TY - JOUR
T1 - Diboron- And Diaza-Doped Anthracenes and Phenanthrenes
T2 - Their Electronic Structures for Being Singlet Fission Chromophores
AU - Pradhan, Ekadashi
AU - Lee, Seunghoon
AU - Choi, Cheol Ho
AU - Zeng, Tao
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/10/8
Y1 - 2020/10/8
N2 - We used quantum chemistry methods at the levels of mixed-reference spin-flip time-dependent density functional theory and multireference perturbation theory to study diboron- and diaza-doped anthracenes and phenanthrenes. This class of structures recently surged as potential singlet fission chromophores. We studied electronic structures of their excited states and clarified the reasons why they satisfy or fail to satisfy the energy criteria for singlet fission chromophores. Many studied structures have their S1 states not dominated by HOMO → LUMO excitation, so they cannot be described using the conventional two site model. This is attributed to frontier orbital energy shifts induced by the doping and different charge-transfer energies in different one-electron singlet excitations or, in other words, different polarizations of hole and/or particle orbitals in their S1 and T1 states. There is a mirror relation between the orbital energy shifts induced by diboron- and diaza-dopings, which together with alternant hydrocarbon pairings of occupied and unoccupied orbitals, leads to more mirror relations between the excited states of the two types of doped structures.
AB - We used quantum chemistry methods at the levels of mixed-reference spin-flip time-dependent density functional theory and multireference perturbation theory to study diboron- and diaza-doped anthracenes and phenanthrenes. This class of structures recently surged as potential singlet fission chromophores. We studied electronic structures of their excited states and clarified the reasons why they satisfy or fail to satisfy the energy criteria for singlet fission chromophores. Many studied structures have their S1 states not dominated by HOMO → LUMO excitation, so they cannot be described using the conventional two site model. This is attributed to frontier orbital energy shifts induced by the doping and different charge-transfer energies in different one-electron singlet excitations or, in other words, different polarizations of hole and/or particle orbitals in their S1 and T1 states. There is a mirror relation between the orbital energy shifts induced by diboron- and diaza-dopings, which together with alternant hydrocarbon pairings of occupied and unoccupied orbitals, leads to more mirror relations between the excited states of the two types of doped structures.
UR - http://www.scopus.com/inward/record.url?scp=85092750346&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.0c06915
DO - 10.1021/acs.jpca.0c06915
M3 - Article
C2 - 32902270
AN - SCOPUS:85092750346
SN - 1089-5639
VL - 124
SP - 8159
EP - 8172
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 40
ER -