Thermoresponsive supramolecular polymer network comprising pyrene-functionalized gold nanoparticles and a chain-folding polydiimide

Vaiyapuri, Rajendran, Greenland, Barnaby w, Rowan, Stuart J, Colquhoun, Howard M, Elliott, Joanne M and Hayes, Wayne (2012) Thermoresponsive supramolecular polymer network comprising pyrene-functionalized gold nanoparticles and a chain-folding polydiimide. Macromolecules, 45 (13). pp. 5567-5574. ISSN 0024-9297

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A thermoresponsive, supramolecular nanocom-
posite has been prepared by the addition of pyrenyl
functionalized gold nanoparticles (AuNPs) to a polydiimide
that contains receptor residues designed to form defined
complexes with pyrene. The novel pyrenyl-functionalized
AuNPs (P-AuNPs) were characterized by transmission
electron microscopy, with surface functionalization confirmed
by infrared and UV−visible spectroscopic analyses. Mixing
solutions of the P-AuNPs and a π-electron-deficient poly-
diimide resulted in the formation of electronically comple-
mentary, chain-folded and π−π-stacked complexes, so affording a new supramolecular nanocomposite network which precipitated from solution. The P-AuNPs bind to the polydiimide via π−π stacking interactions to create supramolecular cross- links. UV−visible spectroscopic analysis confirmed the thermally reversible nature of the complexation process, and transmission electron microscopy (TEM), infrared spectroscopy (IR), and differential scanning calorimetry (DSC) were used to characterize the supramolecular-nanocomposite material. The supramolecular polymer network is insoluble at room temperature, yet may be dissolved at temperatures above 60 °C. The thermal reversibility of this system is maintained over five heat/cool cycles without diminishment of the network characteristics. In contrast to the individual components, the nanocomposite formed self- supporting films, demonstrating the benefit of the supramolecular network in terms of mechanical properties. Control experiments probing the interactions between a model diimide compound that can also form a π-stacked complex with the π- electron rich pyrene units on P-AuNPs showed that, while complexation was readily apparent, precipitation did not occur because a supramolecular cross-linked network system could not be formed with this system.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry
Depositing User: Barnaby Greenland
Date Deposited: 12 Apr 2018 13:31
Last Modified: 12 Apr 2018 13:31

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