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Electronic, Spectroscopic, and Ion-Sensing Properties of a Dehydro[m]pyrido[14]- and [15]annulene Isomer Library

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Institut Charles Sadron, UPR 22-CNRS, 23 rue du Loess, Strasbourg, France
§ Laboratoire d’Electrochimie et de Chimie Physique du Corps Solide and §Laboratoire d’Infochimie, Université de Strasbourg, UMR 7177-CNRS, 4 rue Blaise Pascal, Strasbourg, France
Service de Radiocristallographie, Université de Strasbourg, UMR 7177-CNRS, 1 rue Blaise Pascal, Strasbourg, France
Cite this: J. Org. Chem. 2012, 77, 1, 126–142
Publication Date (Web):December 1, 2011
Copyright © 2011 American Chemical Society

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    Abstract Image

    An isomeric series of dehydro[m]pyrido[n]annulenes incorporating strained 1,4-buta-1,3-diyne units have been synthesized, where m = 2, n = 14 (1ad); m = 2, n = 15 (2a,b); and m = 3, n = 15 (3). The number of pyridine rings and annulene ring π-electrons are denoted by m and n, respectively. The X-ray crystal structures of 1b and 1c confirmed their cyclic formulation. All macrocycles were found to be luminescent chromophores with differing isomer-dependent proton and metal ion-sensory emission responses, which appear collectively as analyte-specific color patterns. Within the series studied, 1a was singular in displaying the highest luminescence quantum yield and sharing the strongest emission energy and molar absorption changes upon protonation and HgII binding. Spectroscopic and electrochemical results were supported by density functional theory calculations in showing 1a, 2a, and 3 to be low bandgap materials with lowest unoccupied molecular orbitals delocalized over the 1,4-di(pyridin-4-yl)buta-1,3-diyne bridges that provide a pathway for electronic communication between the nitrogens. Overall, the investigations suggest that 1a, 2a, and 3 would be excellent ligands for the construction of novel conjugated hybrid metallosupramolecular nanostructures, polymers, and ion-sensory systems.

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    Synthesis of dehydro[m]pyrido[14]- and [15]annulenes 1ad, 2a,b, and 3; general experimental; spectroscopic characterization of macrocycles 1ad, 2a,b, and 3 and precursors 12ad and 13ad; 1H NMR investigation of solution aggregation of 1a; 1H and 13C NMR solution spectra of 1ad, 2a,b, 3, 12ad, 13ad, 1517, 19a,b, 20a,b, 22, and 23; UV–vis spectroscopic properties of precursors 13ad, 20a,b, and 23 and UV–vis absorption spectra of 1ad, 2a,b, and 3 with Hg(CF3SO3)2; general X-ray experimental, crystallographic data, and ORTEP representations for 1b and 1c; HOMO and LUMO plots of 1c,d and 2b; linear regression through origin of optical bandgap vs calculated bandgap for 1a1d, 2a,b, and 3; calculated structure Cartesian coordinates of 1ad, 2a,b, and 3; and references (continued). This material is available free of charge via the Internet at

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