A series of porphyrin dyes with an electron-donating group (EDG) attached at a meso-position (YD1-YD8) have been designed and synthesized for use as sensitizers in dye-sensitized solar cells (DSSC). The nature of the EDG exerts a significant influence on the spectral, electrochemical and photovoltaic properties of these sensitizers. Absorption spectra of porphyrins having an amino group show broadened Soret band and red-shifted Q bands with respect to those of reference porphyrin YD0. This phenomenon is more pronounced for porphyrins YD7 and YD8 that have a pi-conjugated triphenylamine at the meso-position opposite the anchoring group. Upon introduction of an EDG at the meso-position, the potential for the first oxidation alters significantly to the negative whereas that for the first reduction changes inappreciably, indicating a decreased HOMO-LUMO gap. Results of density-functional theory (DFT) calculations support the spectroelectrochemical data for a delocalization of charge between the porphyrin ring and the amino group in the first oxidative state of diarylamino-substituted porphyrins YD1-YD4, which exhibit superior photovoltaic performance among all porphyrins under investigation. With long-chain alkyl groups on the diarylamino substituent, YD2 shows the best cell performance with J(SC) = 13.4 mA cm(-2), V(OC) = 0.71 V, and FF = 0.69, giving an overall efficiency 6.6% of power conversion under simulated one-sun AM1.5 illumination
YD12 (eta = 6.7%) is a green sensitizer remarkable for its outstanding cell performance beyond that of N719 (eta = 6.1%) with no added scattering layer; the additional scattering layer assists N719 in promoting the efficiency in the red shoulder of the spectrum, but has only a small effect on the improvement of the cell performance for porphyrins.
Novel porphyrin dimers with broad and strong absorption in the visible and/or near IR regions have been synthesized; the meso-meso-linked porphyrin dimer (YDD1) exhibited the best photovoltaic performance with power conversion efficiency 5.2% under AM 1.5G one solar illumination.
Novel porphyrin dyes YD14-YD17 with a push-pull framework were synthesized for dye-sensitized solar cells (DSSC); their spectral, electrochemical and photovoltaic properties were investigated. The absorption bands of these porphyrin dyes are broadened and red-shifted upon introduction of electron-donating groups (EDG) to the meso-positions via extension of p-conjugation. Electrochemical tests show that the first oxidation for these porphyrins occurs at a potential greater than that of the I(-)/I(3)(-) redox couple, and attachment of EDGs to the periphery of the porphyrin facilitates electron abstraction. The photovoltaic measurements show that YD14 and YD17 have a power conversion efficiency of similar to 7%. Introduction of EDGs to various meso-positions is demonstrated to be achievable, and porphyrin dyes with appropriate EDGs are promising candidates for highly efficient DSSCs
Keywords: Metal-metal interactions / Nickel / Chromium / Magnetic properties- (6)] were synthesized and structurally characterized. Electrochemical studies showed that heptanickel(II) complexes can undergo one reversible oxidation at +0.46 V for 1 and +0.52 V for 2. Chromium(II) species 3 exhibited two reversible, one-electron oxidation peaks at +0.61 and +0.88 V, and 5 exhibited three reversible, one-electron oxidation peaks at +0.40, +0.68 and +1.07 V. The redox peaks shifted positively when axial ligands changed from chloride to thiocyanate anions, at +0.67 and +0.92 V for 4 and +0.44,
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