Abstract
The morphologies, synthesis, and photophysical characterizations of poly[2,7-(9,9-dihexylfluorene)]-block-poly(2-(diethylamino)ethylmethacrylate) using amphiphilic rod-coil (PF-b-PDEAEMA) were demonstrated. The aggregation morphologies of PF13-b-PDEAEMA100 were manipulated by tuning the selectivity of mixed THF/methanol solvents with methanol contents ranging from 0 to 90 vol%. The morphological transformation of PF13-b-PDEAEMA100 caused significant changes in its photophysical properties, including absorption, fluorescence spectra, and fluorescence quenching. Moreover, the thermal stability of PF13-b-PDEAEMA100 was investigated by varying the annealing temperature. The results of the present study suggest that the solvent selectivity influences the photophysical properties and aggregation morphologies of rod-coil block copolymers in solid and solution states.
Highlights
The potential of self-assembling amphiphilic rod-coil block copolymers in developing polymeric materials with novel supramolecular nanostructures and tunable physical properties has been demonstrated [1,2,3,4]
After cooling to room temperature, the mixture was passed through an Al2O3 column to remove the copper catalyst, precipitated into an excess amount of n-hexane, and filtered; the product was dried under vacuum at 30∘C to obtain 300 mg of PF13b-PDEAEMA100 yellow solid. 1H NMR (CDCl3, 300 MHz) d: 0.78–0.98 (3 H, –CH2C(CH3)–), 1.78–1.91 (2 H, –CH2C(CH3)–), 2.41–2.59 (10H, –N(CH2CH3)2), 2.69 (2 H, –OCH2CH2N(CH2CH3)2), 3.98 (2 H, –OCH2CH2N – (CH2CH3)2), 7.25–7.79 (10 H, fluorene aromatic protons and phenyl end group) (Figure 2)
The thermal properties of the PF macroinitiator and PF-b-PDEAEMA were estimated through thermogravimetric analysis (TGA; Figure 4)
Summary
The potential of self-assembling amphiphilic rod-coil block copolymers in developing polymeric materials with novel supramolecular nanostructures and tunable physical properties has been demonstrated [1,2,3,4]. Such copolymers, which comprise mutually repulsive hydrophobic rod-like and hydrophilic coil-like segments, exhibit various nanoscale aggregation morphologies, such as spherical, lamellar, cylindrical, and worm-like structures [5,6,7,8]. Conjugated rod-coil block copolymers exhibit unusual photophysical characteristics and may serve as novel optoelectronic materials. Jenekhe and Chen demonstrated that poly(phenylquinoline)b-poly(styrene), a rod-coil copolymer, which showed an unusual honeycomb morphology, enhanced the solubility of fullerenes, such as C60 and C70, by encapsulating the fullerenes in the block conjugated copolymer aggregates [16]
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