Journal
SYNTHETIC METALS
Volume 147, Issue 1-3, Pages 49-55Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.synthmet.2004.05.031
Keywords
self-assembly; water-soluble porphyrins; chiral memory
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Hierarchy is a powerful and promising tool to rationally synthesize non-covalent complex species. In this paper we show two different examples of hierarchically driven aggregation processes allowing for the control of aggregation state or shape of the final species. In the first case we propose that water-soluble porphyrins presenting various protonation steps can follow kinetic routes alternative to the thermodynamic pathway; namely for each protonation step is allowed, in principle, an alternative kinetically driven homo-self-aggregation process. Our results indicate that the thermodynamic route leads to a monomeric, protonated final state, but the kinetic pathway ends with self-assemblies of the title porphyrin. The bias between the two final states can be easily pre-determined by going quickly or slowly throughout the thermodynamic-kinetic junction. The second case deals with the so-called chiral memory phenomenon. Also in this case the role of the kinetic control over the assembly process is remarkable. In particular, we have observed that self-aggregation of opposite charged, achiral porphyrins does not lead to induced chirality even if a chiral template is added after their aggregation. The final aggregates are kinetically inert, mostly because stabilized by a network of electrostatic interactions between net charges. However, if the two supramolecular components are mixed in the presence of a chiral template. then an induced circular dichroism signal (ICD) appears in the Soret region (the main absorption feature of porphyrins in the visible region whose maximum and intensity are strongly affected by the aggregation state). Removal of the template does not significantly affect the intensity of the ICD: the inert aggregates have memorized the chiral template shape. Remarkably, these species - now inherently chiral - act as very efficient templates for self-aggregation of additional non-chiral porphyrins. (C) 2004 Elsevier B.V. All rights reserved.
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