Debnath Sashi, Boyle Connor J, Zhou Dongming, Wong Bryan M, Kittilstved Kevin R, Venkataraman D
Department of Chemistry, University of Massachusetts Amherst 710 North Pleasant Street, Amherst Massachusetts 01003 USA
Department of Chemical & Environmental Engineering and Materials Science & Engineering Program, University of California, Riverside 900 University Avenue Riverside CA 925521 USA.
RSC Adv. 2018 Apr 18;8(27):14760-14764. doi: 10.1039/c8ra02417k.
Persistent n-doped conjugated polymers were achieved by doping the electron accepting PDNDIV and PFNDIV polymers with ionic (TBACN) or neutral (TDAE) dopants. The great electron affinities, as indicated by the low LUMO levels of PDNDIV (-4.09 eV) and PFNDIV (-4.27 eV), facilitated the chemical reduction from either TBACN or TDAE. The low-lying LUMOs of the neutral polymers PDNDIV and PFNDIV were achieved by incorporation of vinylene spacers between the electron poor NDI units to increase the conjugation length without the use of an electron donor, and this was lowered further by an electron-withdrawing fluorinated -substituent on the NDI moiety. The polymer radical anions were found to persist for several days under ambient conditions by EPR spectroscopy. A distinguishing and noteworthy feature of these polymers is that they can be consecutively reduced by up to four electrons in acetonitrile. Conductivity measurements demonstrate the prospective impact of PDNDIV and PFNDIV for organic electronics.
通过用离子型（TBACN）或中性（TDAE）掺杂剂对电子接受型聚合物PDNDIV和PFNDIV进行掺杂，制备出了持久性n掺杂共轭聚合物。PDNDIV（-4.09 eV）和PFNDIV（-4.27 eV）的低LUMO能级表明其具有很强的电子亲和力，这促进了来自TBACN或TDAE的化学还原。中性聚合物PDNDIV和PFNDIV的低LUMO能级是通过在缺电子的萘二亚胺（NDI）单元之间引入亚乙烯基间隔基来增加共轭长度而实现的，且未使用电子给体，此外，NDI部分上的吸电子氟化取代基进一步降低了LUMO能级。通过电子顺磁共振（EPR）光谱发现，聚合物自由基阴离子在环境条件下可存在数天。这些聚合物的一个显著且值得注意的特点是，它们在乙腈中最多可连续接受四个电子的还原。电导率测量结果证明了PDNDIV和PFNDIV在有机电子学方面的潜在影响。
