The nano necklace made of single-walled carbon nanotubes and an azo-containing polymer: Island-like carboxyl distribution, bead-like morphology formation, and photophysical properties manipulation

The formation of a bead-shaped microstructure of poly{[3-octylthiophene-2,5-diyl]-[p-amino-azobenzylidenequinomethane]}bonded SWNT (PDTAABQ-SWNT) reveals the inhomogeneous distribution of reactive sites along a SWNT in a covalent functionalization. The bead-shaped microstructure arises from the twisting and entangling of polymer chains due to spatial confinement and geometrical restriction, as a result of dense functionalization into island-like small areas containing a high density of carboxyl groups on the SWNT sidewall. Accordingly a portion of (Ca. 24.14%) trans-azobenzene side groups of PDTAABQ are forced to isomerize to the cis form due to a steric effect arising from the overcrowded environment in the 'bead'. The experimental findings are well-correlated with the molecular simulation, particularly for the physical realization of a bead-shaped microstructure and a trans-cis isomerization. The distortion in morphology due to the inhomogeneous distribution of reactive sites leads to a method for controlling the electronic structure and photophysical properties of SWNT. The transient optical properties of PDTAABQ-SWNT show a faster decaying component on a picosecond timescale but a very unusual slower decaying tail on a nanosecond timescale as compared to the timescale of the parent polymer (PDTADBQ). The severely distorted polymer chains with cis azobenezene side groups result in the reduction of the exciton mobility, leading to the longer fluorescence lifetime. This is confirmed by a similar ratio of the undepleted photoexcitons after 2.2 ns (Ca. 23.28%) and the ratio of the severely distorted polymers (Ca. 24.14%).