Why does the orientation of azulene affect the two-photon activity of a porphyrinoid-azulene system?

Attaching a dipolar molecule in a symmetric system induces a major change in the electronic structure, which may be reflected as the enhancement of the optical and charge-transfer properties of the combined system as compared to the pristine ones. Furthermore, the orientation of the dipolar molecule...

Full description

Saved in:
Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2024-05, Vol.26 (21), p.15611-15619
Main Authors: Rajput, Swati Singh, Raghuvanshi, Nikita, Banana, Tejendra, Yadav, Pooja, Alam, Md. Mehboob
Format: Article
Language:English
Subjects:
Azulene
Dipole moments
Electronic structure
Optical properties
Orientation effects
Photon absorption
Photons
Porphyrins
Citations: Items that this one cites
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Attaching a dipolar molecule in a symmetric system induces a major change in the electronic structure, which may be reflected as the enhancement of the optical and charge-transfer properties of the combined system as compared to the pristine ones. Furthermore, the orientation of the dipolar molecule may also affect the said properties. This idea is explored in this work by taking porphyrinoid molecules as the pristine systems. We attached azulene, a dipolar molecule, at various positions of five porphyrinoid cores and studied the effect on charge-transfer and one- and two-photon absorption properties using the state-of-the-art RICC2 method. The attachment of azulene produces two major effects - firstly it introduces asymmetry in the system and, secondly, being dipolar, it makes the resultant molecule dipolar/quadrupolar. Porphyrin, N -confused porphyrin, sub-porphyrin, sapphyrin, and hexaphyrin are used as core porphyrinoid systems. The change in charge-transfer has been studied using the orbital analysis and charge-transfer distance parameter for the first five singlet states of the systems. The effect of orientation of azulene on the said properties is also explored. The insights gained from our observations are explored further at the dipole and transition dipole moment levels using a three-state model. Attaching a dipolar molecule in a symmetric system induces a major change in the electronic structure, which may be reflected as the enhancement of the optical and charge-transfer properties of the combined system as compared to the pristine ones.
ISSN:1463-9076
1463-9084
DOI:10.1039/d4cp00438h