Preparation of n-type semiconducting polymer nanoarrays by covalent synthesis followed by crystallization

Abstract

In situ covalent synthesis followed by solution crystallization of the n-type semiconducting polymer derived from perylenediimide-bridged silsesquioxanes (PDIB-SSQ) yielded 1D-nanoarrays of 40-100 nm widths and up to 80 mm lengths. Morphologies and dimensions of nanostructures resulting from different base concentrations were characterized by SEM, fluorescence optical microscopy, SAXS, elemental analysis, MALDI-TOF-MS, and absorption and fluorescence spectroscopies. As revealed by SAXS, the nanostructures are composed of crystalline unit cells with cell parameters of d [001] = 24.8 Å and d [100] = 10.3 with multiple p-p stacking distances ranging from 4.71 to 2.57 Å. The ordering in polymer nanoarrays is favoured by the p-p interactions between the cofacially arranged PDI cores, resulting closely packed polymer arrays with the d-spacing ranging from 3.67 Å to 3.24 Å. The spectroscopic traces of nanoarrays in solution resembled that of the monomer except the slightly red shifted features of the emission spectrum associated with p-p stacking of polymer chains in aggregated form. Thin film emission spectra followed the similar spectral pattern with a noticeable shoulder corresponds to cofacial p-p interactions. The excited state lifetimes of aggregated polymer nanoarrays in both solution and solid phase were nearly identical. The electrical characterization of thin films made from polymer nanoarrays shows typical semiconducting behaviour with the electrical conductivity of 0.48 Â 10 À3 S cm À1 . The covalent synthesis followed by solution-based crystallization of PDIB-SSQ reported herein provides a new synthesis path to make orderedcrystalline semiconducting polymer nanoarrays and ultimately a benefit for better understanding of their role in organic electronics.

Oriented perylene incorporated optically anisotropic 2D silica films

“…The observed peak with d ¼ 8.67Å is similar to the width of perylene core (calculated value ¼ 9.2Å). 33,34 Similar ordering was also observed for columnar packing of alkyl substituted perylene diimide liquid crystals. 33,34 Diffractions corresponding to 5.64Å and 3.44Å are attributed to p-p stacking of cofacially stacked perylene cores.…”

“…33,34 Similar ordering was also observed for columnar packing of alkyl substituted perylene diimide liquid crystals. 33,34 Diffractions corresponding to 5.64Å and 3.44Å are attributed to p-p stacking of cofacially stacked perylene cores. 35 Similarly high resolution TEM images and selected area electron diffraction pattern (inset in Fig.…”

Targeted design leads to tunable photoluminescence from perylene dicarboxdiimide–poly(oxyalkylene)/siloxane hybrids for luminescent solar concentrators

“…The in situ polymerisation of a structurally-related perylenediimidebridged-triethoxysilane revealed a similar series of colour transitions as the reaction proceeded. 46 The reaction was also followed by MALDI-TOF mass spectrometry. Following addition of the sol-gel catalyst (aq.…”

A sol–gel polymerization method for creating nanoporous polyimide silsesquioxane nanostructures as soft dielectric materials

“…Herein, PMR‐SSQ nanoparticles were prepared, utilizing a previous method developed by our group . Our group has introduced a modified Stöber sol–gel route to make organic semiconductors‐functionalized SSQ nanostructures, having potential applicability in organic‐based photovoltaic devices . The method developed to make these dye‐functionalized SSQ nanoparticles has shown to be very useful in incorporating a higher load of organic functionality into the SSQ network to obtain highly functionalized dimensional architectures.…”