@article{rosko_espinoza_arteta_kromer_wheeler_castellano_2023, title={Employing Long-Range Inductive Effects to Modulate Metal-to- Ligand Charge Transfer Photoluminescence in Homoleptic Cu(I) Complexes}, volume={62}, ISSN={["1520-510X"]}, url={https://doi.org/10.1021/acs.inorgchem.2c04315}, DOI={10.1021/acs.inorgchem.2c04315}, abstractNote={Four Cu(I) bis(phenanthroline) photosensitizers formulated from a new ligand structural motif (Cu1-Cu4) coded according to their 2,9-substituents were synthesized, structurally characterized, and fully evaluated using steady-state and time-resolved absorption and photoluminescence (PL) measurements as well as electrochemistry. The 2,9-disubstituted-3,4,7,8-tetramethyl-1,10-phenanthroline ligands feature the following six-membered ring systems prepared through photochemical synthesis: 4,4-dimethylcyclohexyl (1), tetrahydro-2H-pyran-4-yl (2), tetrahydro-2H-thiopyran-4-yl (3), and 4,4-difluorocyclohexyl (4). Universally, these Cu(I) metal-to-ligand charge transfer (MLCT) chromophores display excited-state lifetimes on the microsecond time scale at room temperature, including the three longest-lived homoleptic cuprous phenanthroline excited states measured to date in de-aerated CH2Cl2, τ = 2.5-4.3 μs. This series of molecules also feature high PL quantum efficiencies (ΦPL = 5.3-12% in CH2Cl2). Temperature-dependent PL lifetime experiments confirmed that all these molecules exhibit reverse intersystem crossing and display thermally activated delayed PL from a 1MLCT excited state lying slightly above the 3MLCT state, 1050-1490 cm-1. Ultrafast and conventional transient absorption measurements confirmed that the PL originates from the MLCT excited state, which remains sterically arrested, preventing an excessive flattening distortion even when dissolved in Lewis basic CH3CN. Combined PL and electrochemical data provided evidence that Cu1-Cu4 are highly potent photoreductants (Eox* = -1.73 to -1.62 V vs Fc+/0 in CH3CN), whose potentials are altered solely based on which heteroatoms or substituents are resident on the 2,9-appended ring derivatives. It is proposed that long-range electronic inductive effects are responsible for the systematic modulation observed in the PL spectra, excited-state lifetimes, and the ground state absorption spectra and redox potentials. Cu1-Cu4 quantitatively follow the energy gap law, correlating well with structurally related cuprous phenanthrolines and are also shown to triplet photosensitize the excited states of 9,10-diphenylanthracene with bimolecular rate constants ranging from 1.61 to 2.82 × 108 M-1 s-1. The ability to tailor both photophysical and electrochemical properties using long-range inductive effects imposed by the 2,9-ring platforms advocates new directions for future MLCT chromophore discovery.}, number={7}, journal={INORGANIC CHEMISTRY}, author={Rosko, Michael C. and Espinoza, Eli M. and Arteta, Sarah and Kromer, Sarah and Wheeler, Jonathan P. and Castellano, Felix N.}, year={2023}, month={Feb}, pages={3248–3259} }
 @article{espinoza_røise_he_li_agatep_udenyi_han_jackson_kerr_chen_et al._2022, title={A self-immolative linker that releases thiols detects penicillin amidase and nitroreductase with high sensitivity via absorption spectroscopy}, url={https://doi.org/10.1039/D1CC05322A}, DOI={10.1039/D1CC05322A}, abstractNote={This article reports the synthesis and characterization of a novel self-immolative linker, based on thiocarbonates, which releases a free thiol upon activation via enzymes.}, journal={Chemical Communications}, author={Espinoza, Eli M. and Røise, Joachim J. and He, Maomao and Li, I-Che and Agatep, Alvin K. and Udenyi, Patrick and Han, Hesong and Jackson, Nicole and Kerr, D. Lucas and Chen, Dake and et al.}, year={2022} }
 @article{røise_han_li_kerr_taing_behrouzi_he_ruan_chan_espinoza_et al._2022, title={Acid-Sensitive Surfactants Enhance the Delivery of Nucleic Acids}, volume={12}, url={https://doi.org/10.1021/acs.molpharmaceut.1c00579}, DOI={10.1021/acs.molpharmaceut.1c00579}, abstractNote={The development of endosomal disruptive agents is a major challenge in the field of drug delivery and pharmaceutical chemistry. Current endosomal disruptive agents are composed of polymers, peptides, and nanoparticles and have had limited clinical impact. Alternatives to traditional endosomal disruptive agents are therefore greatly needed. In this report, we introduce a new class of low molecular weight endosomal disruptive agents, termed caged surfactants, that selectively disrupt endosomes via reversible PEGylation under acidic endosomal conditions. The caged surfactants have the potential to address several of the limitations hindering the development of current endosomal disruptive agents, such as high toxicity and low excretion, and are amenable to traditional medicinal chemistry approaches for optimization. In this report, we synthesized three generations of caged surfactants and demonstrated that they can enhance the ability of cationic lipids to deliver mRNA into primary cells. We also show that caged surfactants can deliver siRNA into cells when modified with the RNA-binding dye thiazole orange. We anticipate that the caged surfactants will have numerous applications in pharmaceutical chemistry and drug delivery given their versatility.}, journal={Molecular Pharmaceutics}, publisher={American Chemical Society (ACS)}, author={Røise, Joachim Justad and Han, Hesong and Li, Jie and Kerr, D. Lucas and Taing, Chung and Behrouzi, Kamyar and He, Maomao and Ruan, Emily and Chan, Lienna Y. and Espinoza, Eli M. and et al.}, year={2022}, month={Jan} }
 @article{espinoza_clark_pacheco da silva_derr_thalmer de medeiros silva_bilones_morales_quina_vullev_2022, title={Charge transfer vs. proton transfer in the excited-state dynamics of biomimetic pyranoflavylium cations}, volume={10}, DOI={10.1016/j.jpap.2022.100110}, abstractNote={Pyranoflavylium cations are synthetic analogues of pyranoanthocyanin, colored pigments, formed from grape anthocyanins during the maturation of red wines. Studies of a series of monosubstituted pyranoflavylium cations, ranging from methoxy (PF+-OMe) to cyano (PF+-CN), have shown that they display fluorescence and form triplet states that sensitize singlet oxygen formation in acidified acetonitrile. In alcohol-water mixtures, they behave as photoacids, undergoing adiabatic excited state proton transfer (ESPT) to water on a picosecond timescale, as confirmed in this report by femtosecond pump-probe spectroscopy. In contrast, the corresponding dimethylamino substituted pyranoflavylium cation (PF+-NMe2) is virtually non-fluorescent under the same conditions and exhibits a long-wavelength absorption band that has been attributed to a charge-transfer (CT) transition. Indeed, pump-probe spectroscopy of PF+-NMe2 in acidified acetonitrile shows ultrafast (<1 ps) formation of a CT state that decays back to the ground state with a 12–13 ps lifetime. In acidified methanol, the initial Franck-Condon CT state (ca. 3 ps lifetime) converts to a 13 ps lifetime CT state analogous to that in acetonitrile. In 50:50 ethanol:water and 30:70 methanol:water mixtures, PF+-NMe2 exhibits a short-lived (3–8 ps) initial CT state, an intermediate lifetime (30 ps) CT state and a much longer lived (130 ps) species attributed to a twisted intramolecular CT state. Thus, in addition to demonstrating that the photophysics of PF+-NMe2 is dominated by CT rather than ESPT, pump-probe spectroscopy provides details of the solvent-dependent dynamics of the CT decay pathways.}, journal={Journal of Photochemistry and Photobiology}, author={Espinoza, E.M. and Clark, J.A. and Pacheco da Silva, C. and Derr, J.B. and Thalmer de Medeiros Silva, G. and Bilones, M.K. and Morales, M. and Quina, F.H. and Vullev, V.I.}, year={2022}, month={Jun}, pages={100110} }
 @article{espinoza_clark_billones_medeiros silva_silva_quina_vullev_2022, title={Photophysics and Electrochemistry of Biomimetic Pyranoflavyliums: What Can Bioinspiration from Red Wines Offer}, volume={2}, url={https://doi.org/10.3390/photochem2010003}, DOI={10.3390/photochem2010003}, abstractNote={Natural dyes and pigments offer incomparable diversity of structures and functionalities, making them an excellent source of inspiration for the design and development of synthetic chromophores with a myriad of emerging properties. Formed during maturation of red wines, pyranoanthocyanins are electron-deficient cationic pyranoflavylium dyes with broad absorption in the visible spectral region and pronounced chemical and photostability. Herein, we survey the optical and electrochemical properties of synthetic pyranoflavylium dyes functionalized with different electron-donating and electron-withdrawing groups, which vary their reduction potentials over a range of about 400 mV. Despite their highly electron-deficient cores, the exploration of pyranoflavyliums as photosensitizers has been limited to the “classical” n-type dye-sensitized solar cells (DSSCs) where they act as electron donors. In light of their electrochemical and spectroscopic properties, however, these biomimetic synthetic dyes should prove to be immensely beneficial as chromophores in p-type DSSCs, where their ability to act as photooxidants, along with their pronounced photostability, can benefit key advances in solar-energy science and engineering.}, number={1}, journal={Photochem}, publisher={MDPI AG}, author={Espinoza, Eli Misael and Clark, John Anthony and Billones, Mimi Karen and Medeiros Silva, Gustavo Thalmer and Silva, Cassio Pacheco and Quina, Frank Herbert and Vullev, Valentine Ivanov}, year={2022}, month={Jan}, pages={9–31} }
 @article{espinoza_røise_li_das_murthy_2021, title={Advances in Imaging Reactive Oxygen Species}, volume={62}, ISSN={0161-5505 2159-662X}, url={http://dx.doi.org/10.2967/jnumed.120.245415}, DOI={10.2967/jnumed.120.245415}, abstractNote={Reactive oxygen species (ROS) play a pivotal role in many cellular processes and can be either beneficial or harmful. The design of ROS-sensitive fluorophores has allowed for imaging of specific activity and has helped elucidate mechanisms of action for ROS. Understanding the oxidative role of ROS in the many roles it plays allows us to understand the human body. This review provides a concise overview of modern advances in the field of ROS imaging. Indeed, much has been learned about the role of ROS throughout the years; however, it has recently been shown that using nanoparticles, rather than individual small organic fluorophores, for ROS imaging can further our understanding of ROS.}, number={4}, journal={Journal of Nuclear Medicine}, publisher={Society of Nuclear Medicine}, author={Espinoza, Eli M. and Røise, Joachim Justad and Li, I-Che and Das, Riddha and Murthy, Niren}, year={2021}, month={Apr}, pages={457–461} }
 @article{derr_tamayo_clark_morales_mayther_espinoza_rybicka-jasińska_vullev_2021, title={Correction: Multifaceted aspects of charge transfer}, url={https://doi.org/10.1039/D1CP90063C}, DOI={10.1039/D1CP90063C}, abstractNote={Correction for ‘Multifaceted aspects of charge transfer’ by James B. Derr et al., Phys. Chem. Chem. Phys., 2020, 22, 21583–21629, DOI: 10.1039/d0cp01556c.}, journal={Physical Chemistry Chemical Physics}, publisher={Royal Society of Chemistry (RSC)}, author={Derr, James B. and Tamayo, Jesse and Clark, John A. and Morales, Maryann and Mayther, Maximillian F. and Espinoza, Eli M. and Rybicka-Jasińska, Katarzyna and Vullev, Valentine I.}, year={2021} }
 @article{clark_orłowski_derr_espinoza_gryko_vullev_2021, title={How does tautomerization affect the excited-state dynamics of an amino acid-derivatized corrole?}, volume={148}, ISSN={0166-8595 1573-5079}, url={http://dx.doi.org/10.1007/s11120-021-00824-4}, DOI={10.1007/s11120-021-00824-4}, abstractNote={Abstract}, number={1-2}, journal={Photosynthesis Research}, publisher={Springer Science and Business Media LLC}, author={Clark, John A. and Orłowski, Rafał and Derr, James B. and Espinoza, Eli M. and Gryko, Daniel T. and Vullev, Valentine I.}, year={2021}, month={Mar}, pages={67–76} }
 @article{rybicka-jasińska_espinoza_clark_derr_carlos_morales_billones_omar_ågren_baryshnikov_et al._2021, title={Making Nitronaphthalene Fluoresce}, volume={10}, url={https://doi.org/10.1021/acs.jpclett.1c02155}, DOI={10.1021/acs.jpclett.1c02155}, abstractNote={Nitroaromatic compounds are inherently nonfluorescent, and the subpicosecond lifetimes of the singlet excited states of many small nitrated polycyclic aromatic hydrocarbons, such as nitronaphthalenes, render them unfeasible for photosensitizers and photo-oxidants, despite their immensely beneficial reduction potentials. This article reports up to a 7000-fold increase in the singlet-excited-state lifetime of 1-nitronaphthalene upon attaching an amine or an N-amide to the ring lacking the nitro group. Varying the charge-transfer (CT) character of the excited states and the medium polarity balances the decay rates along the radiative and the two nonradiative pathways and can make these nitronaphthalene derivatives fluoresce. The strong electron-donating amine suppresses intersystem crossing (ISC) but accommodates CT pathways of nonradiate deactivation. Conversely, the N-amide does not induce a pronounced CT character but slows down ISC enough to achieve relatively long lifetimes of the singlet excited state. These paradigms are key for the pursuit of electron-deficient (n-type) organic conjugates with promising optical characteristics.}, journal={The Journal of Physical Chemistry Letters}, publisher={American Chemical Society (ACS)}, author={Rybicka-Jasińska, Katarzyna and Espinoza, Eli M. and Clark, John A. and Derr, James B. and Carlos, Gregory and Morales, Maryann and Billones, Mimi Karen and Omar, O’Mari and Ågren, Hans and Baryshnikov, Glib V. and et al.}, year={2021}, month={Oct}, pages={10295–10303} }
 @article{derr_rybicka-jasińska_espinoza_morales_billones_clark_vullev_2021, title={On the Search of a Silver Bullet for the Preparation of Bioinspired Molecular Electrets with Propensity to Transfer Holes at High Potentials}, volume={11}, url={https://doi.org/10.3390/biom11030429}, DOI={10.3390/biom11030429}, abstractNote={Biological structure-function relationships offer incomparable paradigms for charge-transfer (CT) science and its implementation in solar-energy engineering, organic electronics, and photonics. Electrets are systems with co-directionally oriented electric dopes with immense importance for CT science, and bioinspired molecular electrets are polyamides of anthranilic-acid derivatives with designs originating from natural biomolecular motifs. This publication focuses on the synthesis of molecular electrets with ether substituents. As important as ether electret residues are for transferring holes under relatively high potentials, the synthesis of their precursors presents formidable challenges. Each residue in the molecular electrets is introduced as its 2-nitrobenzoic acid (NBA) derivative. Hence, robust and scalable synthesis of ether derivatives of NBA is essential for making such hole-transfer molecular electrets. Purdie-Irvine alkylation, using silver oxide, produces with 90% yield the esters of the NBA building block for iso-butyl ether electrets. It warrants additional ester hydrolysis for obtaining the desired NBA precursor. Conversely, Williamson etherification selectively produces the same free-acid ether derivative in one-pot reaction, but a 40% yield. The high yields of Purdie-Irvine alkylation and the selectivity of the Williamson etherification provide important guidelines for synthesizing building blocks for bioinspired molecular electrets and a wide range of other complex ether conjugates.}, number={3}, journal={Biomolecules}, publisher={MDPI AG}, author={Derr, James Bennett and Rybicka-Jasińska, Katarzyna and Espinoza, Eli Misael and Morales, Maryann and Billones, Mimi Karen and Clark, John Anthony and Vullev, Valentine Ivanov}, year={2021}, month={Mar}, pages={429} }
 @article{orłowski_clark_derr_espinoza_mayther_staszewska-krajewska_winkler_jędrzejewska_szumna_gray_et al._2021, title={Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates}, volume={118}, url={https://doi.org/10.1073/pnas.2026462118}, DOI={10.1073/pnas.2026462118}, abstractNote={Significance}, number={11}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Orłowski, Rafał and Clark, John A. and Derr, James B. and Espinoza, Eli M. and Mayther, Maximilian F. and Staszewska-Krajewska, Olga and Winkler, Jay R. and Jędrzejewska, Hanna and Szumna, Agnieszka and Gray, Harry B. and et al.}, year={2021}, month={Mar} }
 @article{skonieczny_espinoza_derr_morales_clinton_xia_vullev_2020, title={Biomimetic and bioinspired molecular electrets. How to make them and why does the established peptide chemistry not always work?}, volume={92}, ISSN={1365-3075 0033-4545}, url={http://dx.doi.org/10.1515/pac-2019-0111}, DOI={10.1515/pac-2019-0111}, abstractNote={Abstract}, number={2}, journal={Pure and Applied Chemistry}, publisher={Walter de Gruyter GmbH}, author={Skonieczny, Kamil and Espinoza, Eli M. and Derr, James B. and Morales, Maryann and Clinton, Jillian M. and Xia, Bing and Vullev, Valentine I.}, year={2020}, month={Feb}, pages={275–299} }
 @article{silva_silva_costa_carneiro_siddique_aquino_freitas_clark_espinoza_vullev_et al._2020, title={Chromophores inspired by the colors of fruit, flowers and wine}, volume={92}, ISSN={1365-3075 0033-4545}, url={http://dx.doi.org/10.1515/pac-2019-0226}, DOI={10.1515/pac-2019-0226}, abstractNote={Abstract}, number={2}, journal={Pure and Applied Chemistry}, publisher={Walter de Gruyter GmbH}, author={Silva, Cassio P. and Silva, Gustavo T. M. and Costa, Tássia de Sousa and Carneiro, Vânia M. T. and Siddique, Farhan and Aquino, Adelia J. A. and Freitas, Adilson A. and Clark, John A. and Espinoza, Eli M. and Vullev, Valentine I. and et al.}, year={2020}, month={Feb}, pages={255–263} }
 @article{poronik_baryshnikov_deperasińska_espinoza_clark_ågren_gryko_vullev_2020, title={Deciphering the unusual fluorescence in weakly coupled bis-nitro-pyrrolo[3,2-b]pyrroles}, url={https://doi.org/10.1038/s42004-020-00434-6}, DOI={10.1038/s42004-020-00434-6}, abstractNote={Abstract}, journal={Communications Chemistry}, author={Poronik, Yevgen M. and Baryshnikov, Glib V. and Deperasińska, Irena and Espinoza, Eli M. and Clark, John A. and Ågren, Hans and Gryko, Daniel T. and Vullev, Valentine I.}, year={2020}, month={Dec} }
 @misc{espinoza_2020, place={Belem, Brazil}, title={Extending the Lifetime of Nitrated Poliaromatic Hydrocarbons for Photoinduced Hole Transfer Systems}, author={Espinoza, E.}, year={2020}, month={Nov} }
 @article{derr_tamayo_clark_morales_mayther_espinoza_rybicka-jasińska_vullev_2020, title={Multifaceted aspects of charge transfer}, volume={22}, url={https://doi.org/10.1039/D0CP01556C}, DOI={10.1039/D0CP01556C}, abstractNote={Charge transfer is vital for life on Earth and makes our modern ways of living possible.}, number={38}, journal={Physical Chemistry Chemical Physics}, publisher={Royal Society of Chemistry (RSC)}, author={Derr, James B. and Tamayo, Jesse and Clark, John A. and Morales, Maryann and Mayther, Maximillian F. and Espinoza, Eli M. and Rybicka-Jasińska, Katarzyna and Vullev, Valentine I.}, year={2020}, pages={21583–21629} }
 @article{derr_clark_morales_espinoza_vadhin_vullev_2020, title={Solvent-induced selectivity of Williamson etherification in the pursuit of amides resistant against oxidative degradation}, url={https://doi.org/10.1039/D0RA04465B}, DOI={10.1039/D0RA04465B}, abstractNote={Selective etherification produces precursors for amides resistant to oxidative degradation, i.e., showing reversible oxidation at 1.5 to 1.7 V vs. SCE.}, journal={RSC Advances}, author={Derr, James B. and Clark, John A. and Morales, Maryann and Espinoza, Eli M. and Vadhin, Sandra and Vullev, Valentine I.}, year={2020} }
 @article{espinoza_bao_krzeszewski_gryko_vullev_2019, title={Is it common for charge recombination to be faster than charge separation?}, volume={51}, url={https://doi.org/10.1002/kin.21285}, DOI={10.1002/kin.21285}, abstractNote={Abstract}, number={9}, journal={International Journal of Chemical Kinetics}, publisher={Wiley}, author={Espinoza, Eli M. and Bao, Duoduo and Krzeszewski, Maciej and Gryko, Daniel T. and Vullev, Valentine I.}, year={2019}, month={Sep}, pages={657–668} }
 @article{espinoza_clark_soliman_derr_morales_vullev_2019, title={Practical Aspects of Cyclic Voltammetry: How to Estimate Reduction Potentials When Irreversibility Prevails}, volume={166}, ISSN={0013-4651 1945-7111}, url={http://dx.doi.org/10.1149/2.0241905jes}, DOI={10.1149/2.0241905jes}, abstractNote={What is the best approach for estimating standard electrochemical potentials, E (0) , from voltammograms that exhibit chemical irreversibility? The lifetimes of the oxidized or reduced forms of the majority of known redox species are considerably shorter than the voltammetry acquisition times, resulting in irreversibility and making the answer to this question of outmost importance. Half- wave potentials, E (1/2) , provide the best experimentally obtainable representation of E (0) . Due to irreversible oxidation or reduction, however, the lack of cathodic or anodic peaks in cyclic voltammograms renders E (1/2) unattainable. Therefore, we evaluate how closely alternative potentials, readily obtainable from irreversible voltammograms, estimate E (0) . Our analysis reveals that, when E (1/2) is not available, inflection-point potentials provide the best characterization of redox couples. While peak potentials are the most extensively used descriptor for irreversible systems, they deviate significantly from E (0) , especially at high scan rates. Even for partially irreversible systems, when the cathodic peak is not as pronounced as the anodic one, the half-wave potentials still provide the best estimates for E (0) . The importance of these findings extends beyond the realm of electrochemistry and impacts fields, such as materials engineering, photonics, cell biology, solar energy engineering and neuroscience, where cyclic voltammetry is a key tool.}, number={5}, journal={Journal of The Electrochemical Society}, publisher={The Electrochemical Society}, author={Espinoza, Eli M. and Clark, John A. and Soliman, Joey and Derr, James B. and Morales, Maryann and Vullev, Valentine I.}, year={2019}, pages={H3175–H3187} }
 @article{ryu_mayther_tamayo_azarias_espinoza_banasiewicz_łukasiewicz_poronik_jeżewski_clark_et al._2018, title={Bidirectional Solvatofluorochromism of a Pyrrolo[3,2-b]pyrrole–Diketopyrrolopyrrole Hybrid}, volume={122}, ISSN={1932-7447 1932-7455}, url={http://dx.doi.org/10.1021/acs.jpcc.7b11194}, DOI={10.1021/acs.jpcc.7b11194}, abstractNote={Hybridization of electron donors and acceptors provides routes to long-wavelength absorbing and fluorescing dyes. Varying the coupling of low-lying charge-transfer (CT) states with the ground and different locally excited states profoundly affects the photophysics of such donor–acceptor conjugates. Herein, we hybridize an electron-deficient diketopyrrolopyrrole (DPP) moiety with an electron-rich pyrrolopyrrole (PP) that is symmetrically N-arylated with 4-nitrophenyl substituents. The lowest Franck–Condon state is located on the DPP ring structure and dominates the photophysics of the hybrid. Similar to the DPP moiety, the hybrid exhibits optical absorption that is invariant to the solvent media. The PP donor considerably modulates its fluorescence by undergoing electron transfer to the locally excited DPP to form a CT state. For nonpolar media, an increase in solvent polarity causes a bathochromic shift of the fluorescence reaching the longest wavelengths for chloroform and DCM. A further increase in the ...}, number={25}, journal={The Journal of Physical Chemistry C}, publisher={American Chemical Society (ACS)}, author={Ryu, Hye Gun and Mayther, Maximillian F. and Tamayo, Jesse and Azarias, Cloé and Espinoza, Eli M. and Banasiewicz, Marzena and Łukasiewicz, Łukasz G. and Poronik, Yevgen M. and Jeżewski, Artur and Clark, John and et al.}, year={2018}, pages={13424–13434} }
 @misc{espinoza_2018, title={Bioinspired Design for Inducing Charge Transfer in Molecular Electrets}, author={Espinoza, E.}, year={2018}, month={May} }
 @article{krzeszewski_espinoza_červinka_derr_clark_borchardt_beran_gryko_vullev_2018, title={Cover Picture: Dipole Effects on Electron Transfer are Enormous (Angew. Chem. Int. Ed. 38/2018)}, volume={57}, url={https://doi.org/10.1002/anie.201806817}, DOI={10.1002/anie.201806817}, abstractNote={The electric dipole of a donor strongly affects the electron transfer (ET) to a photoexcited acceptor. In their Communication on page 12365 ff., G. J. O. Beran, D. T. Gryko, V. I. Vullev, and co-workers show that lowering the polarity of the medium can allow an electric dipole to enhance the rates of electron-transfer processes along it, while completely suppressing those occurring against it. Favorable dipole orientation makes ET possible even in lipophilic media. The electric dipole of a donor strongly affects the electron transfer (ET) to a photoexcited acceptor. In their Communication on page 12365 ff., G. J. O. Beran, D. T. Gryko, V. I. Vullev, and co-workers show that lowering the polarity of the medium can allow an electric dipole to enhance the rates of electron-transfer processes along it, while completely suppressing those occurring against it. Favorable dipole orientation makes ET possible even in lipophilic media. Biocatalysis Electrocatalysis Protein Labeling}, number={38}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Krzeszewski, Maciej and Espinoza, Eli M. and Červinka, Ctirad and Derr, James B. and Clark, John A. and Borchardt, Dan and Beran, Gregory J. O. and Gryko, Daniel T. and Vullev, Valentine I.}, year={2018}, month={Sep}, pages={12179–12179} }
 @inproceedings{espinoza_2018, title={Design of Electron Deficient Chromophores for Charge Transfer Systems}, author={Espinoza, E.}, year={2018}, month={Aug} }
 @article{krzeszewski_espinoza_červinka_derr_clark_borchardt_beran_gryko_vullev_2018, title={Dipole Effects on Electron Transfer are Enormous}, volume={57}, ISSN={1433-7851 1521-3773}, url={http://dx.doi.org/10.1002/anie.201802637}, DOI={10.1002/anie.201802637}, abstractNote={Abstract}, number={38}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Krzeszewski, Maciej and Espinoza, Eli M. and Červinka, Ctirad and Derr, James B. and Clark, John A. and Borchardt, Dan and Beran, Gregory J. O. and Gryko, Daniel T. and Vullev, Valentine I.}, year={2018}, month={Jun}, pages={12365–12369} }
 @article{krzeszewski_espinoza_červinka_derr_clark_borchardt_beran_gryko_vullev_2018, title={Dipole Effects on Electron Transfer are Enormous}, volume={130}, url={https://doi.org/10.1002/ange.201802637}, DOI={10.1002/ange.201802637}, abstractNote={Abstract}, number={38}, journal={Angewandte Chemie}, publisher={Wiley}, author={Krzeszewski, Maciej and Espinoza, Eli M. and Červinka, Ctirad and Derr, James B. and Clark, John A. and Borchardt, Dan and Beran, Gregory J. O. and Gryko, Daniel T. and Vullev, Valentine I.}, year={2018}, month={Sep}, pages={12545–12549} }
 @misc{espinoza_2018, title={Dipole Modulation of Charge Transfer}, author={Espinoza, E.}, year={2018}, month={Jun} }
 @misc{espinoza_2018, title={Dipole Modulation of Charge Transfer in Anthranilamides}, author={Espinoza, E.}, year={2018}, month={Feb} }
 @inproceedings{espinoza_2018, title={Dipole Modulation of Charge Transfer in Anthranilamides}, author={Espinoza, E.}, year={2018}, month={Feb} }
 @article{derr_tamayo_espinoza_clark_vullev_2018, title={Dipole-induced effects on charge transfer and charge transport. Why do molecular electrets matter?}, volume={96}, ISSN={0008-4042 1480-3291}, url={http://dx.doi.org/10.1139/cjc-2017-0389}, DOI={10.1139/cjc-2017-0389}, abstractNote={ Charge transfer (CT) and charge transport (CTr) are at the core of life-sustaining biological processes and of processes that govern the performance of electronic and energy-conversion devices. Electric fields are invaluable for guiding charge movement. Therefore, as electrostatic analogues of magnets, electrets have unexplored potential for generating local electric fields for accelerating desired CT processes and suppressing undesired ones. The notion about dipole-generated local fields affecting CT has evolved since the middle of the 20th century. In the 1990s, the first reports demonstrating the dipole effects on the kinetics of long-range electron transfer appeared. Concurrently, the development of molecular-level designs of electric junctions has led the exploration of dipole effects on CTr. Biomimetic molecular electrets such as polypeptide helices are often the dipole sources in CT systems. Conversely, surface-charge electrets and self-assembled monolayers of small polar conjugates are the preferred sources for modifying interfacial electric fields for controlling CTr. The multifaceted complexity of such effects on CT and CTr testifies for the challenges and the wealth of this field that still remains largely unexplored. This review outlines the basic concepts about dipole effects on CT and CTr, discusses their evolution, and provides accounts for their future developments and impacts. }, number={9}, journal={Canadian Journal of Chemistry}, publisher={Canadian Science Publishing}, author={Derr, James B. and Tamayo, Jesse and Espinoza, Eli M. and Clark, John A. and Vullev, Valentine I.}, year={2018}, month={Sep}, pages={843–858} }
 @article{espinoza_clark_derr_bao_georgieva_quina_vullev_2018, title={How Do Amides Affect the Electronic Properties of Pyrene?}, volume={3}, ISSN={2470-1343 2470-1343}, url={http://dx.doi.org/10.1021/acsomega.8b01581}, DOI={10.1021/acsomega.8b01581}, abstractNote={The electronic properties of amide linkers, which are intricate components of biomolecules, offer a wealth of unexplored possibilities. Herein, we demonstrate how the different modes of attaching an amide to a pyrene chromophore affect the electrochemical and optical properties of the chromophore. Thus, although they cause minimal spectral shifts, amide substituents can improve either the electron-accepting or electron-donating capabilities of pyrene. Specifically, inversion of the amide orientation shifts the reduction potentials by 200 mV. These trends indicate that, although amides affect to a similar extent the energies of the ground and singlet excited states of pyrene, the effects on the doublet states of its radical ions are distinctly different. This behavior reflects the unusually strong orientation dependence of the resonance effects of amide substituents, which should extend to amide substituents on other types of chromophores in general. These results represent an example where the Hammett sigma constants fail to predict substituent effects on electrochemical properties. On the other hand, Swain-Lupton parameters are found to be in good agreement with the observed trends. Examination of the frontier orbitals of the pyrene derivatives and their components reveals the underlying reason for the observed amide effects on the electronic properties of this polycyclic aromatic hydrocarbon and points to key molecular-design strategies for electronic and energy-conversion systems.}, number={10}, journal={ACS Omega}, publisher={American Chemical Society (ACS)}, author={Espinoza, Eli M. and Clark, John A. and Derr, James B. and Bao, Duoduo and Georgieva, Boriana and Quina, Frank H. and Vullev, Valentine I.}, year={2018}, month={Oct}, pages={12857–12867} }
 @misc{espinoza_2018, title={Photoinitiating Hole Transfer for Harvesting Energy From the Sun}, author={Espinoza, E.}, year={2018}, month={Dec} }
 @article{krzeszewski_espinoza_červinka_derr_clark_borchardt_beran_gryko_vullev_2018, title={Titelbild: Dipole Effects on Electron Transfer are Enormous (Angew. Chem. 38/2018)}, volume={130}, url={https://doi.org/10.1002/ange.201806817}, DOI={10.1002/ange.201806817}, abstractNote={Der elektrische Dipol eines Donors hat große Auswirkungen auf den Elektronentransfer zu einem angeregten Akzeptor. In ihrer Zuschrift auf S. 12545 zeigen G. J. O. Beran, D. T. Gryko, V. I. Vullev und Mitarbeiter, dass ein elektrischer Dipol, bei Senkung der Polarität des Mediums, Elektronentransferprozesse in seine Richtung beschleunigen kann, während Prozesse in die Gegenrichtung unterdrückt werden. Eine günstige Dipolausrichtung ermöglicht Elektronentransfers auch in lipophilen Medien. Der elektrische Dipol eines Donors hat große Auswirkungen auf den Elektronentransfer zu einem angeregten Akzeptor. In ihrer Zuschrift auf S. 12545 zeigen G. J. O. Beran, D. T. Gryko, V. I. Vullev und Mitarbeiter, dass ein elektrischer Dipol, bei Senkung der Polarität des Mediums, Elektronentransferprozesse in seine Richtung beschleunigen kann, während Prozesse in die Gegenrichtung unterdrückt werden. Eine günstige Dipolausrichtung ermöglicht Elektronentransfers auch in lipophilen Medien. Biokatalyse Elektrokatalyse Proteinmarkierung}, number={38}, journal={Angewandte Chemie}, publisher={Wiley}, author={Krzeszewski, Maciej and Espinoza, Eli M. and Červinka, Ctirad and Derr, James B. and Clark, John A. and Borchardt, Dan and Beran, Gregory J. O. and Gryko, Daniel T. and Vullev, Valentine I.}, year={2018}, month={Sep}, pages={12357–12357} }
 @article{espinoza_vullev_2017, title={Bioinspired Molecular Electrets: Bringing Proteomic Approaches to Charge-Transfer Systems}, volume={77}, ISSN={1938-6737 1938-5862}, url={http://dx.doi.org/10.1149/07711.1517ecst}, DOI={10.1149/07711.1517ecst}, abstractNote={Controlling charge transfer (CT) at a molecular level is immensely important for energy and electronic applications. Electrets, which are inherently dielectrics, possess ordered electric dipoles. That is, electrets are electrostatic analogies of magnets and they offer key paradigms for steering photogenerated charge carriers, usually away from each other, improving charge separation efficiencies. As bioinspired molecular electrets, anthranilamides possess an intrinsic dipole moment originating from their ordered amide and hydrogen bonds. The aromatic residues and extended π-conjugation along the backbone provides a means for long-range CT. Composed of non-native amino acids, i.e., derivatives of the anthranilica acid, these electrets are polypeptides and provide a means to employ principles of proteomics in their design and development. Rational functionalization of the non-native residues allows for accessing a wide range of electronic properties, as reveled by varying their reduction potentials. Development of such non-native redox-active non-native amino acids sets the foundation for introducing synthetic proteome to the field of charge transfer.}, number={11}, journal={ECS Transactions}, publisher={The Electrochemical Society}, author={Espinoza, Eli M. and Vullev, Valentine Ivanov}, year={2017}, month={Jul}, pages={1517–1523} }
 @article{espinoza_larsen-clinton_krzeszewski_darabedian_gryko_vullev_2017, title={Bioinspired approach toward molecular electrets: synthetic proteome for materials}, volume={89}, ISSN={1365-3075 0033-4545}, url={http://dx.doi.org/10.1515/pac-2017-0309}, DOI={10.1515/pac-2017-0309}, abstractNote={Abstract}, number={12}, journal={Pure and Applied Chemistry}, publisher={Walter de Gruyter GmbH}, author={Espinoza, Eli M. and Larsen-Clinton, Jillian M. and Krzeszewski, Maciej and Darabedian, Narek and Gryko, Daniel T. and Vullev, Valentine I.}, year={2017}, month={Nov}, pages={1777–1797} }
 @article{larsen-clinton_espinoza_f. mayther_clark_tao_bao_larino_wurch_lara_vullev_2017, title={Fluorinated aminoanthranilamides: non-native amino acids for bringing proteomic approaches to charge-transfer systems}, volume={19}, ISSN={1463-9076 1463-9084}, url={http://dx.doi.org/10.1039/c7cp00432j}, DOI={10.1039/c7cp00432j}, abstractNote={A highly selective substitution leads to a set of unique non-native amino acids that can serve as building blocks for molecular electrets.}, number={11}, journal={Physical Chemistry Chemical Physics}, publisher={Royal Society of Chemistry (RSC)}, author={Larsen-Clinton, Jillian M. and Espinoza, Eli M. and F. Mayther, Maximillian and Clark, John and Tao, Christina and Bao, Duoduo and Larino, Christa M. and Wurch, Michelle and Lara, Stephanie and Vullev, Valentine I.}, year={2017}, pages={7871–7876} }
 @misc{espinoza_2017, title={Inducing Charge Transfer in Molecular Electrets}, author={Espinoza, E.}, year={2017}, month={Mar} }
 @misc{espinoza_2017, title={Making Nitropyrene Fluoresce: Electron deficient sensitizers that are good electron acceptors}, author={Espinoza, E.}, year={2017}, month={Dec} }
 @inproceedings{espinoza_2017, title={Making Nitropyrenes Fluoresce: Electron-Deficient Sensitizers for Bioinspired Charge Transfer Systems}, author={Espinoza, E.}, year={2017}, month={Jul} }
 @article{purc_espinoza_nazir_romero_skonieczny_jeżewski_larsen_gryko_vullev_2016, title={Gating That Suppresses Charge Recombination–The Role of Mono-N-Arylated Diketopyrrolopyrrole}, volume={138}, ISSN={0002-7863 1520-5126}, url={http://dx.doi.org/10.1021/jacs.6b04974}, DOI={10.1021/jacs.6b04974}, abstractNote={Suppressing the charge recombination (CR) that follows an efficient charge separation (CS) is of key importance for energy, electronics, and photonics applications. We focus on the role of dynamic gating for impeding CR in a molecular rotor, comprising an electron donor and acceptor directly linked via a single bond. The media viscosity has an unusual dual effect on the dynamics of CS and CR in this dyad. For solvents with intermediate viscosity, CR is 1.5-3 times slower than CS. Lowering the viscosity below ∼0.6 mPa s or increasing it above ∼10 mPa s makes CR 10-30 times slower than CS. Ring rotation around the donor-acceptor bond can account only for the trends observed for nonviscous solvents. Media viscosity, however, affects not only torsional but also vibrational modes. Suppressing predominantly slow vibrational modes by viscous solvents can impact the rates of CS and CR to a different extent. That is, an increase in the viscosity can plausibly suppress modes that are involved in the transition from the charge-transfer (CT) to the ground state, i.e., CR, but at the same time are not important for the transition from the locally excited to the CT state, i.e., CS. These results provide a unique example of synergy between torsional and vibronic modes and their drastic effects on charge-transfer dynamics, thus setting paradigms for controlling CS and CR.}, number={39}, journal={Journal of the American Chemical Society}, publisher={American Chemical Society (ACS)}, author={Purc, Anna and Espinoza, Eli M. and Nazir, Rashid and Romero, Juan J. and Skonieczny, Kamil and Jeżewski, Artur and Larsen, Jillian M. and Gryko, Daniel T. and Vullev, Valentine I.}, year={2016}, month={Sep}, pages={12826–12832} }
 @article{skonieczny_yoo_larsen_espinoza_barbasiewicz_vullev_lee_gryko_2016, title={How To Reach Intense Luminescence for Compounds Capable of Excited‐State Intramolecular Proton Transfer?}, volume={22}, ISSN={0947-6539 1521-3765}, url={http://dx.doi.org/10.1002/chem.201504944}, DOI={10.1002/chem.201504944}, abstractNote={Abstract}, number={22}, journal={Chemistry – A European Journal}, publisher={Wiley}, author={Skonieczny, Kamil and Yoo, Jaeduk and Larsen, Jillian M. and Espinoza, Eli M. and Barbasiewicz, Michał and Vullev, Valentine I. and Lee, Chang‐Hee and Gryko, Daniel T.}, year={2016}, month={Apr}, pages={7485–7496} }
 @inproceedings{espinoza_2016, title={Inducing Charge Transfer in Molecular Electrets}, author={Espinoza, E.}, year={2016}, month={Oct} }
 @inproceedings{espinoza_2016, title={Modulating Charge Transfer at Nanomaterials Interfaces Using Molecular Electrets}, author={Espinoza, E.}, year={2016}, month={Jul} }
 @article{espinoza_xia_darabedian_larsen_nuñez_bao_mac_botero_wurch_zhou_et al._2016, title={Nitropyrene Photoprobes: Making Them, and What Are They Good for?}, volume={2016}, ISSN={1434-193X}, url={http://dx.doi.org/10.1002/ejoc.201501339}, DOI={10.1002/ejoc.201501339}, abstractNote={Abstract}, number={2}, journal={European Journal of Organic Chemistry}, publisher={Wiley}, author={Espinoza, Eli M. and Xia, Bing and Darabedian, Narek and Larsen, Jillian M. and Nuñez, Vicente and Bao, Duoduo and Mac, Jenny T. and Botero, Fabian and Wurch, Michelle and Zhou, Feimeng and et al.}, year={2016}, month={Jan}, pages={343–356} }
 @article{krzeszewski_kodama_espinoza_vullev_kubo_gryko_2016, title={Nonplanar Butterfly-Shaped π-Expanded Pyrrolopyrroles}, volume={22}, ISSN={0947-6539}, url={http://dx.doi.org/10.1002/chem.201603282}, DOI={10.1002/chem.201603282}, abstractNote={Abstract}, number={46}, journal={Chemistry - A European Journal}, publisher={Wiley}, author={Krzeszewski, Maciej and Kodama, Takuya and Espinoza, Eli M. and Vullev, Valentine I. and Kubo, Takashi and Gryko, Daniel T.}, year={2016}, month={Sep}, pages={16478–16488} }
 @article{espinoza_larsen_vullev_2016, title={What Makes Oxidized N-Acylanthranilamides Stable?}, volume={7}, ISSN={1948-7185 1948-7185}, url={http://dx.doi.org/10.1021/acs.jpclett.5b02881}, DOI={10.1021/acs.jpclett.5b02881}, abstractNote={Oligoamides composed of anthranilic acid derivatives present a promising choice for mediating long-range charge transfer and controlling its directionality. Hole hopping, modulated by the anthranilamide (Aa) permanent dipoles, provides a plausible means for such rectified long-range charge transduction. All aliphatic and most aromatic amides, however, decompose upon oxidation, rendering them unacceptable for hole-hopping pathways. We, therefore, employ electrochemical and computational analysis to examine how to suppress oxidative degradation and stabilize the radical cations of N-acylated Aa derivatives. Our findings reveal two requirements for attaining long-lived radical cations of these aromatic amides: (1) keeping the reduction potentials for oxidizing the Aa residues under about 1.4 V vs SCE and (2) adding an electron-donating group para to the N-terminal amide of the aromatic ring, which prevents the electron spin density of the radical cation from extending over the C-terminal amide. These findings provide essential information for the design of hole-transfer amides.}, number={5}, journal={The Journal of Physical Chemistry Letters}, publisher={American Chemical Society (ACS)}, author={Espinoza, Eli M. and Larsen, Jillian M. and Vullev, Valentine I.}, year={2016}, month={Feb}, pages={758–764} }
 @inproceedings{espinoza_2015, title={Bifunctional Nitropyrene: Synthetic Challenges, Photophysics and Electrochemical Features}, author={Espinoza, E.}, year={2015}, month={Jul} }
 @article{larsen_espinoza_vullev_2015, title={Bioinspired molecular electrets: bottom-up approach to energy materials and applications}, volume={5}, ISSN={1947-7988}, url={http://dx.doi.org/10.1117/1.jpe.5.055598}, DOI={10.1117/1.jpe.5.055598}, abstractNote={Abstract. The diversity of life on Earth is made possible through an immense variety of proteins that stems from less than a couple of dozen native amino acids. Is it possible to achieve similar engineering freedom and precision to design electronic materials? What if a handful of non-native residues with a wide range of characteristics could be rationally placed in sequences to form organic macromolecules with specifically targeted properties and functionalities? Referred to as molecular electrets, dipolar oligomers and polymers composed of non-native aromatic beta-amino acids, anthranilamides (Aa) provide venues for pursuing such possibilities. The electret molecular dipoles play a crucial role in rectifying charge transfer, e.g., enhancing charge separation and suppressing undesired charge recombination, which is essential for photovoltaics, photocatalysis, and other solar-energy applications. A set of a few Aa residues can serve as building blocks for molecular electrets with widely diverse electronic properties, presenting venues for bottom-up designs. We demonstrate how three substituents and structural permutations within an Aa residue widely alter its reduction potential. Paradigms of diversity in electronic properties, originating from a few changes within a basic molecular structure, illustrate the promising potentials of biological inspiration for energy science and engineering.}, number={1}, journal={Journal of Photonics for Energy}, publisher={SPIE-Intl Soc Optical Eng}, author={Larsen, Jillian M. and Espinoza, Eli M. and Vullev, Valentine I.}, year={2015}, month={May}, pages={055598} }
 @article{larsen_espinoza_hartman_lin_wurch_maheshwari_kaushal_marsella_beran_vullev_2015, title={Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics}, volume={87}, ISSN={1365-3075 0033-4545}, url={http://dx.doi.org/10.1515/pac-2015-0109}, DOI={10.1515/pac-2015-0109}, abstractNote={Abstract}, number={8}, journal={Pure and Applied Chemistry}, publisher={Walter de Gruyter GmbH}, author={Larsen, Jillian M. and Espinoza, Eli M. and Hartman, Joshua D. and Lin, Chung-Kuang and Wurch, Michelle and Maheshwari, Payal and Kaushal, Raman K. and Marsella, Michael J. and Beran, Gregory J. O. and Vullev, Valentine I.}, year={2015}, month={Aug}, pages={779–792} }
 @article{espinoza_larsen_vullev_2015, title={Electrochemical Properties of Residues for Bioinspired Molecular Electrets}, volume={66}, ISSN={1938-6737 1938-5862}, url={http://dx.doi.org/10.1149/06623.0001ecst}, DOI={10.1149/06623.0001ecst}, abstractNote={Anthranilamides are a class of bioinspired molecular electrets that have promising characteristics for organic electronics and energy applications. Derivatives of anthranilic acid, i.e., non-native aromatic beta-amino acids, are the principal building blocks for the anthranilamide conjugates. Derivatization with three types of electron-donating substituents results in anthranilamide residues exhibiting a diverse range of reduction potentials (that correlate with their ionization energies). The electrochemical trends reveal a structural and functional means for course- and fine-tuning of the electronic properties of anthranilamides. These findings set a foundation of design principles for easily modifiable organic electrets, and in particular for electrets that mediate charge transfer.}, number={23}, journal={ECS Transactions}, publisher={The Electrochemical Society}, author={Espinoza, E. M. and Larsen, J. M. and Vullev, V. I.}, year={2015}, month={Jul}, pages={1–9} }
 @inproceedings{espinoza_2015, title={Nitropyrene derivatives for bioinspired charge-transfer system}, author={Espinoza, E.}, year={2015}, month={Aug} }
 @article{upadhyayula_nuñez_espinoza_larsen_bao_shi_mac_anvari_vullev_2015, title={Photoinduced dynamics of a cyanine dye: parallel pathways of non-radiative deactivation involving multiple excited-state twisted transients}, volume={6}, ISSN={2041-6520 2041-6539}, url={http://dx.doi.org/10.1039/c4sc02881c}, DOI={10.1039/c4sc02881c}, abstractNote={A photoexcited cyanine dye deactivatesviamultiple non-radiative pathways, only one of which is principally responsible for quenching its fluorescence.}, number={4}, journal={Chemical Science}, publisher={Royal Society of Chemistry (RSC)}, author={Upadhyayula, Srigokul and Nuñez, Vicente and Espinoza, Eli M. and Larsen, Jillian M. and Bao, Duoduo and Shi, Dewen and Mac, Jenny T. and Anvari, Bahman and Vullev, Valentine I.}, year={2015}, pages={2237–2251} }
 @article{bao_upadhyayula_larsen_xia_georgieva_nuñez_espinoza_hartman_wurch_chang_et al._2014, title={Dipole-Mediated Rectification of Intramolecular Photoinduced Charge Separation and Charge Recombination}, volume={136}, ISSN={0002-7863 1520-5126}, url={http://dx.doi.org/10.1021/ja505618n}, DOI={10.1021/ja505618n}, abstractNote={Controlling charge transfer at a molecular scale is critical for efficient light harvesting, energy conversion, and nanoelectronics. Dipole-polarization electrets, the electrostatic analogue of magnets, provide a means for "steering" electron transduction via the local electric fields generated by their permanent electric dipoles. Here, we describe the first demonstration of the utility of anthranilamides, moieties with ordered dipoles, for controlling intramolecular charge transfer. Donor-acceptor dyads, each containing a single anthranilamide moiety, distinctly rectify both the forward photoinduced electron transfer and the subsequent charge recombination. Changes in the observed charge-transfer kinetics as a function of media polarity were consistent with the anticipated effects of the anthranilamide molecular dipoles on the rectification. The regioselectivity of electron transfer and the molecular dynamics of the dyads further modulated the observed kinetics, particularly for charge recombination. These findings reveal the underlying complexity of dipole-induced effects on electron transfer and demonstrate unexplored paradigms for molecular rectifiers.}, number={37}, journal={Journal of the American Chemical Society}, publisher={American Chemical Society (ACS)}, author={Bao, Duoduo and Upadhyayula, Srigokul and Larsen, Jillian M. and Xia, Bing and Georgieva, Boriana and Nuñez, Vicente and Espinoza, Eli M. and Hartman, Joshua D. and Wurch, Michelle and Chang, Andy and et al.}, year={2014}, month={Sep}, pages={12966–12973} }