Self-Assembly of Supramolecular Light-Harvesting Arrays from Covalent Multi-Chromophore Perylene-3,4:9,10-bis(dicarboximide) Building Blocks

Ahrens, Michael J.; Sinks, Louise E.; Rybtchinski, Boris; Liu, Wenhao; Jones, Brian; Giaimo, Jovan M.; Gusev, Alexy V.; Goshe, Andrew J.; Tiede, David M.; Wasielewski, Michael R.

doi:10.1021/ja039820c

Cited by 280 publications

(324 citation statements)

References 92 publications

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“…30. The samples were prepared in glass cuvettes, and the absorbance at the 400-nm excitation wavelength was typically 0.020-0.035.…”

Section: Methodsmentioning

confidence: 99%

“…The instrument response function was 25 ps. Femtosecond transient absorption measurements were made by using the 510-nm 110-fs output of an optical parametric amplifier by using techniques described earlier (30). The absorbance of all samples for femtosecond transient absorption spectroscopy was maintained between 0.3 and 0.5 at 510 nm in a 2-mm cuvette (For PDI, 550 ϭ 46,000 cm Ϫ1 ⅐M Ϫ1 ).…”

Section: Methodsmentioning

confidence: 99%

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Wire-like charge transport at near constant bridge energy through fluorene oligomers

Goldsmith

Sinks

Kelley

et al. 2005

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

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167

187

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The study of photoinitiated electron transfer in donor-bridgeacceptor molecules has helped elucidate the distance dependence of electron transfer rates and behavior of various electron transfer mechanisms. In all reported cases, the energies of the bridge electronic states involved in the electron transfer change dramatically as the length of the bridge is varied. We report here, in contrast, an instance in which the length of the bridge, and therefore the distance over which the electron is transferred, can be varied without significantly changing the energies of the relevant bridge states. A series of donor-bridge-acceptor molecules having phenothiazine (PTZ) donors, 2,7-oligofluorene (FLn) bridges, and perylene-3,4:9,10-bis(dicarboximide) (PDI) acceptors was studied. Photoexcitation of PDI to its lowest excited singlet state results in oxidation of PTZ via the FLn bridge. In toluene, the rate constants for both charge separation and recombination as well as the energy levels of the relevant FL n ؉• bridge states for n ‫؍‬ electron transfer ͉ hopping ͉ superexchange E fficient long-distance electron transfer is a prerequisite for molecular materials designed to serve as active components in solar cells and nanoscale devices. Being able to consistently achieve ''wire-like'' charge transport in synthetic systems requires a thorough understanding of the mechanisms involved. Recently progress has been made toward this goal (1, 2), but the complexity of even simple molecular systems poses a formidable challenge. In particular, the distance dependence of electron transfer has been shown to be a complex function of individual parameters, including molecular geometry and energetics (3,4). While the use of rigidly bound electron donor (D), bridge (B), electron acceptor (A) compounds has simplified the investigation of the distance dependence of electron transfer by keeping the donor-acceptor distance (r DA ) well defined, it is difficult to vary r DA by changing the length of the bridge without substantially altering the energy levels of the bridge.In this report we examine electron transfer in a system in which r DA can be changed considerably, whereas the oxidation potential of the intervening bridge changes very little. Approximate matching between the donor and bridge energy levels (2, 5, 6) has been shown to be critical for promoting incoherent, or ''wire-like,'' transport over coherent, or exponentially distance-dependent, superexchange transport (7). These earlier studies have shown how the energetic convergence of the relevant donor and bridge energy levels results in a minimal injection barrier for hole transfer to the bridge, leading to a striking change in mechanism as the bridge is lengthened.The relative importance of incoherent transport at larger values of r DA has been confirmed by independent measurements of the decreasing contribution of superexchange to the overall electron transfer rate with increasing length (8, 9). The indirect electronic coupling between the electron donor and acceptor via the br...

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“…30. The samples were prepared in glass cuvettes, and the absorbance at the 400-nm excitation wavelength was typically 0.020-0.035.…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Wire-like charge transport at near constant bridge energy through fluorene oligomers

Goldsmith

Sinks

Kelley

et al. 2005

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

Self Cite

167

187

View full text Add to dashboard Cite

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“…The large Stokes shift and the increased width of the new broad emission feature relative to the free SM suggests that this effect is due to exciton-transfer and subsequent emission from lower energy chromophore-aggregate states. 48,49 The pure acceptor polymer AP20:0:1 has an effective acceptor concentration of 0.054 M or 29.51 wt%. AP20:01 also showed a bathochromic shift in emission in the solid state, though to a lesser extent than SP20:1:0 ( Figure 6 (b)).…”

Section: Polymer Thin-film Photophysicsmentioning

confidence: 99%

Energy transfer in pendant perylene diimide copolymers

et al. 2016

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We report the synthesis, characterisation and polymerisation of two novel asymmetric perylene diimide acrylate monomers. The novel monomers form a sensitiser-acceptor pair capable of undergoing Förster resonance energy transfer, and were incorporated as copolymers with tert-butyl acrylate. The tert-butyl acrylate units act as spacers along the polymer chain allowing high concentrations of dye while mitigating aggregate quenching, leading to persistent fluorescence in the solid state at high concentrations of up to 0.3 M. Analysis of fluorescence kinetics showed efficient energy transfer between the optically dense sensitiser and the lower concentration acceptor luminophores within the polymer. This reduced reabsorption within the material demonstrates that the copolymer-scaffold energy transfer system has potential for use in luminescent solar concentrators.

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“…Applications as diverse as patterned deposition of metallic©monolayers© [1],©creation©of©ordered©light-harvesting©arrays© [2],©and©creation©of©new©biological materials based on self assembled peptide structures [3],© have© revolutionized© the© development© of© materials with nanoscale features. Various types of chemical interactions have been used to direct the assembly of individual subunits into the desired products.…”

mentioning

confidence: 99%

Electrospray ionization mass spectrometric detection of self-assembly of a crown ether complex directed by π-stacking interactions

Sherman

Brodbelt

Marchand

et al. 2005

J. Am. Soc. Mass Spectrom.

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The self-assembly of ligand-metal-ligand sandwich complexes involving a novel quinoxalinecontaining crown ether, 1, was studied by electrospray ionization mass spectrometry (ESI-MS). Donor-acceptor -stacking interactions between the electron-poor quinoxaline group of 1 and electron-rich benzene groups from benzo-or dibenzo-18-crown-6 were found to significantly enhance the formation of mixed-ligand sandwich complexes with a free energy gain of up to 17 kJ/mol relative to sandwich formation involving macrocycles without such aromatic functionalities. The relative intensities of the sandwich complexes were greatest with the alkali metals Na In the present report, we present electrospray ionization mass spectrometry (ESI-MS) results on a novel crown ether which demonstrate that donor-acceptor -stacking interactions can be used to direct the self-assembly of noncovalent macrocycle-metal complexes.For probing metal complexation of macrocyclic systems, ESI-MS has proven to be an invaluable tool. Since ESI© is© capable© of© transferring© even© very© weakly© bound noncovalent complexes to the gas phase, mass spectrometry can be used to qualitatively and quantitatively evaluate the binding selectivities of the hosts or the relative binding constants of the resulting host-guest complexes© [4© -22].©Furthermore,©many©studies©have demonstrated that the results of ESI-MS analysis of these host-guest complexes correlate well with mea- Although binding of the second ligand in a ligandmetal-ligand sandwich complex in solution is typically not as strong as for the first ligand for unsubstituted crown©ethers© [27],©it©is©expected©that©the©addition©of certain functional groups on the macrocycle could enhance the formation of sandwich complexes. An analogous result has been observed for the formation of bis-crown ether-metal complexes studied by ESI-MS [13,© 23,© 28].© For© these© macrocycles,© the© preorganization offered by the covalently linked crown ethers results in very strong metal complexation in which the metal cation is simultaneously coordinated by both crown ethers.Rather than rely on covalently linked structures, such as those used in bis-crown ethers, other chemical interactions must be leveraged to create sandwich complexes which can self-assemble. -Stacking interactions, present in many biological systems and having demonstrated utility in strengthening other types of molecular interactions© [32][33][34][35],© represent© a© novel© means© of© enhanc-

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Self-Assembly of Supramolecular Light-Harvesting Arrays from Covalent Multi-Chromophore Perylene-3,4:9,10-bis(dicarboximide) Building Blocks

Cited by 280 publications

References 92 publications

Wire-like charge transport at near constant bridge energy through fluorene oligomers

Wire-like charge transport at near constant bridge energy through fluorene oligomers

Energy transfer in pendant perylene diimide copolymers

Electrospray ionization mass spectrometric detection of self-assembly of a crown ether complex directed by π-stacking interactions

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