Enhancing the efficiency of two-photon absorption by metal coordination

Literature Information

Publication Date 2009-08-18
DOI 10.1039/B911268E
Impact Factor 3.676
Authors

Luca Grisanti, Cristina Sissa, Francesca Terenziani, Anna Painelli, Dominique Roberto, Francesca Tessore, Renato Ugo, Silvio Quici, Ilaria Fortunati, Eleonora Garbin, Camilla Ferrante, Renato Bozio


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Abstract

The intensity of the two-photon absorption (TPA) spectrum of a terpyridine ligand acting as a D–π–A chromophore (D = donor and A = acceptor) is enhanced by a factor of about 2 upon coordination to ZnCl2. Based on an analysis of linear absorption and fluorescence spectra of both the ligand and its Zn(II) complex, we have defined essential-state models for the two species. Linear and TPA spectra of the ligand are well reproduced in terms of a two-state model accounting for the D–π–A ↔ D+–π–A− charge resonance. However, the enhancement of the TPA response of its Zn(II) complex can only be understood by extending the model to account for the active role of the “ZnCl2” moiety acting as a virtual Av acceptor group of a D–π–AAv structure. The virtual D+AAv− state of the relevant three-state model has negligible weight in the ground state but contributes to the first excited state. The resulting increase of the excited-state dipole moment is responsible for the enhancement of the TPA cross section, and also explains the increase of the second order nonlinear optical response upon coordination.

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Contents list

Front/Back Matter

DOI: 10.1039/C7CP90121F

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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