Theoretical Solar-to-Electrical Energy-Conversion Efficiencies of Perylene−Porphyrin Light-Harvesting Arrays

Hasselman, Georg M.; Watson, David F.; Stromberg, Jonathan R.; Bocian, David F.; Holten, Dewey; Lindsey, Jonathan S.; Meyer, Gerald J.

doi:10.1021/jp064547x

Cited by 113 publications

(91 citation statements)

References 44 publications

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Abstract 8,18, undergoes regioselective electrophilic bromination with NBS to give the 15-bromo analogue (MeO-BC-Br 15 ) in 85% yield. By contrast, the bacteriochlorin lacking the 5-methoxy group (8,8,18,18-tetramethyl-2,12-di-p-tolylbacteriochlorin, H-BC) gives a mixture of two mono-bromo and two dibromobacteriochlorins.

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confidence: 99%

“…By contrast, the bacteriochlorin lacking the 5-methoxy group (8,8,18,18-tetramethyl-2,12-di-p-tolylbacteriochlorin, H-BC) gives a mixture of two mono-bromo and two dibromobacteriochlorins. Deuterium exchange of both bacteriochlorins (H-BC and MeO-BC) in acidic media (TFA-d) occurs preferentially at the β-pyrrole positions (3, 13) > unhindered meso-positions (5, 15 for H-BC; 15 for MeO-BC) > hindered meso-positions (10, 20).…”

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Regioselective 15-Bromination and Functionalization of a Stable Synthetic Bacteriochlorin

2007

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8,18, undergoes regioselective electrophilic bromination with NBS to give the 15-bromo analogue (MeO-BC-Br 15 ) in 85% yield. By contrast, the bacteriochlorin lacking the 5-methoxy group (8,8,18,18-tetramethyl-2,12-di-p-tolylbacteriochlorin, H-BC) gives a mixture of two mono-bromo and two dibromobacteriochlorins. Deuterium exchange of both bacteriochlorins (H-BC and MeO-BC) in acidic media (TFA-d) occurs preferentially at the β-pyrrole positions (3, 13) > unhindered meso-positions (5, 15 for H-BC; 15 for MeO-BC) > hindered meso-positions (10, 20). The 15-bromo-5-methoxybacteriochlorin MeO-BC-Br 15 was subjected to three types of Pd-mediated coupling reactions (Suzuki, Sonogashira, Hartwig-Buchwald) to give six bacteriochlorins bearing functional groups at the 15-position (49% to 85% yield). The groups include 4-(tert-butoxycarbonylmethoxy) phenyl, 3, phenylethynyl,. The presence of the 15-ethynyl moiety shifts the position of the long-wavelength Q y band from 732 nm to ∼753 nm. The ability to introduce a range of groups at a specific site enables synthetic bacteriochlorins to be tailored for a variety of applications.

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Regioselective 15-Bromination and Functionalization of a Stable Synthetic Bacteriochlorin

2007

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“…23 The density functional theory (DFT) with Becke's three-parameter functional and Lee-Yang-Parr functional (B3LYP), [21][22][23][24][25][26] and the 6-31G(d,p) basis set were employed to investigate the optimization of structures in the gas phase, without any symmetry constrains. The excitation energies and oscillator strengths of the oligomers were obtained by TD-DFT, in the gas phase, in conjunction with a polarizable continuum model (PCM), [27][28] to evaluate the effect of the solvent (Chloroform).…”

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“…Moreover, it is possible to evaluate the light harvesting efficiency (LHE), which is directly linked with and has to be as high as possible to maximize the photo current response. LHE can be expressed as: 20,21 (8) where f is the oscillator strength of the oligomers associated to the maximum absorption of charge transfer interaction. Also, it is important to consider that the sunlight-to-electricity conversion efficiency (PCE), is evaluated through the open-circuit photo voltage (V OC ), J SC and the fill factor (FF) as compared to the incident solar power (P in ).…”

Section: Theoretical Backgroundmentioning

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Tuning the Electronic, Photophysical and Charge Transfer Properties of Small D-a Molecules Based on Thienopyrazine-Terthienyls by Changing the Donor Fragment: A DFT Study

Aicha

Bouzzine²,

Zair

et al. 2017

J. Chil. Chem. Soc.

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Four acceptor-donor organic conjugated molecules based on thieno [3,4-b]pyrazine-terthienyls were analyzed in order to explore the effect of the donor substituent on their molecular structures, electronic and optical properties. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD/DFT) calculations were carried out employing the B3LYP hybrid functional in combination with the 6-31G(d,p) basis set. The results suggests that the addition of electron-donating substituents to the conjugated molecules can diminish their energy gap value, which is beneficial to the photon harvesting. The lowest-lying absorption spectra of compounds substituted with electron donor groups exhibited a red-shift and a high oscillation factor compared with the unsubstituted molecule. Additionally, the ionization potential (IP), electron affinity (EA), reorganization energy (λ) and open-circuit voltage (V oc ) of the molecules were evaluated. According to these values, the molecules show good photovoltaic properties, and efficient charge transfer for hole and electron and balanced charges.

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“…The rutile TiO 2 reported in their classical study would not provide adequate surface area for attachment of the Zheng dyad as far more sunlight light would be transmitted than would be absorbed. Monolayers of even the most strongly absorbing pigments are not generally useful for solar light harvesting on planar materials (12). However, the mesoporous nanocrystalline TiO 2 thin films used in dyesensitized solar cells (13,14) circumvent this issue and would provide a surface area for the Zheng dyad that is ∼1,000 times that of a planar material.…”

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Antenna molecule drives solar hydrogen generation

Meyer

2015

Proc. Natl. Acad. Sci. U.S.A.

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It would be convenient if gigantic reservoirs of molecular hydrogen H 2(g) existed in the earth's crust that could be safely tapped as an energy source. Instead, most hydrogen found near the earth's surface is bound up in water as protons, H + (aq) that must be reduced before utilization as a fuel (1). When the electrons for proton reduction come from the oxidation of water to O 2(g) , this redox chemistry is commonly referred to as "water splitting": 2H 2 O ðaqÞ → 2H 2ðgÞ + O 2ðgÞ ðΔG°= 4.92eVÞ.[1]As shown in Eq. 1, water splitting is thermodynamically uphill and hence provides a means for storing energy in chemical bonds. The reverse reaction produces water and energy. The identification of an inexpensive scalable process for water splitting has been a "holy grail" of science for decades that could one day enable a "hydrogen economy" (2). Electrolysis accomplishes water splitting, but practical utility requires an inexpensive source of electrical power that ideally would not involve greenhouse gas formation from fossil fuel combustion. Electricity generated from wind or photovoltaic panels could be used for this purpose, but this does not yet appear to be cost-effective. Approaches that integrate solar energy harvesting and catalysis are particularly attractive as they afford the real possibility for inexpensive production of H 2(g) . In 1972, Fujishima and Honda (3) reported sustained water splitting from a relatively simple photoelectrochemical cell based on TiO 2 and Pt electrodes separated by a membrane (Fig. 1). The drawback was that sunlight absorption was limited to the UV region, comprising less than 3% of the solar spectrum. Since that time, alternative semiconductor materials have been identified that effectively harvest sunlight and split water more efficiently (4, 5); however, the associated costs are not economically competitive with today's fossil fuels. In a step toward simple low-cost approaches to solar hydrogen generation, Zheng et al. (6) report sustained H 2(g) generation over periods of 12 d with ∼40,000 turnovers by a dye molecule anchored to TiO 2 /Pt particles in an aqueous suspension. The turnover numbers are unprecedented for solar fuel production and may enable practically useful molecular approaches to solar hydrogen production.Light absorption by "dyads" drives the newly discovered hydrogen generation (6). The particular dyad that proved to be the most efficient is shown in Fig. 1 and referred to herein as the "Zheng dyad." It is composed of an organic dye molecule (Bodipy) covalently linked to a transition metal complex (PtN 2 S 2 ). The transition metal complex absorbs light across much of the visible region, but only weakly. In contrast, the organic Bodipy dye has a sharp intense absorption band in the green region with an extinction coefficient that is about two orders of magnitude larger. When linked together in the dyad, the optical and redox properties were well modeled as sum of the two individual parts, indicative of weak electronic coupling. Nevertheless, rapid energy tra...

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Theoretical Solar-to-Electrical Energy-Conversion Efficiencies of Perylene−Porphyrin Light-Harvesting Arrays

Cited by 113 publications

References 44 publications

Regioselective 15-Bromination and Functionalization of a Stable Synthetic Bacteriochlorin

Regioselective 15-Bromination and Functionalization of a Stable Synthetic Bacteriochlorin

Tuning the Electronic, Photophysical and Charge Transfer Properties of Small D-a Molecules Based on Thienopyrazine-Terthienyls by Changing the Donor Fragment: A DFT Study

Antenna molecule drives solar hydrogen generation

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