meso-Arylethynyl subporphyrins as efficient and tunable photo-induced electron transfer units

2017 ◽  
Vol 21 (02) ◽  
pp. 152-157 ◽  
Author(s):  
Won-Young Cha ◽  
Juwon Oh ◽  
Masaaki Kitano ◽  
Atsuhiro Osuka ◽  
Dongho Kim

Excited state dynamics of meso-arylethynyl-substituted subporphyrins can be tuned by 4-substituent at the arylethynyl group and solvent polarity. In polar acetonitrile, phenylethynyl subporphyrin 1 exhibited enhanced fluorescence, while (4-dimethylaminophenyl)ethynyl subporphyrin 2 showed red-shifted fluorescence from its charge-separated state and (4-nitrophenyl)ethynyl subporphyrin 3 displayed efficient fluorescence quenching due to charge separation.

2021 ◽  
Vol 133 (3) ◽  
Author(s):  
PRASHANTH K PODDUTOORI ◽  
NOAH HOLZER ◽  
BRANDON J BAYARD ◽  
YURI E KANDRASHKIN ◽  
GARY LIM ◽  
...  

2009 ◽  
Vol 113 (42) ◽  
pp. 18358-18368 ◽  
Author(s):  
Nguyen Vân Anh ◽  
Felix Schlosser ◽  
Michiel M. Groeneveld ◽  
Ivo H. M. van Stokkum ◽  
Frank Würthner ◽  
...  

Author(s):  
Dili R. Subedi ◽  
Youngwoo Jang ◽  
Ashwin Ganesan ◽  
Sydney Schoellhorn ◽  
Ryan Reid ◽  
...  

Two types of cobalt porphyrins, viz., meso-tetrakis(tolylporphyrinato)cobalt(II), (TTP)Co (1), and meso-tetrakis(triphenylamino porphyrinato)cobalt(II), [(TPA)4P]Co, (2) were self-assembled via metal-ligand axial coordination of phenyl imidazole functionalized fulleropyrrolidine, ImC[Formula: see text] to form a new series of donor–acceptor constructs. A 1:2 complex formation with ImC[Formula: see text] was established in the case of (TTP)Co while for [(TPA)4P]Co only a 1:1 complex was possible to positively identify. The binding constants [Formula: see text] and [Formula: see text] for step-wise addition of ImC[Formula: see text] to (TTP)Co were found to be 1.07 × 105 and 3.20 × 104 M[Formula: see text], respectively. For [(TPA)4P]Co:ImC[Formula: see text], the measured [Formula: see text] values was found to be 6.48 × 104 M[Formula: see text], slightly smaller than that observed for (TTP)Co. Although both cobalt porphyrins were non-fluorescent, they were able to quench the fluorescence of ImC[Formula: see text] indicating occurrence of excited state events in the supramolecular donor-acceptor complexes. Electrochemistry coupled with spectroelectrochemistry, revealed the formation of cobalt(III) porphyrin cation instead of a cobalt(II) porphyrin radical cation, as the main product, during oxidation of phenyl imidazole coordinated cobalt porphyrin. With the help of computational and electrochemical results, an energy level diagram was constructed to witness excited state photo-events. Competitive energy and electron transfer from excited CoP to coordinated ImC[Formula: see text], and electron transfer from Im1C[Formula: see text]* to cobalt(II) porphyrin resulting into the formation of PCo[Formula: see text]:ImC[Formula: see text] charge separated state was possible to envision from the energy diagram. Finally, using femtosecond transient absorption spectroscopy and data analysis by Glotaran, it was possible to establish sequential occurrence of energy transfer and charge separation processes. The lifetime of the final charge separated state was [Formula: see text] 2 ns. A slightly better charge stabilization was observed in the case of [(TPA)4P]Co:ImC[Formula: see text] due to the presence of electron rich, peripheral triphenylamine substituents on the cobalt porphyrin.


Author(s):  
Carolin Müller ◽  
Ilse Friedländer ◽  
Benedikt Bagemihl ◽  
Sven Rau ◽  
Benjamin Dietzek

In situ spectroelectrochemical studies focussing on the Franck-Condon region and sub-ns electron transfer processes in Ru(II)-tpphz-Pt(II) based photocatalysts reveal that single-electron reduction effectively hinders intramolecular electron transfer between the photoexcited...


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