Struct Bond (2020) 183: 321–370
https://doi.org/10.1007/430_2020_64
# Springer Nature Switzerland AG 2020
Published online: 14 August 2020
Photophysicochemical Processes Directed
Within Nano-Containers
Mahesh Pattabiraman and Arunkumar Natarajan
Contents
1 Introduction . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . 324
2 Host-Guest Chemistry and Nano-Containers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
3 Fluorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
4 Phosphorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
5 Twisted-Intramolecular Charge Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
6 Excimers and Exciplexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
7 Energy Transfer Cascade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
8 Singlet Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
9 Photocycloaddition Reactions Within Cavitands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
10 Photo-Fries Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
11 Conclusion and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
Abstract Directing excited-state behavior of photoactive molecules without covalent modification has been more frequently achieved through inclusion within
cavitands than by any other supramolecular approach. Such efforts have led to
interesting photophysicochemical phenomena and their applications. This includes
employing strategies such as use of chromo-/luminophore-cavitand interactions to
perturb the electronic states to affect quantum efficiencies of radiative processes or
structural pre-orientation of reactants to achieve chemoselectivity. The influence of
nano-containers such as macrocyclic cavitands, nanocages, and capsules on the
photoactive molecules has been observed in solution phase as well as the solid
state, which has been studied through spectroscopy, product selectivity analysis, and
computational chemistry. This chapter will highlight prominent works in the past
M. Pattabiraman (*)
Department of Chemistry, University of Nebraska Kearney, Kearney, NE, USA
e-mail: pattabiramm2@unk.edu
A. Natarajan
GE Aviation, West Chester, OH, USA
e-mail: natararu@ge.com
https://doi.org/10.1007/430_2020_64
# Springer Nature Switzerland AG 2020
Published online: 14 August 2020
Photophysicochemical Processes Directed
Within Nano-Containers
Mahesh Pattabiraman and Arunkumar Natarajan
Contents
1 Introduction . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . 324
2 Host-Guest Chemistry and Nano-Containers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
3 Fluorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
4 Phosphorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
5 Twisted-Intramolecular Charge Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
6 Excimers and Exciplexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
7 Energy Transfer Cascade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
8 Singlet Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
9 Photocycloaddition Reactions Within Cavitands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
10 Photo-Fries Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
11 Conclusion and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
Abstract Directing excited-state behavior of photoactive molecules without covalent modification has been more frequently achieved through inclusion within
cavitands than by any other supramolecular approach. Such efforts have led to
interesting photophysicochemical phenomena and their applications. This includes
employing strategies such as use of chromo-/luminophore-cavitand interactions to
perturb the electronic states to affect quantum efficiencies of radiative processes or
structural pre-orientation of reactants to achieve chemoselectivity. The influence of
nano-containers such as macrocyclic cavitands, nanocages, and capsules on the
photoactive molecules has been observed in solution phase as well as the solid
state, which has been studied through spectroscopy, product selectivity analysis, and
computational chemistry. This chapter will highlight prominent works in the past
M. Pattabiraman (*)
Department of Chemistry, University of Nebraska Kearney, Kearney, NE, USA
e-mail: pattabiramm2@unk.edu
A. Natarajan
GE Aviation, West Chester, OH, USA
e-mail: natararu@ge.com