Phosphorus(V)corrole- Porphyrin Based Hetero Trimers: Synthesis, Spectroscopy and Photochemistry

Abstract

'Axial-bonding'-type hetero trimers have been constructed by employing a simple 'inorganic' reaction such as axial bond formation of main group element containing phosphorus corrole. The approach is simple and modular in nature. The architecture of these hetero trimers such that, while a phosphorus(V)corrole forms the basal scaffolding unit, either two free-base porphyrins [(H 2 ) 2 -PCor] or Zn(II) porphyrins [(Zn) 2 -PCor] occupy the two axial sites via an aryloxy bridge. Both hetero trimeric species have been completely characterized by mass (FAB), UV/Vis, proton nuclear magnetic resonance spectroscopies and also by the differential pulse voltammetric method. Comparison of their spectroscopic and electrochemical data of these trimers with those of the corresponding reference compounds reveal that there is no apparent ring-to-ring interactions in these 'vertically' linked hetero trimers. Reduced fluorescence quantum yields were observed for [(H 2 ) 2 -PCor] and [(Zn) 2 -PCor] when compared to corresponding monomeric chromophores. Finally, a comparison is made between the presently reported phosphorus(V)corrole based hetero arrays and the previously reported analogous arrays based on Ge(IV)corrole with regard to their spectroscopic properties and photochemical activities.

Femtosecond to Microsecond Dynamics of Soret-Band Excited Corroles

“…The synthesis procedures are reported elsewhere (TTC, 47 P-TTC, 45 Ge-TTC 46 ). Their respective molecular structures are presented in Figure 1.…”

Ultrafast Dynamics of Sb-Corroles: A Combined Vis-Pump Supercontinuum Probe and Broadband Fluorescence Up-Conversion Study

“…The simple and efficient procedure of corrole synthesis, combined with the pre-tuning of physical and chemical characteristics by varying the peripheral substituents [ 5 , 6 , 7 , 8 ], central metal [ 6 , 9 , 10 ], and axial ligands [ 11 , 12 ], has revived substantial interest in employing these contracted porphyrinoids in various fields. A wide range of applications has been reported: corroles are used in dye-sensitized solar cells [ 9 , 13 ], as photosensitizers in photodynamic therapy and photodynamic detection [ 14 , 15 , 16 , 17 ], for the photodynamic inactivation of mold fungi and green algae [ 18 , 19 ], for regular and sophisticated optical imaging [ 20 , 21 ], for the formation of singlet oxygen for catalysis [ 22 , 23 , 24 ] and for corrole-based electron and energy transfer systems [ 25 , 26 , 27 ]. Since many of the processes involving corroles proceed via transient paramagnetic states, revealing the mechanisms and parameters of these states as well as identifying their reaction pathways is central to the optimized application of corroles [ 8 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ].…”

Pyrene Appended Free‐base, Phosphorus(V) and Gallium(III) Corroles and Their β,β′‐Linked Corrole Dimers: Synthesis, Photophysical and Electrochemical Properties

“…Recently, many corrole conjugates having donor (D) – acceptor (A) units have been reported with a variety of chromophores, possessing various connectivities. For example, corrole‐ BODIPY conjugates, [31–34] PBI‐corrole‐diphenylamine triad, [35] corrole‐fullerene dyad, [36] corrole‐porphyrin conjugates, [37–44] corrole‐anthraquinone dyad, [45] corrole‐ferrocene conjugates, [45,46] and corrole‐fluorene dyad, [47] have been investigated. In most of these examples, the electronic effect of the two chromophores has been probed and their utility for light harvesting applications investigated.…”