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Squaraines as Reporter Units: Insights into their Photophysics, Protonation, and Metal‐Ion Coordination Behaviour
Author(s) -
RosLis Jose V.,
MartínezMáñez Ramón,
Sancenón Félix,
Soto Juan,
Spieles Monika,
Rurack Knut
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800300
Subject(s) - protonation , chemistry , photochemistry , coordination complex , fluorescence , excited state , metal , absorption (acoustics) , ion , absorption band , coordination sphere , metal ions in aqueous solution , inorganic chemistry , crystallography , materials science , atomic physics , organic chemistry , physics , optics , quantum mechanics , composite material
The synthesis, photophysical properties, protonation, and metal‐ion coordination features of a family of nine aniline‐based symmetrical squaraine derivatives are reported. The squaraine scaffold displays very attractive photophysical properties for a signalling unit. These dyes show absorption and weakly Stokes‐shifted, mirror‐image‐shaped emission bands in the visible spectral range and there are no hints of multiple emission bands. The mono‐exponential fluorescence decay kinetics observed for all the derivatives indicate that only one excited state is involved in the emission. These data stress the interpretation that squaraines can be regarded as polymethine‐type dyes. From a coordination chemistry point of view, the squaraines possess four potential binding sites; that is, two nitrogen atoms from the anilino groups and two oxygen atoms from the central C 4 O 2 four‐membered ring. These coordination sites are part of a cross‐conjugated π‐system and coordination events with protons or certain metal ions affect the electronic properties of the delocalised π‐system dramatically, resulting in a rich modulation of the colour of the squaraines. The absorption band at around 640 nm is blue‐shifted when coordination at the anilino nitrogen atoms occurs, whereas coordination to the C 2 O 4 oxygen atoms results in the development of red‐shifted bands. Addition of more than one equivalent of protons or metal cations could additionally entail mixed N , O ‐ or N , N ‐coordinated complexes, manifested in the development of a broad band at 480 nm or complete bleaching in the visible range, respectively. Analysis of the spectrophotometric titration data with HYPERQUAD yielded the macroscopic and microscopic stability constants of the complexes. Theoretical modelling of the various protonated species by molecular mechanics methods and consideration of some of the title dyes within the framework of molecular chemosensing and molecular‐scale “logic gates” complement this contribution.