Photoinduced charge separation in donor-acceptor conjugates play a pivotal role in technology breakthroughs, especially in the areas of efficient conversion of solar energy into electrical energy and fuels. Extending the lifetime of the charge separated species is a necessity for their practical utilization, and this is often achieved by following the mechanism of natural photosynthesis where the process of electron/hole migration occurs distantly separating the radical ion-pairs. Here, we hypothesize and demonstrate a new mechanism to stabilize the charge separated states via the process of electron exchange among the different acceptor entities in multimodular donor-acceptor conjugates. For this, star-shaped, central triphenylamine derived, dimethylamine-tetracyanobutadiene conjugates have been newly designed and characterized. Electron exchange was witnessed upon electroreduction in conjugates having multiple numbers of electron acceptors. Using ultrafast spectroscopy, occurrence of excited state charge separation, and the effect of electron exchange in prolonging the lifetime of charge separated states in the conjugates having multiple acceptors has been successfully demonstrated. This work constitutes the first example of stabilizing charge-separated states via the process of electron exchange.
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Inverse photochromism in viologen–tetraarylborate ion-pair complexes: optical write/microwave erase switching in polymer matrices
With the aim to construct a new type of photoswitchable photochromic material modulated by specific radiation in the microwave region, the spin dynamics of radical pairs (RPs) from ion-pair complexes between viologen and tetraarylborate compounds have been investigated in the presence of microwave (μw) radiation, using steady-state electron paramagnetic resonance (SSEPR) to follow the radical pair (RP) dynamics. This strategy is realized by excitation of the charge transfer (CT) absorption band of the ion-pair complex in the solid phase (powders and dispersed in polymer matrices) at 410 nm, which leads to electron transfer from borate to viologen, producing RPs. In the singlet excited state or Partially Separated Charge (PSC) state, an electron transfer process occurs between the ions, and the subsequent (purple) viologen radical is observed as a Fully Charge Separated (FCS) state. In solid state SSEPR experiments, μw radiation deactivates the FSC state by inducing back electron transfer, which subsequently increases the population of a Partially Separated Charge (PSC) state, recovering the initial color of the ion-pair complex. State-of-the-art photophysical and photochemical studies show that deactivation of the FSC state can take place using μw radiation on the RPs in a switchable, reversible fashion. The results have potential impact for a number of applications including photo-writing and photo-erasing processes and spintronics. Examples of laser writing using a polymer matrix to lock the relative positions of the radicals, and then erasing the color using microwaves, are presented and discussed.
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- Award ID(s):
- 1900541
- PAR ID:
- 10334979
- Date Published:
- Journal Name:
- Materials Advances
- Volume:
- 3
- Issue:
- 9
- ISSN:
- 2633-5409
- Page Range / eLocation ID:
- 3862 to 3874
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1MA01030A
