title: Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission.
abstract: Intramolecular singlet fission (ISF) is a promising photophysical process to construct more efficient light energy conversion systems as one excited singlet state converts into two excited triplet states. Herein we synthesized and evaluated bent-shaped pentacene dimers as a prototype of ISF to reveal intrinsic characters of triplet states (e.g., lifetimes of triplet excited states). In this study, meta-phenylene-bridged TIPS-pentacene dimer (PcD-3Ph) and 2,2'-bipheynyl bridged TIPS-pentacene dimer (PcD-Biph) were newly synthesized as bent-shaped dimers. In the steady-state spectroscopy, absorption and emission bands of these dimers were fully characterized, suggesting the appropriate degree of electronic coupling between pentacene moieties in these dimers. In addition, the electrochemical measurements were also performed to check the electronic interaction between two pentacene moieties. Whereas the successive two oxidation peaks owing to the delocalization were observed in a directly linked-pentacene dimer (PcD) by a single bond, the cyclic voltammograms in PcD-Biph and PcD-3Ph implied the weaker interaction compared to that of p-phenylene-bridged TIPS-pentacene dimer (PcD-4Ph) and PcD. The femtosecond and nanosecond transient absorption spectra clearly revealed the slower ISF process in bent-shaped pentacene dimers (PcD-Biph and PcD-3Ph), more notably, the slower relaxation of the excited triplet states in PcD-Biph and PcD-3Ph. Namely, the quantum yields of triplet states (ΦT) by ISF approximately remain constant (ca. 180-200%) in all dimer systems, whereas the lifetimes of the triplet excited states became much longer (up to 360 ns) in PcD-Biph as compared to PcD-4Ph (15 ns). Additionally, the lifetimes of the corresponding triplet states in PcD-Biph and PcD-3Ph were sufficiently affected by solvent viscosity. In particular, the lifetimes of PcD-Biph triplet state in THF/paraffin (1.0 μs) increased up to approximately three times as compared to that in THF (360 ns), whereas those of PcD-4Ph were quite similar in both solvent.
authors.affiliation: Department of Chemistry, Faculty of Science and Technology, Keio University , Yokohama, 223-8522, Japan.
authors.forename: Takao
authors.initials: T
authors.lastname: Sakuma
authors.affiliation: Department of Chemistry, Faculty of Science and Technology, Keio University , Yokohama, 223-8522, Japan.
authors.forename: Hayato
authors.initials: H
authors.lastname: Sakai
authors.affiliation: Institute of Multidisciplinary Research for Advanced Materials, Tohoku University , 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan.
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Araki
authors.affiliation: Department of Applied Chemistry, Osaka University , 2-1 Yamada-oka, Suita 565-0871, Japan.
authors.forename: Tadashi
authors.initials: T
authors.lastname: Mori
authors.affiliation: Institute of Multidisciplinary Research for Advanced Materials, Tohoku University , 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan.
authors.forename: Takehiko
authors.initials: T
authors.lastname: Wada
authors.affiliation: Department of Chemistry and Bioengineering, Tampere University of Technology , 33720 Tampere, Finland.
authors.forename: Nikolai V
authors.initials: NV
authors.lastname: Tkachenko
authors.affiliation: Department of Chemistry, Faculty of Science and Technology, Keio University , Yokohama, 223-8522, Japan.
authors.forename: Taku
authors.initials: T
authors.lastname: Hasobe