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Jonathan S Lindsey - One of the best experts on this subject based on the ideXlab platform.
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panchromatic chromophore tetrapyrrole light harvesting arrays constructed from bodipy Perylene terrylene porphyrin chlorin and bacteriochlorin building blocks
New Journal of Chemistry, 2016Co-Authors: Rui Liu, David F Bocian, Dewey Holten, Amit Kumar Mandal, Eric J Alexy, Jonathan S LindseyAbstract:Panchromatic absorbers are potentially valuable for use in molecular-based energy-conversion schemes. A prior dyad composed of a Perylene-monoimide joined at the 9-position via an ethyne to the porphyrin meso-position afforded panchromatic absorption (350–700 nm). To explore the effects of structure on panchromaticity, five new arrays were synthesized from eight (four new) chromophore or tetrapyrrole building blocks. Two dyads contain a dipyrrinatoboron difluoride (bodipy) or terrylene chromophore in lieu of the Perylene to assess the effects of the chromophore π-system on panchromaticity. The long-wavelength absorption band of sparsely substituted variants of the three chromophores (dipyrrinatoboron difluoride, Perylene-monoimide, terrylene-monoimide) is generally in the range 480–550 nm, 490–540 nm and 600–660 nm. Three Perylene–tetrapyrrole constructs were prepared wherein the Perylene–ethyne is attached at the β-pyrrole position of a porphyrin, chlorin, or bacteriochlorin, versus the meso-site used previously. The latter set addresses the effect of linker connection site on the spectral properties, which is prompted by the differing electron densities at these positions of the three tetrapyrrole macrocycles. A new route is reported for the synthesis of a β-bromoporphyrin building block. Static absorption and emission spectra, fluorescence yields and singlet excited-state lifetimes were examined for all arrays and nine (five new) ethynyl-bearing benchmarks. Four guidelines emerge: (1) panchromaticity decreases in the order Perylene > dipyrrinatoboron difluoride > terrylene; (2) the porphyrin meso-site affords far greater panchromaticity than the β-site; (3) panchromaticity for chlorins and bacteriochlorins is less affected by linker site; and (4) the chromophore–porphyrin dyad with Perylene (versus boron-dipyrrin or terrylene) affords the most porphyrin-like and robust lowest singlet excited state for utilization of the harvested energy. Collectively, the new synthetic constructs (5 arrays, 5 benchmarks, 4 building blocks) have elicited heuristics for the de novo design of panchromatic light-harvesting architectures.
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probing electronic communication for efficient light harvesting functionality dyads containing a common Perylene and a porphyrin chlorin or bacteriochlorin
Journal of Physical Chemistry B, 2014Co-Authors: Eunkyung Yang, Dariusz M Niedzwiedzki, Christine Kirmaier, David F Bocian, Jonathan S Lindsey, Jieqi Wang, James R Diers, Dewey HoltenAbstract:The synthesis, photophysical, redox, and molecular-orbital characteristics of three Perylene-tetrapyrrole dyads were investigated to probe the efficacy of the arrays for use as light-harvesting constituents. Each dyad contains a common Perylene-monoimide that is linked at the N-imide position via an arylethynyl group to the meso-position of the tetrapyrrole. The tetrapyrroles include a porphyrin, chlorin, and bacteriochlorin, which have zero, one, and two reduced pyrrole rings, respectively. The increased pyrrole-ring reduction results in a progressive red shift and intensification of the lowest-energy absorption band, as exemplified by benchmark monomers. The arylethyne linkage affords moderate Perylene-tetrapyrrole electronic coupling in the dyads as evidenced by the optical, molecular-orbital, and redox properties of the components of the dyads versus the constituent parts. All three dyads in nonpolar solvents exhibit relatively fast (subpicosecond) energy transfer from the Perylene to the tetrapyrrole. Competing charge-transfer processes are also absent in nonpolar solvents, but become active for both the chlorin and bacteriochlorin-containing dyads in polar solvents. Calculations of energy-transfer rates via the Forster, through-space mechanism reveal that these rates are, on average, 3-fold slower than the observed rates. Thus, the Dexter through-bond mechanism contributes more substantially than the through-space mechanism to energy transfer in the dyads. The electronic communication between the Perylene and tetrapyrrole falls in a regime intermediate between those operative in other classes of Perylene-tetrapyrrole dyads that have previously been studied.
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Probing Electronic Communication for Efficient Light-Harvesting Functionality: Dyads Containing a Common Perylene and a Porphyrin, Chlorin, or Bacteriochlorin
2014Co-Authors: Eunkyung Yang, Dariusz M Niedzwiedzki, Christine Kirmaier, David F Bocian, Jonathan S Lindsey, Jieqi Wang, James R. Diers, Dewey HoltenAbstract:The synthesis, photophysical, redox, and molecular-orbital characteristics of three Perylene–tetrapyrrole dyads were investigated to probe the efficacy of the arrays for use as light-harvesting constituents. Each dyad contains a common Perylene–monoimide that is linked at the N-imide position via an arylethynyl group to the meso-position of the tetrapyrrole. The tetrapyrroles include a porphyrin, chlorin, and bacteriochlorin, which have zero, one, and two reduced pyrrole rings, respectively. The increased pyrrole-ring reduction results in a progressive red shift and intensification of the lowest-energy absorption band, as exemplified by benchmark monomers. The arylethyne linkage affords moderate Perylene–tetrapyrrole electronic coupling in the dyads as evidenced by the optical, molecular-orbital, and redox properties of the components of the dyads versus the constituent parts. All three dyads in nonpolar solvents exhibit relatively fast (subpicosecond) energy transfer from the Perylene to the tetrapyrrole. Competing charge-transfer processes are also absent in nonpolar solvents, but become active for both the chlorin and bacteriochlorin-containing dyads in polar solvents. Calculations of energy-transfer rates via the Förster, through-space mechanism reveal that these rates are, on average, 3-fold slower than the observed rates. Thus, the Dexter through-bond mechanism contributes more substantially than the through-space mechanism to energy transfer in the dyads. The electronic communication between the Perylene and tetrapyrrole falls in a regime intermediate between those operative in other classes of Perylene–tetrapyrrole dyads that have previously been studied
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theoretical solar to electrical energy conversion efficiencies of Perylene porphyrin light harvesting arrays
Journal of Physical Chemistry B, 2006Co-Authors: Georg M Hasselman, David F Bocian, Jonathan S Lindsey, Dewey Holten, David F Watson, Jonathan R Stromberg, Gerald J MeyerAbstract:The efficiencies of organic solar cells that incorporate light-harvesting arrays of organic pigments were calculated under 1 sun of air mass 1.5 solar irradiation. In one set of calculations, photocurrent efficiencies were evaluated for porphyrin, phthalocyanine, chlorin, bacteriochlorin, and porphyrin−bis(Perylene) pigment arrays of different length and packing densities under the assumption that each solar photon absorbed quantitatively yielded one electron in the external circuit. In another more realistic set of calculations, solar conversion efficiencies were evaluated for arrays comprising porphyrins or porphyrin−(Perylene)2 units taking into account competitive excited-state relaxation pathways. A system of coupled differential equations for all reactions in the arrays was solved on the basis of previously published rate constants for (1) energy transfer between the Perylene and porphyrin pigments, (2) excited-state relaxation of the Perylene and porphyrin pigments, and (3) excited-state electron i...
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synthesis and excited state photodynamics of Perylene porphyrin dyads 1 parallel energy and charge transfer via a diphenylethyne linker
Journal of Physical Chemistry B, 2001Co-Authors: Sreedharan Prathapan, David F Bocian, Mark A Miller, Sung Ik Yang, Jyoti Seth, Dewey Holten And, Jonathan S LindseyAbstract:The photophysical properties of a Perylene−porphyrin dyad have been examined with the aim of using this construct for molecular photonics applications. The dyad consists of a Perylene-bis(imide) dye (PDI) connected to a zinc porphyrin (Zn) via a diphenylethyne linker (pep). In both polar and nonpolar solvents, the photoexcited Perylene unit (PDI*) decays very rapidly (lifetimes of 2.5 (toluene) and 2.4 ps (acetonitrile)) by energy transfer to the porphyrin, forming PDI−pep−Zn* in high yield (80%, toluene; 70% acetonitrile), and hole transfer to the porphyrin, forming PDI-−pep−Zn+ in lesser yield (20%, toluene; 30% acetonitrile). In both toluene and acetonitrile, the Zn* excited state subsequently decays with a lifetime of 0.4 ns primarily (80%) by electron transfer to the Perylene (forming PDI-−pep−Zn+). In the nonpolar solvent (toluene), the PDI-−pep−Zn+ charge-transfer product has a lifetime of >10 ns and decays by charge recombination primarily to the ground state but also by thermal repopulation of th...
Wolter F Jager - One of the best experts on this subject based on the ideXlab platform.
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overcoming the exciton binding energy in two dimensional perovskite nanoplatelets by attachment of conjugated organic chromophores
Nature Communications, 2020Co-Authors: Maria C Gelvezrueda, Rajeev K Dubey, Wolter F Jager, Magnus B Fridriksson, Ward Van Der Stam, Ferdinand C GrozemaAbstract:In this work we demonstrate a novel approach to achieve efficient charge separation in dimensionally and dielectrically confined two-dimensional perovskite materials. Two-dimensional perovskites generally exhibit large exciton binding energies that limit their application in optoelectronic devices that require charge separation such as solar cells, photo-detectors and in photo-catalysis. Here, we show that by incorporating a strongly electron accepting moiety, Perylene diimide organic chromophores, on the surface of the two-dimensional perovskite nanoplatelets it is possible to achieve efficient formation of mobile free charge carriers. These free charge carriers are generated with ten times higher yield and lifetimes of tens of microseconds, which is two orders of magnitude longer than without the peryline diimide acceptor. This opens a novel synergistic approach, where the inorganic perovskite layers are combined with functional organic chromophores in the same material to tune the properties for specific applications.
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substitution effects on the photoinduced charge transfer properties of novel Perylene 3 4 9 10 tetracarboxylic acid derivatives
Journal of Physical Chemistry A, 2017Co-Authors: Damla Inan, Rajeev K Dubey, Nick Westerveld, Jorrit Bleeker, Wolter F Jager, Ferdinand C GrozemaAbstract:We report here the synthesis and photophysical study of a series of electron donor–acceptor molecules, in which electron-donating 4-methoxyphenoxy groups are attached to the 1,7-bay positions of four different Perylene tetracarboxylic acid derivatives, namely, Perylene tetraesters 1, Perylene monoimide diesters 2, Perylene bisimides 3, and Perylene monobenzimidazole monoimides 4. These Perylene derivatives are used because of their increasing order of electron-accepting capability upon moving from 1 to 4. Two additional donor–acceptor molecules are synthesized by linking electron-donating 4-methoxyphenyl groups to the imide position of Perylene monoimide diester 2 and Perylene bisimide 3. The motivation for this study is to achieve a good control over the photoinduced charge-transfer (CT) process in Perylene-based systems by altering the position of electron donors and tuning the electron deficiency of Perylene core. A comprehensive study of the photophysical properties of these molecules has shown a high...
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tunable and highly efficient light harvesting antenna systems based on 1 7 Perylene 3 4 9 10 tetracarboxylic acid derivatives
Chemical Science, 2016Co-Authors: Rajeev K Dubey, Damla Inan, Ferdinand C Grozema, Sanchita Sengupta, Ernst J R Sudholter, Wolter F JagerAbstract:We report the synthesis and excited-state dynamics of a series of five bichromophoric light-harvesting antenna systems, which are capable of efficient harvesting of solar energy in the spectral range of 350–580 nm. These antenna systems have been synthesized in a modular fashion by the covalent attachment of blue light absorbing naphthalene monoimide energy donors (D1, D2, and D3) to green light absorbing Perylene-3,4,9,10-tetracarboxylic acid derived energy acceptors, 1,7-Perylene-3,4,9,10-tetracarboxylic tetrabutylester (A1), 1,7-Perylene-3,4,9,10-tetracarboxylic monoimide dibutylester (A2), and 1,7-Perylene-3,4,9,10-tetracarboxylic bisimide (A3). The energy donors have been linked at the 1,7-bay-positions of the Perylene derivatives, thus leaving the peri positions free for further functionalization and device construction. A highly stable and rigid structure, with no electronic communication between the donor and acceptor components, has been realized via an all-aromatic non-conjugated phenoxy spacer between the constituent chromophores. The selection of donor naphthalene derivatives for attachment with Perylene derivatives was based on the effective matching of their respective optical properties to achieve efficient excitation energy transfer (EET) by the Forster mechanism. A comprehensive study of the excited-state dynamics, in toluene, revealed quantitative and ultrafast (ca. 1 ps) intramolecular EET from donor naphthalene chromophores to the acceptor Perylenes in all the studied systems. Electron transfer from the donor naphthalene chromophores to the acceptor Perylenes has not been observed, not even for antenna systems in which this process is thermodynamically allowed. Due to the combination of an efficient and fast energy transfer along with broad absorption in the visible region, these antenna systems are promising materials for solar-to-electric and solar-to-fuel devices.
Ferdinand C Grozema - One of the best experts on this subject based on the ideXlab platform.
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overcoming the exciton binding energy in two dimensional perovskite nanoplatelets by attachment of conjugated organic chromophores
Nature Communications, 2020Co-Authors: Maria C Gelvezrueda, Rajeev K Dubey, Wolter F Jager, Magnus B Fridriksson, Ward Van Der Stam, Ferdinand C GrozemaAbstract:In this work we demonstrate a novel approach to achieve efficient charge separation in dimensionally and dielectrically confined two-dimensional perovskite materials. Two-dimensional perovskites generally exhibit large exciton binding energies that limit their application in optoelectronic devices that require charge separation such as solar cells, photo-detectors and in photo-catalysis. Here, we show that by incorporating a strongly electron accepting moiety, Perylene diimide organic chromophores, on the surface of the two-dimensional perovskite nanoplatelets it is possible to achieve efficient formation of mobile free charge carriers. These free charge carriers are generated with ten times higher yield and lifetimes of tens of microseconds, which is two orders of magnitude longer than without the peryline diimide acceptor. This opens a novel synergistic approach, where the inorganic perovskite layers are combined with functional organic chromophores in the same material to tune the properties for specific applications.
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substitution effects on the photoinduced charge transfer properties of novel Perylene 3 4 9 10 tetracarboxylic acid derivatives
Journal of Physical Chemistry A, 2017Co-Authors: Damla Inan, Rajeev K Dubey, Nick Westerveld, Jorrit Bleeker, Wolter F Jager, Ferdinand C GrozemaAbstract:We report here the synthesis and photophysical study of a series of electron donor–acceptor molecules, in which electron-donating 4-methoxyphenoxy groups are attached to the 1,7-bay positions of four different Perylene tetracarboxylic acid derivatives, namely, Perylene tetraesters 1, Perylene monoimide diesters 2, Perylene bisimides 3, and Perylene monobenzimidazole monoimides 4. These Perylene derivatives are used because of their increasing order of electron-accepting capability upon moving from 1 to 4. Two additional donor–acceptor molecules are synthesized by linking electron-donating 4-methoxyphenyl groups to the imide position of Perylene monoimide diester 2 and Perylene bisimide 3. The motivation for this study is to achieve a good control over the photoinduced charge-transfer (CT) process in Perylene-based systems by altering the position of electron donors and tuning the electron deficiency of Perylene core. A comprehensive study of the photophysical properties of these molecules has shown a high...
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tunable and highly efficient light harvesting antenna systems based on 1 7 Perylene 3 4 9 10 tetracarboxylic acid derivatives
Chemical Science, 2016Co-Authors: Rajeev K Dubey, Damla Inan, Ferdinand C Grozema, Sanchita Sengupta, Ernst J R Sudholter, Wolter F JagerAbstract:We report the synthesis and excited-state dynamics of a series of five bichromophoric light-harvesting antenna systems, which are capable of efficient harvesting of solar energy in the spectral range of 350–580 nm. These antenna systems have been synthesized in a modular fashion by the covalent attachment of blue light absorbing naphthalene monoimide energy donors (D1, D2, and D3) to green light absorbing Perylene-3,4,9,10-tetracarboxylic acid derived energy acceptors, 1,7-Perylene-3,4,9,10-tetracarboxylic tetrabutylester (A1), 1,7-Perylene-3,4,9,10-tetracarboxylic monoimide dibutylester (A2), and 1,7-Perylene-3,4,9,10-tetracarboxylic bisimide (A3). The energy donors have been linked at the 1,7-bay-positions of the Perylene derivatives, thus leaving the peri positions free for further functionalization and device construction. A highly stable and rigid structure, with no electronic communication between the donor and acceptor components, has been realized via an all-aromatic non-conjugated phenoxy spacer between the constituent chromophores. The selection of donor naphthalene derivatives for attachment with Perylene derivatives was based on the effective matching of their respective optical properties to achieve efficient excitation energy transfer (EET) by the Forster mechanism. A comprehensive study of the excited-state dynamics, in toluene, revealed quantitative and ultrafast (ca. 1 ps) intramolecular EET from donor naphthalene chromophores to the acceptor Perylenes in all the studied systems. Electron transfer from the donor naphthalene chromophores to the acceptor Perylenes has not been observed, not even for antenna systems in which this process is thermodynamically allowed. Due to the combination of an efficient and fast energy transfer along with broad absorption in the visible region, these antenna systems are promising materials for solar-to-electric and solar-to-fuel devices.
Damian Plazuk - One of the best experts on this subject based on the ideXlab platform.
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functionalization of the bay region of Perylene in reaction with 1 arylalk 2 yn 1 ones catalyzed by trifluoromethanesulfonic acid one step approach to 1 acyl 2 alkylbenzo ghi Perylenes
Journal of Organic Chemistry, 2018Co-Authors: Marta Glodek, Anna Makal, Damian PlazukAbstract:We describe a convenient method of the synthesis of 1-acyl-2-alkylbenzo[ghi]Perylenes via functionalization of the “bay region” of Perylene in the reaction with 1-arylalk-2-yn-1-ones catalyzed by t...
Frank Wurthner - One of the best experts on this subject based on the ideXlab platform.
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a Perylene bisimide cyclophane as a turn on and turn off fluorescence probe
Angewandte Chemie, 2015Co-Authors: Peter Spenst, Frank WurthnerAbstract:A rigid, covalently linked Perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) cyclophane was synthesized by imidization of a bay-substituted Perylene bisanhydride with p-xylylenediamine. The interchromophoric distance of approximately 6.5 A establishes an ideal rigid cavity for the encapsulation of large aromatic compounds such as Perylene and anthracene with binding constants up to 4.6×104 M−1 (in CHCl3). For electron-poor guest molecules, the complexation process is accompanied by a significantly increased fluorescence, whereas the emission intensity is dramatically quenched by more electron-rich guests because of the formation of charge-transfer complexes. Furthermore, the influence of the PBI core twist on the binding constant results in a remarkable selectivity towards more flexible aromatic guest molecules.
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halochromic and hydrochromic squaric acid functionalized Perylene bisimide
Chemical Communications, 2015Co-Authors: Takeshi Maeda, Frank WurthnerAbstract:The functionalization of Perylene bisimide by squaric acid afforded halochromic dyes with pronounced acidity. The dye senses solvent polarity, pH and humidity by means of pronounced changes in absorption spectra and thin film color through the intramolecular charge transfer between Perylene and cyclobutene cores initiated by protonation/deprotonation.
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molecular assemblies of Perylene bisimide dyes in water
Angewandte Chemie, 2012Co-Authors: Daniel Gorl, Xin Zhang, Frank WurthnerAbstract:Perylene bisimides are among the most valuable functional dyes and have numerous potential applications. As a result of their chemical robustness, photostability, and outstanding optical and electronic properties, these dyes have been applied as pigments, fluorescence sensors, and n-semiconductors in organic electronics and photovoltaics. Moreover, the extended quadrupolar π system of this class of dyes has facilitated the construction of numerous supramolecular architectures with fascinating photophysical properties. However, the supramolecular approach to the formation of Perylene bisimide aggregates has been restricted mostly to organic media. Pleasingly, considerable progress has been made in the last few years in developing water-soluble Perylene bisimides and their application in aqueous media. This Review provides an up-to-date overview on the self-assembly of Perylene bisimides through π–π interactions in aqueous media. Synthetic strategies for the preparation of water-soluble Perylene bisimides and the influence of water on the π–π stacking of Perylene bisimides as well as the resulting applications are discussed.
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effects of bay substituents on the racemization barriers of Perylene bisimides resolution of atropo enantiomers
Journal of the American Chemical Society, 2007Co-Authors: Peter Osswald, Frank WurthnerAbstract:The activation parameters for the interconversion of atropisomers (P- and M-enantiomer) of core-twisted Perylene bisimides have been determined by dynamic NMR spectroscopy (DNMR) and time- and temperature-dependent CD spectroscopy. By comparing the activation parameters of a series of Perylene bisimides containing halogen or aryloxy substituents in the bay area (1,6,7,12-positions), a clear structure−property relationship has been found that demonstrates that the kinetic and thermodynamic parameters for the inversion of enantiomers are dependent on the apparent overlap parameter ∑r* of the bay substituents. This study reveals a high stability (ΔG⧧368 K = 118 kJ/mol) for the atropo-enantiomers of tetrabromo-substituted Perylene bisimide in solution. Accordingly, the enantiomers of this derivative could be resolved by HPLC on a chiral column. These enantiomers do not racemize in solution at room temperature and, thus, represent the first examples of enantiomerically pure core-twisted Perylene bisimides.
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energy transfer in calixarene based cofacial positioned Perylene bisimide arrays
Journal of the American Chemical Society, 2006Co-Authors: Catharina Hippius, Felix Schlosser, Myroslav O Vysotsky, Volker Bohmer, Frank WurthnerAbstract:The synthesis of multichromophoric Perylene bisimide-calix[4]arene arrays with up to five Perylene units (containing orange, violet, and green Perylene bisimide chromophores) and of monochromophoric model compounds was achieved by subsequent imidization of mono-Boc functionalized calix[4]arene linkers with three different types of Perylene bisimide dye units. The optical properties of all compounds were studied with UV/vis absorption and steady state and time-resolved fluorescence spectroscopy. Upon excitation of the inner orange dye at 490 nm of array 3, strong fluorescence emission of the outer green Perylene bisimide (PBI) chromophore at 744 nm is observed. The fluorescence excitation spectra of compounds 3 and 4 (lambdadet = 850 nm) show all absorption bands of the parent chromophores (e.g., all Perylene units contribute to the emission from S1 state of the green PBI). Thus, the fluorescence emission and excitation spectra as well as time-resolved data of fluorescence lifetimes in the absence (tauD = 5.1 ns) and in the presence of an acceptor (tauDA = 0.8 ns) suggest efficient energy transfer processes between the Perylene bisimide dye units. For the bichromophoric array 4, the energy transfer rate is calculated to a value of 1.05 x 109 s-1. These results demonstrate highly efficient energy transfer in cofacially assembled dye arrays.
