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- Copolymer sequence (1)
- MALDI-TOF MS/MS (1)
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- Photoligation (1)
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Designing artificial macromolecules with absolute sequence order represents a considerable challenge. Here we report an advanced light-induced avenue to monodisperse sequencedefined functional linear macromolecules up to decamers via a unique photochemical approach. The versatility of the synthetic strategy—combining sequential and modular concepts—enables the synthesis of perfect macromolecules varying in chemical constitution and topology. Specific functions are placed at arbitrary positions along the chain via the successive addition of monomer units and blocks, leading to a library of functional homopolymers, alternating copolymers and block copolymers. The in-depth characterization of each sequence-defined chain confirms the precision nature of the macromolecules. Decoding of the functional information contained in the molecular structure is achieved via tandem mass spectrometry without recourse to their synthetic history, showing that the sequence information can be read.We submit that the presented photochemical strategy is a viable and advanced concept for coding individual monomer units along a macromolecular chain.
The development of a facile covalent strategy for the fabrication of organic conducting polymers (OCPs)/carbon nanotubes (CNTs) based molecular hybrid materials remains a challenge and is expected to address the detrimental intrinsic bundling issue of CNTs. In view of the pristine CNTs' ability to undergo Diels–Alder reactions with dienes, we report the synthesis of a novel poly(3-hexylthiophene) (P3HT) based organic conducting polymer (OCP) with terminal cyclopentadienyl (Cp) groups. The synthetic strategy employed is based on a combination of in situ end group functionalization via Grignard metathesis (GRIM) polymerization and a subsequent end group switching via reaction with nickelocene. Characterization data from Matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDITOF MS) fully support the successful synthesis of monofunctional Cp-capped P3HT, which was found to be highly reactive toward dienophile end-capped polystyrene (PS). The Cp-capped P3HT was subsequently ligated to the surface of pristine single walled CNTs (SWCNTs). The resulting P3HT/SWCNTs molecular hybrid material was characterized using thermogravimetric analysis (TGA), elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), and high resolution transmission electron microscopy (HRTEM). The data from TGA, EA, and XPS were used to quantitatively deduce the grafting density. P3HT/SWCNTs prepared with Cp capped P3HT was found to contain 2 times more P3HT than the reference sample, featuring a grafting density of 0.0510 chains·nm–2 and a periodicity of 1 P3HT chain per 748 carbon atoms of the SWCNTs. HRTEM revealed individual SWCNTs wrapped with P3HT whereas in the reference sample P3HT was adsorbed on the bundles of the SWCNTs. The results presented here provide a new avenue for designing novel materials based on CNTs and OCPs.