2‐(1‐Acetyl‐2‐oxopropyl)‐5,10,15,20‐tetraphenylporphyrin and Its Transition‐Metal Complexes

Abstract

The 2-(1-acetyl-2-oxopropyl)-5,10,15,20-tetraphenylporphyrin free base (H 2 TPP-AOP) and its transition-metal complexes (MTPP-AOP, M = Cu 2+ , Zn 2+ ) have been synthesized. Single-crystal X-ray diffraction analysis revealed that the 1-acetyl-2-oxopropyl (AOP) group is attached to a β-pyrrolic position through the methylene group. The mean plane of the AOP is almost perpendicular to the porphyrin ring. The zinc(II) complex crystallizes as a five-coordinate species with one methanol/water solvate in the axial position, whereas the copper(II) complex is four-coordinate. These compounds exhibit strong absorption in the UV and visible regions. The fluorescence lifetimes are 1.85 and 8.0 ns for the free base

Synthesis and Electrochemical Characterization of Acetylacetone (acac) and Ethyl Acetate (EA) Appended β-Trisubstituted Push–Pull Porphyrins: Formation of Electronically Communicating Porphyrin Dimers

“…16 A Zn(II) complex of the acac-porphyrin was also examined for dye-sensitized solar cell applications. 17 Most recently, free base and Zn(II) porphyrins linked to acac complexed with BF 2 were reported by Toméand co-workers. 18 We wished to understand the behavior of push−pull porphyrins having a moderate electronwithdrawing acac or EAA substituent at one β-position of the porphyrin and two bromo or two phenyl groups at the antipodal positions.…”

“…Cavaleiro and co-workers have described the synthesis of tetraarylporphyrins with a single acetylacetone (acac) or ethyl acetoacetate (EAA) β-pyrrole substituent . A Zn­(II) complex of the acac-porphyrin was also examined for dye-sensitized solar cell applications . Most recently, free base and Zn­(II) porphyrins linked to acac complexed with BF 2 were reported by Tomé and co-workers .…”

Porphyrin Dyes on TiO2 Surfaces with Different Orientations: A Photophysical, Photovoltaic, and Theoretical Investigation

“…The dye structure is of importance to the cell performance. Its structural characteristics will not only affect the light absorption properties but also impact the dye–dye and dye–TiO 2 communication. − The dye–TiO 2 interaction in turn will affect the electron injection, electron recombination, and dye aggregation, which could result in very different current density, open-circuit voltage, and therefore energy conversion efficiency. − In the state-of-the-art porphyrin dyes, a para -benzoic acid is often used as an anchoring group. ,,,,− It binds to the surface of TiO 2 nanoparticles in the bidentate mode. Porphyrin molecules align on the surface of TiO 2 , and the electron injection goes from the dye molecule to the conduction band of TiO 2 .…”

Dual-channel anchorable organic dyes with well-defined structures for highly efficient dye-sensitized solar cells

“…Dye-sensitized solar cells (DSSCs) are promising hybrid/organic photovoltaic devices for high efficiency, low cost solar energy conversion. [1][2][3][4] In these cells, the sensitizer is one of the key components for high power-conversion efficiency; the Ru(II) complex is the most efficient heterogeneous charge-transfer sensitizer and is widely used in nanocrystalline TiO 2 -based DSSCs. [5][6][7][8][9] However, the main drawback of Ru(II) complex sensitizers is the cost of ruthenium metal, the requirement for careful synthesis, and tricky purication steps.…”