New naphthalene polyimide with unusual molar absorption coefficient and excited state properties: Synthesis, photophysics and electrochemistry

Abstract

A high molecular weight 1,4,5,8-naphthalene polyimide (ENPI) by one-step polycondensation mechanism and for comparison its monomeric diimide (ENDI) were synthesized; the photophysical and electrochemical properties were studied in detail for ENPI. Monomer has shown unusual insolubility so that the characterization proven to be difficult, whereas ENPI has shown better solubility. The molecular weight data obtained by GPC for the polymer were M-n = 8240 and M-w=34,000 g mol(-1) respectively with a polydispersity of 4.13. The polyimide exhibited outstandingly high molar absorption coefficients as 599,000, 1,021,000, and 972,700 M-1 cm(-1), which is first time reported in literature for the characteristic 0-2, 0-1, and 0-0 electronic transitions, respectively. ENPI showed concentration dependent and red shifted excimer emission in 1,1,2,2-tetrachloroethane (TCE). The polymer has undergone multielectron reductions in CHCl3 solution below 100 mV s(-1) scan rates which merged into two reversible one-electron reduction peaks at higher scan rates. In solid-state, similar scan rate dependent reduction peaks were noticed. The LUMO, HOMO and optical band gap values obtained for ENPI were -3.73, -6.91, and 3.18 eV respectively. ENDI polymer with striking features has great potential as new sensitizer for efficient dye sensitized organic cells. (C) 2013 Elsevier B.V. All rights reserved.