Photogenerated triplet states in supramolecular porphyrin ladder assemblies: an EPR study

文献情報

出版日 2016-08-17

DOI 10.1039/C6CP04444A

インパクトファクター 3.676

著者

Sabine Richert, Martin D. Peeks, Claudia E. Tait, Harry L. Anderson, Christiane R. Timmel

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要旨

Introducing bridging ligands such as DABCO to solutions of linear zinc porphyrin oligomers has previously been shown to lead to the formation of ladder-type assemblies in which the single porphyrin units in each strand adopt a predominantly co-planar conformation. Here, we employ transient Electron Paramagnetic Resonance (EPR) to study photogenerated triplet states of these complexes in frozen solution with a particular focus on the extent of spin delocalisation. We make use of two different techniques: (i) the zero-field splitting parameters D and E are determined using transient continuous wave (cw) EPR spectroscopy and (ii) the hyperfine coupling constants, which directly reveal the extent of spin delocalisation, are quantified by orientation-selective proton Electron Nuclear DOuble Resonance (ENDOR) spectroscopy. It is found that ladder formation does not encourage triplet state delocalisation either across the bridging ligand DABCO or along the individual porphyrin strands despite their co-planar conformation, which was previously shown to allow increased electronic delocalisation.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 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.

Photogenerated triplet states in supramolecular porphyrin ladder assemblies: an EPR study

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