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  1. Medium viscosity strongly affects the dynamics of solvated species and can drastically alter the deactivation pathways of their excited states. This study demonstrates the utility of poly(dimethylsiloxane) (PDMS) as a room-temperature solid-state medium for optical spectroscopy. As a thermoset elastic polymer, PDMS is transparent in the near ultraviolet, visible, and near infrared spectral regions. It is easy to mould into any shape, forming surfaces with a pronounced smoothness. While PDMS is broadly used for the fabrication of microfluidic devices, it swells in organic solvents, presenting severe limitations for the utility of such devices for applications employing non-aqueous fluids. Nevertheless, this swelling is reversible, which proves immensely beneficial for loading samples into the PDMS solid matrix. Transferring molecular-rotor dyes (used for staining prokaryotic cells and amyloid proteins) from non-viscous solvents into PDMS induces orders-of-magnitude enhancement of their fluorescence quantum yield and excited-state lifetimes, providing mechanistic insights about their deactivation pathways. These findings demonstrate the unexplored potential of PDMS as a solid solvent for optical applications. 
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    Free, publicly-accessible full text available February 5, 2025
  2. null (Ed.)
    Abstract In the first two decades of the XXI century, corroles have emerged as an important class of porphyrinoids for photonics and biomedical photonics. In comparison with porphyrins, corroles have lower molecular symmetry and higher electron density, which leads to uniquely complementary properties. In macrocycles of free-base corroles, for example, three protons are distributed among four pyrrole nitrogens. It results in distinct tautomers that have different thermodynamic energies. Herein, we focus on the excited-state dynamics of a corrole modified with l -phenylalanine. The tautomerization in the singlet-excited state occurs in the timescales of about 10–100 picoseconds and exhibits substantial kinetic isotope effects. It, however, does not discernably affect nanosecond deactivation of the photoexcited corrole and its basic photophysics. Nevertheless, this excited-state tautomerization dynamics can strongly affect photoinduced processes with comparable or shorter timescales, considering the 100-meV energy differences between the tautomers in the excited state. The effects on the kinetics of charge transfer and energy transfer, initiated prior to reaching the equilibrium thermalization of the excited-state tautomer population, can be indeed substantial. Such considerations are crucially important in the design of systems for artificial photosynthesis and other forms of energy conversion and charge transduction. 
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  3. This article reports two discoveries. (1) 2-Methoxyethanol induces unprecedented selectivity for etherification of 5-hydroxy-2-nitrobenzic acids without forming undesired esters. (2) Such compounds are precursors for amides showing unusual robustness against oxidative degradation, essential for molecular electrets that transfer strongly oxidizing holes at about −6.4 eV vs. vacuum. 
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  4. null (Ed.)
    Elucidating the factors that control charge transfer rates in relatively flexible conjugates is of importance for understanding energy flows in biology as well as assisting the design and construction of electronic devices. Here, we report ultrafast electron transfer (ET) and hole transfer (HT) between a corrole (Cor) donor linked to a perylene-diimide (PDI) acceptor by a tetrameric alanine (Ala) 4 . Selective photoexcitation of the donor and acceptor triggers subpicosecond and picosecond ET and HT. Replacement of the (Ala) 4 linker with either a single alanine or phenylalanine does not substantially affect the ET and HT kinetics. We infer that electronic coupling in these reactions is not mediated by tetrapeptide backbone nor by direct donor–acceptor interactions. Employing a combination of NMR, circular dichroism, and computational studies, we show that intramolecular hydrogen bonding brings the donor and the acceptor into proximity in a “scorpion-shaped” molecular architecture, thereby accounting for the unusually high ET and HT rates. Photoinduced charge transfer relies on a (Cor)NH … O=C–NH … O=C(PDI) electronic-coupling pathway involving two pivotal hydrogen bonds and a central amide group as a mediator. Our work provides guidelines for construction of effective donor–acceptor assemblies linked by long flexible bridges as well as insights into structural motifs for mediating ET and HT in proteins. 
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  5. Abstract

    Electron-deficient π-conjugated functional dyes lie at the heart of organic optoelectronics. Adding nitro groups to aromatic compounds usually quenches their fluorescence via inter-system crossing (ISC) or internal conversion (IC). While strong electronic coupling of the nitro groups with the dyes ensures the benefits from these electron-withdrawing substituents, it also leads to fluorescence quenching. Here, we demonstrate how such electronic coupling affects the photophysics of acceptor–donor–acceptor fluorescent dyes, with nitrophenyl acceptors and a pyrrolo[3,2-b]pyrrole donor. The position of the nitro groups and the donor-acceptor distance strongly affect the fluorescence properties of thebis-nitrotetraphenylpyrrolopyrroles. Concurrently, increasing solvent polarity quenches the emission that recovers upon solidifying the media. Intramolecular charge transfer (CT) and molecular dynamics, therefore, govern the fluorescence of these nitro-aromatics. While balanced donor-acceptor coupling ensures fast radiative deactivation and slow ISC essential for large fluorescence quantum yields, vibronic borrowing accounts for medium dependent IC via back CT. These mechanistic paradigms set important design principles for molecular photonics and electronics.

     
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  6. Abstract “Biomimetic” and “bioinspired” define different aspects of the impacts that biology exerts on science and engineering. Biomimicking improves the understanding of how living systems work, and builds tools for bioinspired endeavors. Biological inspiration takes ideas from biology and implements them in unorthodox manners, exceeding what nature offers. Molecular electrets, i.e. systems with ordered electric dipoles, are key for advancing charge-transfer (CT) science and engineering. Protein helices and their biomimetic analogues, based on synthetic polypeptides, are the best-known molecular electrets. The inability of native polypeptide backbones to efficiently mediate long-range CT, however, limits their utility. Bioinspired molecular electrets based on anthranilamides can overcome the limitations of their biological and biomimetic counterparts. Polypeptide helices are easy to synthesize using established automated protocols. These protocols, however, fail to produce even short anthranilamide oligomers. For making anthranilamides, the residues are introduced as their nitrobenzoic-acid derivatives, and the oligomers are built from their C- to their N-termini via amide-coupling and nitro-reduction steps. The stringent requirements for these reduction and coupling steps pose non-trivial challenges, such as high selectivity, quantitative yields, and fast completion under mild conditions. Addressing these challenges will provide access to bioinspired molecular electrets essential for organic electronics and energy conversion. 
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  7. Abstract Anthocyanins, which are responsible for most of the red, blue and purple colors of fruits and flowers, are very efficient at absorbing and dissipating light energy via excited state proton transfer or charge-transfer mediated internal conversion without appreciable excited triplet state formation. During the maturation of red wines, grape anthocyanins are slowly transformed into pyranoanthocyanins, which have a much more chemically stable pyranoflavylium cation chromophore. Development of straightforward synthetic routes to mono- and disubstituted derivatives of the pyranoflavylium cation chromophore has stimulated theoretical and experimental studies that highlight the interesting absorption and emission properties and redox properties of pyranoflavylium cations. Thus, p-methoxyphenyl substitution enhances the fluorescence quantum yield, while a p-dimethylaminophenyl substituent results in fast decay via a twisted intramolecular charge-transfer (TICT) state. Unlike anthocyanins and their synthetic analogs (flavylium cations), a variety of pyranoflavylium cations form readily detectable excited triplet states that sensitize singlet oxygen formation in solution and exhibit appreciable two-photon absorption cross sections for near-infrared light, suggesting a potential for applications in photodynamic therapy. These excited triplet states have microsecond lifetimes in solution and excited state reduction potentials of at least 1.3 V vs. SCE, features that are clearly desirable in a triplet photoredox catalyst. 
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