Department of Chemistry and Biochemistry, Miami University, 701 East High Street, Oxford, OH 45056, USA.
Chem Asian J. 2012 Nov;7(11):2662-9. doi: 10.1002/asia.201200507. Epub 2012 Aug 27.
New opp-dibenzoporphyrins were prepared in a concise method that was based on a Pd(0)-catalyzed cascade reaction. These porphyrins, which contained carboxylic-acid linker groups on benzene rings that were fused to the porphyrin at their β,β'-positions, were examined as sensitizers for dye-sensitized solar cells for the first time. Whereas all of the porphyrins showed solar-energy-to-electricity conversion, an opp-dibenzoporphyrin with conjugated carboxylic-acid linkers displayed the highest conversion efficiency and an exceptionally high J(sc) value. Cyclic voltammetry of these porphyrins suggested that the fusion of two aromatic benzene rings onto the periphery of the porphyrin lowered the HOMO-LUMO energy gap; the incorporation of a conjugated carboxylic-acid linker group decreased the HOMO-LUMO gap even further. These CV data are consistent with DFT calculations for these porphyrins and agree well with the UV/Vis absorption- and fluorescence spectra of these porphyrins.
新的稠合二苯并卟啉通过一种简洁的方法制备，该方法基于 Pd(0)催化的级联反应。这些卟啉在 β,β'-位上与苯环融合，在苯环上带有羧酸连接基团，它们首次被用作染料敏化太阳能电池的敏化剂。虽然所有卟啉都显示出了将太阳能转化为电能的能力，但具有共轭羧酸连接基团的稠合二苯并卟啉显示出了最高的转化效率和异常高的 J(sc) 值。这些卟啉的循环伏安法表明，将两个芳香苯环融合到卟啉的外围降低了 HOMO-LUMO 能隙；引入共轭羧酸连接基团进一步降低了 HOMO-LUMO 能隙。这些 CV 数据与这些卟啉的 DFT 计算一致，并且与这些卟啉的 UV/Vis 吸收和荧光光谱吻合良好。
