);4. Centre of Mathematics and Physics, Technical University of ?ód?, Al. Politechniki 11, 90‐924 ?ód? (Poland) |
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Abstract: | A new modification of the Friedel–Crafts type intramolecular cyclization involving O‐protected ortho‐acetal diarylmethanols as a new type of reactant, was carried out for the first time in a medium containing a large amount of water at room temperature and enabled synthesis of a series of electron‐rich, hexahydroxylated 10‐O‐R‐substituted anthracenes, where R is an alkyl (Me, nBu, n‐C16H33) or arylalkyl group (CH2Ph, CH2‐2‐Napht, CH2C6H4CH2OAr) and also evaluation of their electronic and optoelectronic properties in solution, crystal, and solid thin film. In this transformation, a central 10‐O‐R‐substituted benzene ring was formed, fused to rings originating from two independent aromatic aldehydes. The reaction proceeded via two identified mechanisms involving acetal and/or free aldehyde groups. The acid sensitive acetal and dibenzyl alkoxy functions have never been used together in the intramolecular Friedel–Crafts type cyclization. The new compounds revealed deep blue fluorescence and quantum yields in solution around 0.3. The electrical properties investigated for thin films obtained by vacuum deposition on glass were 10‐O‐R‐substituent dependent and showed much faster transient current decay in the case of the 10‐O‐CH2Ph derivative than for the material with a 10‐O‐Me substituent (the lifetime of charge carriers was 25 times shorter in this case). The AFM images of thin films, Stokes shifts, and X‐ray analysis of π‐stacking interactions in crystals of the new materials have been also obtained. |
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Keywords: | anthracenes cyclization fluorescence Friedel– Crafts optoelectronic properties |
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