Reversible excited state electron transfer in an acceptor-acceptor hetero dyad
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| Názov: | Reversible excited state electron transfer in an acceptor-acceptor hetero dyad |
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| Autori: | Jensen, Jesper Dahl, Louie, Shayan, He, Yanmei, Chen, Junsheng, Nuckolls, Colin, Laursen, Bo W. |
| Prispievatelia: | Lund University, Faculty of Science, Department of Chemistry, Physical and theoretical chemistry, Chemical Physics, Lunds universitet, Naturvetenskapliga fakulteten, Kemiska institutionen, Enheten för fysikalisk och teoretisk kemi, Kemisk fysik, Originator, Lund University, Profile areas and other strong research environments, Strategic research areas (SRA), NanoLund: Centre for Nanoscience, Lunds universitet, Profilområden och andra starka forskningsmiljöer, Strategiska forskningsområden (SFO), NanoLund: Centre for Nanoscience, Originator, Lund University, Faculty of Engineering, LTH, LTH Profile areas, LTH Profile Area: Nanoscience and Semiconductor Technology, Lunds universitet, Lunds Tekniska Högskola, LTH profilområden, LTH profilområde: Nanovetenskap och halvledarteknologi, Originator, Lund University, Profile areas and other strong research environments, Lund University Profile areas, LU Profile Area: Light and Materials, Lunds universitet, Profilområden och andra starka forskningsmiljöer, Lunds universitets profilområden, LU profilområde: Ljus och material, Originator |
| Zdroj: | Chemical Science. 16(21):9525-9534 |
| Predmety: | Natural Sciences, Chemical Sciences, Theoretical Chemistry (including Computational Chemistry), Naturvetenskap, Kemi, Teoretisk kemi (Här ingår: Beräkningskemi), Physical Sciences, Condensed Matter Physics (including Material Physics, Nano Physics), Fysik, Den kondenserade materiens fysik (Här ingår: Materialfysik, nanofysik), Atom and Molecular Physics and Optics, Atom- och molekylfysik och optik (Här ingår: Kemisk fysik, kvantoptik) |
| Popis: | In this manuscript, we create a new hetero dyad consisting of two electron acceptors with nearly isoenergetic HOMO and LUMO levels, namely perylene diimide (PDI) and aza dioxa triangulenium (ADOTA). This dyad system displays an unusual and reversible excited state electron transfer process. Upon excitation, the dyad shows complete energy transfer from the locally excited PDI to the ADOTA moiety in ∼1 ps, followed by photoinduced electron transfer (PET), forming oxidized PDI and reduced ADOTA. While this PET process is fast (kPET≈ 150 ps), the reversibility establishes an equilibrium between fluorescent locally excited ADOTA and the dark charge shifted PET state. We investigate the formation of and decay from this unusual reversible excited state electron transfer system by fs transient absorption and time-resolved fluorescence spectroscopy in different solvent mixtures because the solvent modulates the deactivation rate of the PET state. Electrochemistry confirms that both the local HOMOs and LUMOs of PDI andADOTA are nearly isoenergetic but can be shifted by solvent polarity, which elucidates the reason for the unusual reversible electron transfer process and its sensitivity to the solvent. We further investigate near degeneracy of the LUMOs through spectroscopy of the chemically reduced dyad. We find that there is an equilibrium between the reduction of the cationic ADOTA to a neutral dyad, which is favored in DCM. However, in DMF, we find reduction of the PDI leads to formation of the zwitterionic dyad. |
| Prístupová URL adresa: | https://doi.org/10.1039/d5sc01397f |
| Databáza: | SwePub |
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Nájsť tento článok vo Web of Science | Abstrakt: | In this manuscript, we create a new hetero dyad consisting of two electron acceptors with nearly isoenergetic HOMO and LUMO levels, namely perylene diimide (PDI) and aza dioxa triangulenium (ADOTA). This dyad system displays an unusual and reversible excited state electron transfer process. Upon excitation, the dyad shows complete energy transfer from the locally excited PDI to the ADOTA moiety in ∼1 ps, followed by photoinduced electron transfer (PET), forming oxidized PDI and reduced ADOTA. While this PET process is fast (kPET≈ 150 ps), the reversibility establishes an equilibrium between fluorescent locally excited ADOTA and the dark charge shifted PET state. We investigate the formation of and decay from this unusual reversible excited state electron transfer system by fs transient absorption and time-resolved fluorescence spectroscopy in different solvent mixtures because the solvent modulates the deactivation rate of the PET state. Electrochemistry confirms that both the local HOMOs and LUMOs of PDI andADOTA are nearly isoenergetic but can be shifted by solvent polarity, which elucidates the reason for the unusual reversible electron transfer process and its sensitivity to the solvent. We further investigate near degeneracy of the LUMOs through spectroscopy of the chemically reduced dyad. We find that there is an equilibrium between the reduction of the cationic ADOTA to a neutral dyad, which is favored in DCM. However, in DMF, we find reduction of the PDI leads to formation of the zwitterionic dyad. |
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| ISSN: | 20416520 20416539 |
| DOI: | 10.1039/d5sc01397f |