Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 19, Issue 39, Pages 12991-13001Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201301539
Keywords
gels; hybrid materials; nucleation and growth; sonication; squaraine
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Funding
- European Commission at CNR-ISOF [PIIF-GA-2010-276574, PITN-GA-2008-215399]
- Italian Ministry of Research (MIUR)
- Consiglio Nazionale delle Ricerche (CNR) [CX2TLM]
- FIRB Futuro in Ricerca SUPRACARBON [RBFR10DAK6]
- MACOL PM [P04. 010]
- Progetto Bandiera N-CHEM
- Istituto di Studi Avanzati, University of Bologna
- Council of Scientific and Industrial Research (CSIR), Government of India
- Department of Atomic Energy (DAE), Government of India
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A squaraine dye functionalized with a bulky trialkoxy phenyl moiety through a flexible diamide linkage (GA-SQ) capable of undergoing self-assembly has been synthesized and fully characterized. Rapid cooling of a hot solution of GA-SQ to 0 degrees C results in self-assembled precipitates consisting of two types of nanostructures, rings and ill-defined short fibers. The application of ultrasound modifies the conditions for the supersaturation-mediated nucleation, generating only one kind of nuclei and prompting the formation of crystalline fibrous structures, inducing gelation of solvent molecules. The unique self-assembling behavior of GA-SQ under ultrasound stimulus has been investigated in detail by using absorption, emission, FT-IR, XRD, SEM, AFM and TEM techniques. These studies reveal a nucleation growth mechanism of the self-assembled material, an aspect rarely scrutinized in the area of sonication-induced gelation. Furthermore, in order to probe the effects of nanoscale substrates on the sonication-induced self-assembly, a minuscule amount of single-walled carbon nanotubes was added, which leads to acceleration of the self-assembly through a heterogeneous nucleation process that ultimately affords a supramolecular gel with nanotape-like morphology. This study demonstrates that self-assembly of functional dyes can be judiciously manipulated by an external stimulus and can be further controlled by the addition of carbon nanotubes.
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