Synthesis of Perylene-3,4,9,10-tetracarboxylic Acid Derivatives Bearing Four Different Substituents at the Perylene Core

Dubey, Rajeev K.; Westerveld, Nick; Eustace, Stephen; Sudhölter, Ernst J. R.; Grozema, Ferdinand C.; Jager, Wolter F.

doi:10.1021/acs.orglett.6b02887

Cited by 11 publications

(14 citation statements)

References 25 publications

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“…This induces a distinct reactivity difference between the highly reactive "imide-activated" 7/12 and the less reactive "esteractivated" 1/6 bay positions. 48 In this work, we have utilized this pronounced difference in reactivity of the bay halogens of 1,6,7,12-tetrachloro-perylene monoimide diester 1 to achieve sequential functionalizations at both imide and bay positions. This eventually led to the PBI dyes with up to five independently introduced substituents, which were not accessible with the conventional protocols.…”

Section: ■ Introductionmentioning

confidence: 69%

“…For this reaction, we observed exchange of phenols at higher temperatures and longer reaction times. 48,52 Therefore, careful optimization of the reaction temperature and time was required to obtain good yields. It is important to note that compounds 9 and 12 are the two regioisomers in which the location of 4-methoxyphenoxy- and 4- tert -butylphenoxy groups has been reversed with respect to the imide groups.…”

Section: Resultsmentioning

confidence: 99%

“…This induces a distinct reactivity difference between the highly reactive “imide-activated” 7/12 and the less reactive “ester-activated” 1/6 bay positions. 48…”

Section: Introductionmentioning

confidence: 99%

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Perylene Bisimide Dyes with up to Five Independently Introduced Substituents: Controlling the Functionalization Pattern and Photophysical Properties Using Regiospecific Bay Substitution

et al. 2019

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We report herein a versatile and user-friendly synthetic methodology based on sequential functionalization that enables the synthesis of previously unknown perylene bisimide (PBI) dyes with up to five different substituents attached to the perylene core (e.g., compound 15 ). The key to the success of our strategy is a highly efficient regiospecific 7-mono- and 7,12-di-phenoxy bay substitution at the “imide-activated” 7- and 12-bay positions of 1,6,7,12-tetrachloroperylene monoimide diester 1 . The facile subsequent conversion of the diester groups into an imide group resulted in novel PBIs (e.g., compound 14 ) with two phenoxy substituents specifically at the 7- and 12-bay positions. This conversion led to the activation of C-1 and C-6 bay positions, and thereafter, the remaining two chlorine atoms were substituted to obtain tetraphenoxy-PBI (compound 15 ) that has two different imide and three different bay substituents. The methodology provides excellent control over the functionalization pattern, which enables the synthesis of various regioisomeric pairs bearing the same bay substituents. Another important feature of this strategy is the high sensitivity of HOMO–LUMO energies and photoinduced charge transfer toward sequential functionalization. As a result, systematic fluorescence on–off switching has been demonstrated upon subsequent substitution with the electron-donating 4-methoxyphenoxy substituent.

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Section: ■ Introductionmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

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Perylene Bisimide Dyes with up to Five Independently Introduced Substituents: Controlling the Functionalization Pattern and Photophysical Properties Using Regiospecific Bay Substitution

et al. 2019

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“…This can be achieved by starting the antenna synthesis from tetrachloro- 41,51 instead of dibromoperylenes and by implementing the recently developed chemistry for regioselective substitution of bay halogens. 52…”

Section: Discussionmentioning

confidence: 99%

Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity

et al. 2018

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The excited-state dynamics of perylene-based bichromophoric light harvesting antenna systems has been tailored by systematic modification of the molecular structure and by using solvents of increasing polarity in the series toluene, chloroform, and benzonitrile. The antenna systems consist of blue light absorbing naphthalene monoimide (NMI) energy donors (D1, D2, and D3) and the perylene derived green light absorbing energy acceptor moieties, 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 design of these antenna systems is such that all exhibit ultrafast excitation energy transfer (EET) from the excited donor to the acceptor, due to the effective matching of optical properties of the constituent chromophores. At the same time, electron transfer from the donor to the excited acceptor unit has been limited by the use of a rigid and nonconjugated phenoxy bridge to link the donor and acceptor components. The antenna molecules D1A1, D1A2, and D1A3, which bear the least electron-rich energy donor, isopentylthio-substituted NMI D1, exhibited ultrafast EET (τEET ∼ 1 ps) but no charge transfer and, resultantly, emitted a strong yellow-orange acceptor fluorescence upon excitation of the donor. The other antenna molecules D2A2, D2A3, and D3A3, which bear electron-rich energy donors, the amino-substituted NMIs D2 and D3, exhibited ultrafast energy transfer that was followed by a slower (ca. 20–2000 ps) electron transfer from the donor to the excited acceptor. This charge transfer quenched the acceptor fluorescence to an extent determined by molecular structure and solvent polarity. These antenna systems mimic the primary events occurring in the natural photosynthesis, i.e., energy capture, efficient energy funneling toward the central chromophore, and finally charge separation, and are suitable building blocks for achieving artificial photosynthesis, because of their robustness and favorable and tunable photophysical properties.

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“…It would be better if the ETL is thickness-insensitive and can be efficient in different interlayer thickness. Perylene diimide (PDI) is a famous n-type material, which has many strong points, such as good electron affinities, high conductivities and facile modification by simple substitution reaction [35,36,37,38]. Moreover, the high conductivity of the PDI originated from self-organized p-stacks in solid film can endow the PDT-based ETL with thickness-insensitive superiority, which can conquer the thickness restriction (<10 nm) of the reported organic ETL.…”

Section: Introductionmentioning

confidence: 99%

Water/Alcohol Soluble Thickness-Insensitive Hyperbranched Perylene Diimide Electron Transport Layer Improving the Efficiency of Organic Solar Cells

et al. 2019

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The electron transport layer (ETL) is very crucial for enhancing the device performance of polymer solar cells (PSCs). Meanwhile, thickness-insensitive and environment-friendly water/alcohol soluble processing are two essential requirements for large-scale roll-to-roll commercial application. Based on this, we designed and synthesized two new n-type ETLs with tetraethylene pentamine or butyl sulfonate sodium substituted tetraethylene pentamine as the branched side chains and high electron affinities perylene diimide (PDI) as the central core, named as PDIPN and PDIPNSO3Na. Encouragingly, both PDIPN and PDIPNSO3Na can effectively reduce the interfacial barrier and improve the interfacial contact. In addition, both of them can exhibit strong n-type self-doping effects, especially the PDIPN with higher density of negative charge. Consequently, compared to bare ITO, the PCE of the devices with ITO/PDIPN and ITO/PDIPNSO3Na ETLs has increased to 3–4 times. Our research results indicate that n-type self-doping PDI-based ETL PDIPN and PDIPNSO3Na could be promising candidates for ETL in environment-friendly water/alcohol soluble processing large-scale PSCs.

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Synthesis of Perylene-3,4,9,10-tetracarboxylic Acid Derivatives Bearing Four Different Substituents at the Perylene Core

Cited by 11 publications

References 25 publications

Perylene Bisimide Dyes with up to Five Independently Introduced Substituents: Controlling the Functionalization Pattern and Photophysical Properties Using Regiospecific Bay Substitution

Perylene Bisimide Dyes with up to Five Independently Introduced Substituents: Controlling the Functionalization Pattern and Photophysical Properties Using Regiospecific Bay Substitution

Tailoring Photophysical Processes of Perylene-Based Light Harvesting Antenna Systems with Molecular Structure and Solvent Polarity

Water/Alcohol Soluble Thickness-Insensitive Hyperbranched Perylene Diimide Electron Transport Layer Improving the Efficiency of Organic Solar Cells

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