TY - JOUR
T1 - Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems
AU - Alsam, Amani A.
AU - Adhikari, Aniruddha
AU - Parida, Manas R.
AU - Aly, Shawkat Mohammede
AU - Bakr, Osman
AU - Mohammed, Omar F.
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work was supported by King Abdullah University of Science and Technology (KAUST). Part of this work was supported by Saudi Basic Industries Corporation (SABIC) grant RGC/3/2470-01.
PY - 2017/3/29
Y1 - 2017/3/29
N2 - Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.
AB - Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.
UR - http://hdl.handle.net/10754/623797
UR - http://pubs.acs.org/doi/full/10.1021/acs.jpcc.7b00072
UR - http://www.scopus.com/inward/record.url?scp=85020032284&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.7b00072
DO - 10.1021/acs.jpcc.7b00072
M3 - Article
SN - 1932-7447
VL - 121
SP - 7837
EP - 7843
JO - The Journal of Physical Chemistry C
JF - The Journal of Physical Chemistry C
IS - 14
ER -