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Cooperative Au(I)···Au(I) Interactions and Hydrogen Bonding as Origin of a Luminescent Adeninate Hydrogel Formed by Ultrathin Molecular Nanowires
journal contribution
posted on 2018-03-22, 11:18 authored by Daniel Blasco, José M. López-de-Luzuriaga, Miguel Monge, M. Elena Olmos, David Pascual, María Rodríguez-CastilloTwo water-soluble
[Au(9N-adeninate)(PR3)] complexes
(PR3 = PMe3 (1); PTA (3)) were synthesized by the coordination of the respective cationic
[Au(PR3)]+ fragment to the 9N position of the adeninate anion. Both complexes crystallize
as dimers by aurophilic contacts of 3.2081(6) Å in 1 and 3.0942(7) and 3.0969(7) Å in 3, but different
packings are observed due to the crystallizing solvent choice and
the nature of the ancillary phosphine ligand. At this regard, different
supramolecular behavior is observed in water, ranges from the formation
of ultrathin nanowires of 5.3 ± 1.9 nm of diameter and up to
1.5 μm in length and leads to a blue-luminescent hydrogel for 1, to the single-crystallization of 3. Parallel
computational studies carried out show that aurophilicity and N–H···N
or O–H···N hydrogen bonding are comparable in
strength, suggesting a competition between all types of weak forces
in the final observed macroscopic properties.
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phosphine ligandUltrathin Molecular Nanowirescoordinationsupramolecular behaviorParalleldimersfragmentchoiceaurophilicitymacroscopic propertiesOriginPR 31.9PMe 3aurophilic contactssingle-crystallizationPTAInteractionnaturepackingformationblue-luminescent hydrogellengthCooperativediameterultrathin nanowiresLuminescent Adeninate Hydrogelcationic1.5 μ mtyperegard5.3nmcomplexHydrogen Bondingstrength9 N positionadeninate anion
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