MALDI-ToF analysis of polythiophene: use of trans-2-[3-(4-t-butyl-phenyl)-2-methyl-2-propenylidene]malononitrile - DCTB - as matrix

Nowadays, numerous experimental and theoretical studies are devoted to the research field of polythiophenes and other electroconjugated polymers due to the huge potentialities of those conducting polymers. Synthetic procedures are now developed to reach the highest control over both polymerization and analytical methodologies allowing an in-depth and straightforward characterization of the polymer samples without any required doubt. Mass spectrometry methodologies and in particular MALDI-ToF measurements are definitively suitable to meet the characterization requirements. In the present study, trans-2-[3-(4-t-butyl-phenyl)-2-methyl-2-propenylidene]malononitrile (DCTB) was shown to afford better results than the reported terthiophene and dithranol matrices as far as sensitivity and signal-to-noise ratio are concerned. We tentatively proposed that the ionization of the P3HT molecules is performed by charge exchange in the condensed phase (clusters) with matrix molecule radical cations and subsequent neutral matrix molecule evaporation from the clusters. The putative key parameters to account for the really high efficiency of DCTB for the MALDI analysis of P3HT are (1) the highest ionization energy of DCTB amongst the three matrices, (2) the really high absorptivity of the matrix molecule at the laser wavelength and (3) the presence of the tertiobutyl group on the matrix molecule. The presence of this substituent is likely to decrease the intermolecular interactions in the condensed phase rendering the evaporation of the neutral matrix molecules less energy demanding. We also demonstrated for polymer samples presenting an average number molecular weight (M-n) below 10 000 g mol(-1) that the systematic overestimation of the low mass oligomers upon MALDI measurements ends up with wrong M-n and polydispersity index (PDI) values. A systematic Soxhlet extraction against heptane was shown to allow the recording of absolute M-n and PDI. Copyright (C) 2011 John Wiley & Sons, Ltd.