284
T. Hasobe
mixed tetracene SAMs on gold nanoclusters, which are synthesized by a tetracenemodified hetero-disulfide with two different chain lengths, demonstrated high-yield
SF (Φ SF : ~90%). Individual triplet yields (Φ T : ~160%) were also estimated by singlet
oxygen generation (
1 O 2 ).
16.5 Conclusion
In this chapter, we discussed pentacene and tetraene molecular assemblies using
covalently linked dimers and monolayered-protected nanoclusters for efficient occurrence of singlet fission. The proper structural control of two acene neighboring
molecules enables to demonstrate the generation of high-yield and long-lived triplet
excited states, which resulted in the observation of quantitative two-electron transfer
process and high-yield singlet oxygen generation. This photophysical information
will provide a new perspective for future applications in various areas such as
photovoltaics, photocatalysis, electronics and organic synthesis, and phototherapy.
Acknowledgements We deeply appreciate to Professors N. V. Tkachenko, Y. Kobori, Drs. H.
Sakai, H. Nagashima, Mrs. D. Kato S. Nakamura, T. Saegusa, R. Inaya for their collaboration.
The present work was supported by JSPS KAKENHI Grant Number 17H05270, Grant-in-Aid for
Scientific Research on Innovative Areas “Photosynergetics.”
References
1. Smith MB, Michl J (2010) Singlet fission. Chem Rev 110(11):6891–6936
2. Miyata K, Conrad-Burton FS, Geyer FL, Zhu XY (2019) Triplet pair states in singlet fission.
Chem Rev 119(6):4261–4292
3. Casanova D (2018) Theoretical modeling of singlet fission. Chem Rev 118(15):7164–7207
4. Lee J, Jadhav P, Reusswig PD, Yost SR, Thompson NJ, Congreve DN, Hontz E, Van Voorhis
T, Baldo MA (2013) Singlet exciton fission photovoltaics. Acc Chem Res 46(6):1300–1311
5. Krishnapriya KC, Musser AJ, Patil S (2019) Molecular design strategies for efficient
intramolecular singlet exciton fission. ACS Energy Lett 4(1):192–202
6. Yang L, Tabachnyk M, Bayliss SL, Böhm ML, Broch K, Greenham NC, Friend RH, Ehrler B
(2015) Solution-processable singlet fission photovoltaic devices. Nano Lett 15(1):354–358
7. Chan W-L, Ligges M, Jailaubekov A, Kaake L, Miaja-Avila L, Zhu XY (2011) Observing
the multiexciton state in singlet fission and ensuing ultrafast multielectron transfer. Science
334(6062):1541–1545
8. Rao A, Wilson MWB, Hodgkiss JM, Albert-Seifried S, Bässler H, Friend RH (2010) Exciton
fission and charge generation via triplet excitons in pentacene/c60 bilayers. J Am Chem Soc
132(36):12698–12703
9. Sanders SN, Kumarasamy E, Pun AB, Trinh MT, Choi B, Xia J, Taffet EJ, Low JZ, Miller JR,
Roy X, Zhu XY, Steigerwald ML, Sfeir MY, Campos LM (2015) Quantitative intramolecular
singlet fission in bipentacenes. J Am Chem Soc 137(28):8965–8972
10. Zirzlmeier J, Lehnherr D, Coto PB, Chernick ET, Casillas R, Basel BS, Thoss M, Tykwinski RR,
Guldi DM (2015) Singlet fission in pentacene dimers. Proc Natl Acad Sci USA 112(17):5325–
5330
T. Hasobe
mixed tetracene SAMs on gold nanoclusters, which are synthesized by a tetracenemodified hetero-disulfide with two different chain lengths, demonstrated high-yield
SF (Φ SF : ~90%). Individual triplet yields (Φ T : ~160%) were also estimated by singlet
oxygen generation (
1 O 2 ).
16.5 Conclusion
In this chapter, we discussed pentacene and tetraene molecular assemblies using
covalently linked dimers and monolayered-protected nanoclusters for efficient occurrence of singlet fission. The proper structural control of two acene neighboring
molecules enables to demonstrate the generation of high-yield and long-lived triplet
excited states, which resulted in the observation of quantitative two-electron transfer
process and high-yield singlet oxygen generation. This photophysical information
will provide a new perspective for future applications in various areas such as
photovoltaics, photocatalysis, electronics and organic synthesis, and phototherapy.
Acknowledgements We deeply appreciate to Professors N. V. Tkachenko, Y. Kobori, Drs. H.
Sakai, H. Nagashima, Mrs. D. Kato S. Nakamura, T. Saegusa, R. Inaya for their collaboration.
The present work was supported by JSPS KAKENHI Grant Number 17H05270, Grant-in-Aid for
Scientific Research on Innovative Areas “Photosynergetics.”
References
1. Smith MB, Michl J (2010) Singlet fission. Chem Rev 110(11):6891–6936
2. Miyata K, Conrad-Burton FS, Geyer FL, Zhu XY (2019) Triplet pair states in singlet fission.
Chem Rev 119(6):4261–4292
3. Casanova D (2018) Theoretical modeling of singlet fission. Chem Rev 118(15):7164–7207
4. Lee J, Jadhav P, Reusswig PD, Yost SR, Thompson NJ, Congreve DN, Hontz E, Van Voorhis
T, Baldo MA (2013) Singlet exciton fission photovoltaics. Acc Chem Res 46(6):1300–1311
5. Krishnapriya KC, Musser AJ, Patil S (2019) Molecular design strategies for efficient
intramolecular singlet exciton fission. ACS Energy Lett 4(1):192–202
6. Yang L, Tabachnyk M, Bayliss SL, Böhm ML, Broch K, Greenham NC, Friend RH, Ehrler B
(2015) Solution-processable singlet fission photovoltaic devices. Nano Lett 15(1):354–358
7. Chan W-L, Ligges M, Jailaubekov A, Kaake L, Miaja-Avila L, Zhu XY (2011) Observing
the multiexciton state in singlet fission and ensuing ultrafast multielectron transfer. Science
334(6062):1541–1545
8. Rao A, Wilson MWB, Hodgkiss JM, Albert-Seifried S, Bässler H, Friend RH (2010) Exciton
fission and charge generation via triplet excitons in pentacene/c60 bilayers. J Am Chem Soc
132(36):12698–12703
9. Sanders SN, Kumarasamy E, Pun AB, Trinh MT, Choi B, Xia J, Taffet EJ, Low JZ, Miller JR,
Roy X, Zhu XY, Steigerwald ML, Sfeir MY, Campos LM (2015) Quantitative intramolecular
singlet fission in bipentacenes. J Am Chem Soc 137(28):8965–8972
10. Zirzlmeier J, Lehnherr D, Coto PB, Chernick ET, Casillas R, Basel BS, Thoss M, Tykwinski RR,
Guldi DM (2015) Singlet fission in pentacene dimers. Proc Natl Acad Sci USA 112(17):5325–
5330