Probing the excited state dynamics of a new family of Cu(i)-complexes with an enhanced light absorption capacity: excitation-wavelength dependent population of states through branching

Literature Information

Publication Date 2013-05-09
DOI 10.1039/C3CP50838B
Impact Factor 3.676
Authors

Panagiotis A. Papanikolaou, Nikolai V. Tkachenko


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Abstract

The ultrafast dynamics of six homoleptic Cu(I)-complexes and their respective ligands was examined through time-resolved electronic absorption spectroscopy in the subpicosecond time domain, in a variety of solvents, and at different excitation wavelengths. Results indicate that after excitation of the complexes in the blue part of the spectrum, the initially formed intraligand (IL) singlet excited state decays via two pathways yielding simultaneously both the lower-lying MLCT excited state and the ligand locally excited triplet state. The latter is also observed in the case of the free ligands and relaxes back to the ground state in a timescale of 40 ps. Excitation in the red part results in the formation of the MLCT excited state of the complexes which decays to the ground state through the same intraligand triplet excited state. The solvent viscosity does not affect the overall relaxation kinetics. The short time constant observed for the intersystem crossing of the MLCT singlet excited state is discussed in terms of the contribution of the d-orbitals of copper to the wavefunction of these states.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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