Rational design of a phthalocyanine–perylenediimide dyad with a long-lived charge-separated state

Blas‐Ferrando, Vicente M.; Ortíz, Javier; Bouissane, Latifa; Ohkubo, Kei; Fukuzumi, Shunichi; Fernández‐Lázaro, Fernando; Sastre‐Santos, Ángela

doi:10.1039/c2cc31087b

Cited by 57 publications

(30 citation statements)

References 42 publications

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“…66,67,70 This agrees with our calculated values, 1.23 eV for PDI and 1.17 for PBI (Figures S13 and S14 of the Supporting Information). The introduction of the two electron-donating p-tert-butylphenoxy groups to PDI to form PBI clearly reduced the energy level of singlet excited states of the perylene bisimide module from 2.32 eV in MTPA-TRC-PDI to 2.15 eV in MTPA-TRC-PBI.…”

Section: Determination Of Frontier Orbital Energies Forsupporting

confidence: 92%

Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A₁-A₂ Organic Semiconductors

et al. 2016

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An ambipolar organic semiconductor with styrene based triphenylamine derivative (MTPA) as an electron donor (D), triazine group (TRC) as an electron acceptor (A 1 ), and 9,10-anthraquinone (AEAQ) as a second electron acceptor (A 2 ) has shown an 8-fold increase in the lifetime of charge separation with a high performance as solar cell materials with respect to the D-A 1 architecture and demonstrated a general D-A 1 -A 2 architecture as a promising materials design strategy for photovoltaics. Here we synthesized and characterized two new D-A 1 -A 2 compounds with perylene bisimide derivatives (PDI and PBI) as A 2 using an integrated experimental and computational method to study and compare the kinetics of three MTPA-TRC-A 2 systems. A two-step sequential decay pathway was observed in both MTPA-TRC-PDI and MTPA-TRC-PBI but a direct decay pathway in MTPA-TRC-AEAQ. The charge separated state with a lifetime of 22 ns in the PDI system and 75 ns in the PBI system relaxes to the corresponding triplet state followed by the decay to ground state in 827 ns and 29.2 μs, respectively. Thus, a triplet state with a lower energy than the charge separated state shortens the lifetime of the charge separated state but increases the overall lifetime of excited states.

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Section: Determination Of Frontier Orbital Energies Forsupporting

confidence: 92%

Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A₁-A₂ Organic Semiconductors

et al. 2016

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“…72 A transient absorption spectrum observed at 1 ps after laser pulse excitation (λ ex = 393 nm) is shown in Figure 6a. The transient absorption band observed at 1 ps clearly showed the singlet excited state of zinc phthalocyanine 1 ZnPc * (λ max = 590 nm) 62,63,73,74 which is overlapped with the strong ground--state bleaching and emission at 680 nm for the ZnPc moiety and Vis--NIR region for the graphene entity. As electron transfer from 1 ZnPc * to graphene proceeds, the transient absorption due to 1 ZnPc* disappears, accompanied by the appearance of the transient absorption band due to ZnPc •+ .…”

Section: Resultsmentioning

confidence: 99%

Zinc Phthalocyanine–Graphene Hybrid Material for Energy Conversion: Synthesis, Characterization, Photophysics, and Photoelectrochemical Cell Preparation

et al. 2012

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Graphene exfoliation upon tip sonication in o--DCB was accomplished. Then, covalent grafting of (2--aminoethoxy)(tri--tert--butyl) zinc phthalocyanine (ZnPc), to exfoliated graphene sheets was achieved. The newly formed ZnPc--graphene hybrid material was found soluble in common organic solvents without any precipitation for several weeks. Application of diverse spectroscopic techniques verified the successful formation of ZnPc--graphene hybrid materi--al, while thermogravimetric analysis revealed the amount of ZnPc loading onto graphene. Microscopy analysis based on AFM and TEM was applied to probe the morphological characteristics and to investigate the exfoliation of graphene sheets. Efficient fluorescence quenching of ZnPc in the ZnPc--graphene hybrid material suggested that photoinduced events occur from the photoexcited ZnPc to exfoliated graphene. The dynamics of the photoinduced electron transfer was evaluated by femtosecond transient absorption spectroscopy, thus, revealing the formation of transient species such as ZnPc + yielding the charge--separated state ZnPc •+ -graphene •-. Finally, the ZnPc--graphene hybrid material was integrated into a photoactive electrode of an optical transparent electrode (OTE) cast with nanostructured SnO 2 films (OTE/SnO 2 ), which exhibited stable and reproducible photocurrent responses and the incident photon--to--current conversion efficien--cy was determined.

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“…[1][2][3][4][5] Considering their electrochemical behavior we can find electron-donor subunits, such as porphyrins [6] and phthalocyanines, [7] combined with electron-acceptor moieties, such as [60]fullerene, [8] carbon nanotubes [9] or perylenediimides (PDI), [10] which give mixed donor-acceptor systems 11] These systems are suitable for generating long-lived charge-separated states with high quantum yields [12] due to their high light-harvesting ability, fast charge separation, and slow charge recombination.…”

Section: Introductionmentioning

confidence: 99%

Macrocyclic Dyads Based on C₆₀ and Perylenediimides Connected by Click Chemistry

et al. 2014

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Two sets of perylenediimide‐[60]fullerene dyads PDI‐C60 connected through 1,2,3‐triazole units have been synthesized and characterized. The cyclic dyad PDICl4‐C60 has four chlorine atoms in the 1,6,7,12‐PDI positions, whereas the cyclic dyad PDIPip2‐C60 has two piperidine units in the 1,7‐PDI positions. On the other hand, PDICl4‐C60 and PDIPip2‐C60 dyads were synthesized as linear counterparts with the same substitution pattern. Also, a C60‐PDICl4‐C60 triad has been prepared. A small interaction between C60 and PDI moieties in the ground state was detected by UV/vis and electrochemical measurements in both PDI‐C60 cyclic systems. The occurrence of photoinduced energy‐transfer processes between PDI and C60 units was confirmed by time‐resolved emission and transient absorption techniques. Femtosecond laser flash photolysis showed energy transfer from 1PDI* to C60 followed by intersystem crossing from 1C60* to 3C60* in the case of the PDICl4‐C60 systems. The energy transfer rate for PDICl4‐C60 in the cyclic dyad and the triad is one order of magnitude faster than that in PDICl4‐C60 in the linear dyad. The fast energy transfer rate together with the enhanced molar absorption coefficient by perylenediimide functionalization will be highly beneficial for applications as acceptors in polymer solar cells. On the other hand, no electron transfer from the donor PDIpip2 units to the acceptor C60 moiety was detected in the case of PDIPip2‐C60 dyads.

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Rational design of a phthalocyanine–perylenediimide dyad with a long-lived charge-separated state

Cited by 57 publications

References 42 publications

Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A₁-A₂ Organic Semiconductors

Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A₁-A₂ Organic Semiconductors

Zinc Phthalocyanine–Graphene Hybrid Material for Energy Conversion: Synthesis, Characterization, Photophysics, and Photoelectrochemical Cell Preparation

Macrocyclic Dyads Based on C₆₀ and Perylenediimides Connected by Click Chemistry

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Rational design of a phthalocyanine–perylenediimide dyad with a long-lived charge-separated state

Cited by 57 publications

References 42 publications

Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A1-A2 Organic Semiconductors

Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A1-A2 Organic Semiconductors

Zinc Phthalocyanine–Graphene Hybrid Material for Energy Conversion: Synthesis, Characterization, Photophysics, and Photoelectrochemical Cell Preparation

Macrocyclic Dyads Based on C60 and Perylenediimides Connected by Click Chemistry

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Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A₁-A₂ Organic Semiconductors

Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A₁-A₂ Organic Semiconductors

Macrocyclic Dyads Based on C₆₀ and Perylenediimides Connected by Click Chemistry