Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule

Hartnett, Patrick E.; Dyar, Scott M.; Margulies, Eric A.; Shoer, Leah E.; Cook, Andrew W.; Eaton, Samuel W.; Marks, Tobin J.; Wasielewski, Michael R.

doi:10.1039/c4sc02551b

Cited by 68 publications

(93 citation statements)

References 70 publications

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“…Compared to most of liquid-crystalline D-A dyads/triads reported so far, [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] the spacing between the discotic D and A units controlled by the aliphatic periphery is larger in the present molecular architecture. On the one hand, small spacing is generally preferred in order to ensure the fast and efficient formation of photoinduced CT states.…”

Section: Subpicosecond Transient Absorption Measurements In Self-orgamentioning

confidence: 79%

“…When increasing the dyad concentration in MCH, the molar absorption coefficient of the perylene bisimide moiety decreases and the absorption band prole becomes broader and less structured, in relation with the formation of aggregates. No clear spectral shi is associated to the aggregation process contrarily to other perylene derivatives, 46 but an isobestic point nevertheless appears at about 530 nm, above which the absorption of the concentrated solution is higher, which reveals the interactions between loosely aggregated dyad molecules at higher concentration. The associated broader absorption band and hypochromic effect moreover indicate that aggregates are not ideal and that some disorder is induced by the presence of triphenylene-containing side chains.…”

Section: Absorption and Steady-state Uorescence Emission Spectra In mentioning

confidence: 97%

“…Among the variety of LC donor-acceptor (D-A) materials developed so far, [25][26][27][28] covalently linked electron D-A dyad and triad molecules are of interest as their self-assembly can produce highly ordered wellseparated structures of well-stacked D and A p-molecules. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] In such supramolecular systems, excitons are photogenerated close to the D-A interface and pathways for hole and electron transport are well dened, providing a suitable conguration for efficient formation of excited charge transfer (CT) states and ambipolar charge transport. While the power conversion efficiency of organic solar cells based on a LC nematic donor material blended with a fullerene derivative has recently reached 9.3%, 47 the highest efficiency reported in devices based on D-A liquid crystals is about 2.7%.…”

Section: Introductionmentioning

confidence: 99%

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Structure–charge transfer property relationship in self-assembled discotic liquid-crystalline donor–acceptor dyad and triad thin films

et al. 2016

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The photophysical properties of donor-acceptor (D-A) and donor-acceptor-donor (D-A-D) liquid crystalline dyads and triads based on two different discotic mesogens are examined in thin films by steady-state optical spectroscopy and subpicosecond transient absorption measurements. In these systems, triphenylene and perylene bisimide units are covalently linked by flexible decyloxy chain(s) and act as an electron donor (D) and acceptor (A), respectively. These discotic liquid-crystalline systems form well-separated D and A p-stacked columnar structures in thin films. The absorption spectra of the films indicate an aggregation of the perylene bisimide and triphenylene moieties along the columns. Steadystate photoluminescence measurements show a strong fluorescence quenching that is mainly attributed to a photo-induced charge transfer process taking place between the triphenylene and perylene bisimide units. Subpicosecond transient absorption measurements show that the photoinduced charge transfer (CT) states in the dyad and triad films are formed within 0.3 ps and recombine on a 150-360 ps time scale. In addition, a correlation between the dynamics of the charge recombination process and the spacing distances between D and A units can be established in the dyad and triad films. This study provides important information on the relationship between molecular packing and the charge transfer properties in such self-organized D and A columnar nanostructures.

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Section: Subpicosecond Transient Absorption Measurements In Self-orgamentioning

confidence: 79%

Section: Absorption and Steady-state Uorescence Emission Spectra In mentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Structure–charge transfer property relationship in self-assembled discotic liquid-crystalline donor–acceptor dyad and triad thin films

et al. 2016

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“…In toluene, the charge separation energy (ΔG CS ) is estimated to be 2.0 eV (620 nm), and this peak appears in both solution aggregates (622 nm) and the supramolecular polymer film presented here (626 nm). The ground state recovery of the charge transfer band at 622 nm follows the charge recombination of mDPP •+ and PDI •− radical ions previously reported by us 29 and others, 24 with both ions absorbing broadly from 700−800 nm. Individual kinetics fit as a sum of exponentials of the ground state charge transfer band bleach at 622 nm and the radical ions at 722 nm are identical.…”

Section: ■ Transient Absorption Spectroscopymentioning

confidence: 84%

Extended Charge Carrier Lifetimes in Hierarchical Donor–Acceptor Supramolecular Polymer Films

Guzman

Calderón

et al. 2015

J. Phys. Chem. C

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We report that supramolecular polymer films composed of a 2:1 mixture of monodiamidopyridine diketopyrrolopyrrole (DPP) electron donors and perylene bisdiimide (PDI) electron acceptors undergo photoinduced charge transfer in the solid state. Film formation is guided by complementary noncovalent interactions programmed into the molecular components, resulting in a film architecture comprised of polymer wires with order across the molecular-to-macroscopic continuum. Using ultrafast transient absorption spectroscopy, we show that recombination lifetimes increase 1000-fold compared to the same supramolecular polymers in solution. Supramolecular donor−acceptor polymer films, such as these, that are designed by considering structure and electron transfer dynamics synergistically could lead to breakthroughs in organic optoelectronics. ■ INTRODUCTIONSignificant efforts have been devoted toward improving the performance of small molecule organic photovoltaics (OPVs); 1−4 however, challenges still remain with regard to understanding, controlling, and ultimately optimizing the photon-to-current conversion within the photoactive layer. Natural photosynthetic processes that efficiently convert sunlight to fuel rely upon precisely positioned assemblies of photofunctional chromophores for light harvesting, charge separation, and catalysis. 5 Light conversion in the reaction center involves the synergistic combination of superstructure and ultrafast electron transfer to form long-lived radical pairs. 6,7 The near unity conversion of light to chemical energy in the reaction center is a compelling model for future solar technologies 8 and has inspired the design of organic materials for artificial photosynthesis. 9−11 Similar to the reaction center, the photoactive layers of OPVs require appropriately matched donor and acceptor frontier molecular orbital levels and electronic coupling that enable rapid charge generation, and the resulting films must also possess multilength scale order for charge migration through the films. 12,13 Approaches for designing these materials must consider ease of preparation, solar spectrum absorption, electron transfer dynamics, and film order together to achieve efficient charge generation. Supramolecular polymers are a promising class of materials that could potentially be used for preparing organized films that undergo photoinduced charge separation. Supramolecular polymers are macromolecules whose monomeric repeat units are held together by noncovalent bonds, and their noteworthy characteristics include assembly from easy-to-prepare small molecules, hierarchical structure, and stimuli responsiveness. 14−19 Several supramolecular polymer systems have been explored in the context of photoinduced charge separation in solution 20−23 and the solid-state, 24−27 including a system we developed composed of a monodiamidopyridine diketopyrrolopyrrole (mDPP) electron donor and a perylene bisimide (PDI) electron acceptor 28 that assembles into 2:1 mDPP:PDI helical supramolecular polymers ( Figure 1a) as a re...

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“…So far, the first aspect has been investigated as conventional singlecomponent photovoltaic materials, while the second one is still a challenge and makes slow progress. However, the use of self-assembly strategy offers the opportunity to achieve the ordered structure and improved charge carrier mobility in the solid state [20,21].…”

Section: Introductionmentioning

confidence: 99%

Mesogenic complementary absorbing dyads based on porphyrin and perylene units

Kong

Gong

Dai

et al. 2018

J. Porphyrins Phthalocyanines

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Five novel dyads, consisting of a tetraphenylporphyrine unit connected to a perylene monoimide diester unit via a flexible bridge -CONH-(CH 2 ) n -(n = 4, 6, 8, 10 and 12), have been synthesized. Their structures were characterized by 13 C and 1 H nuclear magnetic resonance spectroscopy, infrared spectroscopy, mass spectrometry and elemental analysis. The UV-vis absorption spectra revealed these dyads have broad optical absorption in the ultraviolet and visible regions due to the complementary absorption of the two units. The differential scanning calorimetry traces and polarized optical microscopy textures showed all these dyads have columnar liquid crystal phases. Cyclic voltammetry revealed the highest occupied molecular orbitals of the dyads located on the porphyrin units, and the lowest unoccupied molecular orbitals located on the perylene units. In addition, these results were in agreement with that of the theoretical modeling. When excited at 423 or 473 nm, the photoluminescent emission spectra showed that the degree of fluorescence quenching of porphyrin units increased as the spacers became shorter. This quenching was ascribed to intramolecular photoinduced electron transfer, which also induced the dyad molecules to form the charge-separated states. The charge-separated molecules were further confirmed by the photocurrent response curves. These behaviors of broad absorption of the ultraviolet-visible light, yielding the charge-separated states of the molecules when excited and the formation of columnar liquid crystal phase made these dyads candidates for single-component photovoltaic active materials.

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Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule

Abstract: Self-ordering of covalent electron donor–acceptor building blocks in thin films upon solvent vapor annealing results in a 104 increase in photo-generated charge carrier lifetime.

Cited by 68 publications

References 70 publications

Structure–charge transfer property relationship in self-assembled discotic liquid-crystalline donor–acceptor dyad and triad thin films

Structure–charge transfer property relationship in self-assembled discotic liquid-crystalline donor–acceptor dyad and triad thin films

Extended Charge Carrier Lifetimes in Hierarchical Donor–Acceptor Supramolecular Polymer Films

Mesogenic complementary absorbing dyads based on porphyrin and perylene units

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