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Metal ion linked multilayers offer a means of controlling interfacial energy and electron transfer for a range of applications including solar energy conversion, catalysis, sensing, and more. Despite the importance of structure to these interlayer transfer processes, little is known about the distance and orientation between the molecules/surface of these multilayer films. Here we gain structural insights into these assemblies using a combination of UV-Vis polarized visible attenuated total reflectance (p-ATR) and Förster Resonance Energy Transfer (FRET) measurements. The bilayer of interest is composed of a metal oxide surface, phosphonated anthracene molecule, Zn(II) linking ion, and a platinum porphyrin with one (P1), two (P2), or three (P3) phenylene spacers between the chromophoric core and the metal ion binding carboxylate group. As observed by both time-resolved emission and transient absorption, the FRET rate and efficiency decreases with an increasing number of phenylene spacers (P1 > P2 > P3). However, from p-ATR measurements we observe a change in orientation of porphyrins in the bilayer, which inhibits a uniform determination of the orientation factor (κ2) across the series. Instead, we narrow the scope of viable structures by determining the best agreement between experimental and calculated FRET efficiencies. Additionally, we provide evidence that suggests, for the first time, that the bilayer structure is similar on both planar and mesoporous substrates.
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Förster resonance energy transfer in absorbing environment
We present an analytical model for Förster resonance energy transfer between donors and acceptors in the presence of a metal surface. We find that energy transfer to the metal results in a reduction of the Förster radius, leading to a suppression of concentration quenching for high molecule concentrations.
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- PAR ID:
- 10557743
- Editor(s):
- Engheta, Nader; Noginov, Mikhail A; Zheludev, Nikolay I
- Publisher / Repository:
- SPIE
- Date Published:
- Page Range / eLocation ID:
- 27
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Conference Paper:
- https://doi.org/10.1117/12.3027550
