A “click-chemistry” approach for the synthesis of porphyrin dyads as sensitizers for dye-sensitized solar cells

Abstract

Two novel porphyrin dyads (9 and 11) consisting of two zinc-metallated porphyrin units, covalently linked at their peripheries through 1,2,3-triazole containing bridges and functionalized by a terminal carboxylic acid group, have been synthesized via "click" reactions, which are Cu-catalyzed Huisgen 1,3-dipolar cycloadditions between azide- and acetylene-containing porphyrins. Photophysical and electrochemical measurements, together with DFT calculations, showed that the two dyads possess suitable frontier orbital energy levels for use as sensitizers in DSSCs. The 9 and 11 based solar cells were fabricated resulting in power conversion efficiencies (PCEs) of 3.82 and 5.16%, respectively. As shown by photovoltaic measurements (J-V curves) and incident photon to current conversion efficiency (IPCE) spectra of the two solar cells, the higher PCE value of the latter is attributed to its enhanced photovoltaic parameters, and particularly its enhanced short circuit current (Jsc). This is related to the stronger absorption profile of the sensitizing dyad 11 (the dyad with the shorter triazole containing bridge) and the higher dye loading of the corresponding solar cell. Furthermore, electrochemical impedance spectra (EIS) demonstrated that the 11 based solar cell exhibits longer electron lifetime (τe) and more effective suppression of the recombination between the injected electrons and the electrolyte.

Benefits of using BODIPY–porphyrin dyads for developing deep-red lighting sources

“…† In short, two new dyads have been prepared through ''click'' reaction. (Zn)DMP-N 3 -COOH was derived from (Zn)DMP-N 3 -COOCH 3 though hydrolysis of the ester group, 28 while the BDP-Triple and the BDP-O-Triple were prepared according to previously published procedures. 29,30 The composition of 1 and 2 has been verified by NMR spectroscopy -see Fig.…”

Azides and Porphyrinoids: Synthetic Approaches and Applications. Part 1—Azides, Porphyrins and Corroles

“…Basic hydrolysis of the methyl ester groups of precursors P128a and P109a gave rise to target porphyrinic dyads P128b and P129b at a 91% yield. Compound P129b, with a smaller triazolyl bridge, displayed a higher photovoltaic performance than the analogous derivative P128b (5.1% vs. 3.8%) when attached to titanium oxide via the carboxyl group [82].…”

“…The resulting porous frameworks P118 exhibited enhanced CO 2 sorption properties. Coutsolelos and co-workers explored the potential application as sensitizers for DSSCs of two porphyrin-based dyads linked by a variable-length triazole bridge [82]. The A 2 BC porphyrin derivative P125 bearing an ester and an amino group at para positions of two opposite meso-phenyl rings was functionalized with an azide group by following two different synthetic pathways.…”

“…Porphyrin-azide adduct P126b was reacted with porphyrin-alkyne P67 via a click CuAAC reaction in the presence of CuSO 4 /ascorbate catalytic system affording the triazolyl bridged porphyrin dyad P128a at a 42% yield. Dyad P129a was synthesized (41% yield) by following an analogous synthetic approach; however, since the azide is directly linked to a phenyl ring, the replacement of the CuSO 4 /ascorbate catalytic system by catalytic amounts of CuI in the presence of DIPEA was required [82,83]. Basic hydrolysis of the methyl ester groups of precursors P128a and P109a gave rise to target porphyrinic dyads P128b and P129b at a 91% yield.…”

“Click”-reaction: An alternative tool for new architectures of porphyrin based derivatives

“…Compounds 56 and 57 were used as dyes in DSSC measurements resulting power conversion efficiencies (PCEs) of 3.82 and 5.16%, respectively. Porphyrin sensitizers 56 and 57 for dye-sensitized solar cells[111].…”