Axially Substituted Silicon Phthalocyanine as Electron Donor in a Dyad and Triad with Azafullerene as Electron Acceptor for Photoinduced Charge Separation.
The synthesis of a donor-acceptor silicon phthalocyanine (SiPc)-azafullerene (C59N) dyad 1 and of the first acceptor-donor-acceptor C59N-SiPc-C59N dumbbell triad 2 was accomplished. The two C59N-based materials were comprehensively characterized with the aid of NMR spectroscopy, MALDI-MS as well as DFT calculations and their redox and photophysical properties were evaluated with CV and steady-state and time-resolved absorption and photoluminescence spectroscopy measurements. Notably, femtosecond transient absorption spectroscopy assays revealed that both dyad 1 and triad 2 undergo, after selective photoexcitation of the SiPc moiety, photoinduced electron transfer from the singlet excited state of the SiPc moiety to the azafullerene counterpart to produce the charge-separated state, with lifetimes of 660 ps, in the case of dyad 1, and 810 ps, in the case of triad 2. The current results are expected to have significant implications en route to the design of advanced C59N-based donor-acceptor systems targeting energy conversion applications.
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 116 35 Athens, Greece.
Georgios
G
Rotas
División de Química Orgánica Instituto de Bioingeniería, Universidad Miguel Hernández, Avda. de la Universidad s/n, 03203, Elche, Spain.
Luis
L
Martín-Gomis
Division of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka, 565-0871, Japan.|Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 120-750, Korea.
Kei
K
Ohkubo
División de Química Orgánica Instituto de Bioingeniería, Universidad Miguel Hernández, Avda. de la Universidad s/n, 03203, Elche, Spain.
Fernando
F
Fernández-Lázaro
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 120-750, Korea. fukuzumi@chem.eng.osaka-u.ac.jp.|Faculty of Science and Technology, Meijo University, SENTAN, Japan Science and Technology Agency (JST), Nagoya, Aichi, 468-8502, Japan. fukuzumi@chem.eng.osaka-u.ac.jp.
Shunichi
S
Fukuzumi
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 116 35 Athens, Greece. tagmatar@eie.gr.
Nikos
N
Tagmatarchis
División de Química Orgánica Instituto de Bioingeniería, Universidad Miguel Hernández, Avda. de la Universidad s/n, 03203, Elche, Spain. asastre@umh.es.
Ángela
http://orcid.org/0000-0002-8835-2486
Á
Sastre-Santos
azafullerene; donor-acceptor systems; materials science; photoinduced electron transfer; silicon phthalocyanine