Selective Bromination of Perylene Diimides under Mild Conditions

Rajasingh, Paramasivan; Cohen, Revital; Shirman, Elijah; Shimon, Linda J. W.; Rybtchinski, Boris

doi:10.1021/jo070367n

Cited by 206 publications

(146 citation statements)

References 46 publications

Supporting

Mentioning

143

Contrasting

Unclassified

Order By: Relevance

“…The solubility of the ligands and their respective metal complexes are comparable: 1 and 3 are very soluble in toluene, CH 2 Cl 2 , and benzonitrile, but they are less soluble in butyronitrile and only 3 is soluble in acetonitrile, and in these two latter solvents the UV-Vis spectra show evidence of PDI aggregation (28,29). Dyad 2 and ligand 4 are soluble in the entire range of solvents, as a result of the 3-pentyl tail at the imide that hinders π-π stacking of PDI aromatic cores (30) and the direct attachment of the phenyl side-groups, which may cause even greater distortion of the PDI core from planarity relative to the phenoxy-substituted dyes (31,32).…”

Section: Resultsmentioning

confidence: 97%

Ultrafast photodriven intramolecular electron transfer from an iridium-based water-oxidation catalyst to perylene diimide derivatives

Vagnini

Smeigh

Blakemore

et al. 2012

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

123

106

View full text Add to dashboard Cite

Photodriving the activity of water-oxidation catalysts is a critical step toward generating fuel from sunlight. The design of a system with optimal energetics and kinetics requires a mechanistic understanding of the single-electron transfer events in catalyst activation. To this end, we report here the synthesis and photophysical characterization of two covalently bound chromophore-catalyst electron transfer dyads, in which the dyes are derivatives of the strong photooxidant perylene-3,4:9,10-bis(dicarboximide) (PDI) and the molecular catalyst is the Cp Ã IrðppyÞCl metal complex, where ppy ¼ 2-phenylpyridine. Photoexcitation of the PDI in each dyad results in reduction of the chromophore to PDI •− in less than 10 ps, a process that outcompetes any generation of 3Ã PDI by spin-orbit-induced intersystem crossing. Biexponential charge recombination largely to the PDI-Ir(III) ground state is suggestive of multiple populations of the PDI •− -IrðIVÞ ion-pair, whose relative abundance varies with solvent polarity. Electrochemical studies of the dyads show strong irreversible oxidation current similar to that seen for model catalysts, indicating that the catalytic integrity of the metal complex is maintained upon attachment to the high molecular weight photosensitizer.photoinduced electron transfer | solar fuels | ultrafast optical spectroscopy | water oxidation A rtificial photosynthetic systems for solar fuels generation must integrate the functions of light harvesting, charge separation, and catalysis, with water as the source of electrons for reductive fuel-forming chemistry (1-5). The design of a lightdriven water-splitting system based on molecular catalysts requires a fundamental understanding of the individual electron transfer steps involved in multielectron catalyst activation. To investigate the energetic and kinetic demands of coupling photodriven charge separation and catalysis, many research groups have studied the photophysical properties of covalently linked redox-active organic dyes and transition metal complexes (6-16). In several cases, electron transfer to or from the metal has been observed and characterized, though energy transfer and intersystem crossing to the chromophore triplet state can be significant competing processes. In this work, we use derivatives of perylene-3,4∶9,10-bis(dicarboximide) (PDI) linked to an iridium complex of the type Cp Ã IrðN-CÞX to demonstrate light-driven single-electron oxidation of a highly active molecular catalyst precursor for water oxidation.Derivatives of PDI are useful organic chromophores for solar device applications (5,17,18). Their high molar absorptivity, stability, low cost, ease of synthetic manipulation, and often advantageous self-assembly properties have led to their use in molecular electronics and a variety of solar energy conversion systems (19). For solar fuels applications, the mild reduction potentials of PDI derivatives make their excited states powerful photooxidants, though there are only a few literature examples in which 1Ã PDI is used to ...

show abstract

Section: Resultsmentioning

confidence: 97%

Ultrafast photodriven intramolecular electron transfer from an iridium-based water-oxidation catalyst to perylene diimide derivatives

Vagnini

Smeigh

Blakemore

et al. 2012

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

123

106

View full text Add to dashboard Cite

show abstract

“…N-N-(n-butylamino)-1,7-Dibromoperylenetetracarboxylic acid diimide was synthesized according to the literature [16]. Other reagents were commercially available and used without further purification.…”

Section: Chemicals and Instrumentsmentioning

confidence: 99%

A photochromic diarylethene dyad based on perylene diimide

Tan

Zhang

et al. 2011

Dyes and Pigments

View full text Add to dashboard Cite

“…The electronic characteristics of PBIs can also be fine-tuned by the substitution of the conjugated aromatic core. Based on these principles, many perylene bisimide derivatives with either electron-withdrawing or electron-donating groups have been reported in the literature, including: (1) cyano-substituted PBIs [56,57]; (2) nitro-substituted PBIs [58,59,60]; (3) perfluoroalkyl-substituted PBIs [61,62]; (4) aryl-substituted PBIs [63,64]; (5) ferrocenyl-substituted PBIs [65,66]; (6) boryl-substituted PBIs [67]; (7) alkyl-substituted PBIs [68]; (8) hydroxy-substituted PBIs [69,70]; (9) alkoxy-substituted PBIs [71,72,73,74,75]; (10) amino-substituted PBIs [76,77]; (11) alkylamino-substituted PBIs [78,79,80]; (12) pyrrolidinyl-substituted PBIs [81,82,83]; (13) piperidinyl-substituted PBIs [84,85,86]; etc .…”

Section: Introductionmentioning

confidence: 99%

Green Perylene Bisimide Dyes: Synthesis, Photophysical and Electrochemical Properties

Chang¹,

Tsai²,

Chen³

2014

Materials

View full text Add to dashboard Cite

Three asymmetric amino-substituted perylene bisimide dyes with different n-alkyl chain lengths (n = 6, 12, or 18), 1-(N,N-dialkylamino)perylene bisimides (1a-1c), were synthesized under mild condition in high yields and were characterized by 1 H NMR, 13C NMR (nuclear magnetic resonance), HRMS (High Resolution Mass Spectrometer), UV-Vis and fluorescence spectra, as well as cyclic voltammetry (CV). These molecules show intense green color in both solution and solid state and are highly soluble in dichloromethane and even in nonpolar solvents, such as hexane. The shapes of the absorption spectra of 1a-1c in solid state and in solution were found to be virtually the same, indicating that the long alkyl chains could efficiently prevent aggregation. They exhibit a unique charge transfer emission in the near-infrared region, of which the peak wavelengths show strong solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1-aminoperylene bisimide (2). Furthermore, all of the compounds exhibit two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory (DFT) calculations performed on these dyes are reported in order to rationalize their molecular structures and electronic properties.

show abstract

Selective Bromination of Perylene Diimides under Mild Conditions

Cited by 206 publications

References 46 publications

Ultrafast photodriven intramolecular electron transfer from an iridium-based water-oxidation catalyst to perylene diimide derivatives

Ultrafast photodriven intramolecular electron transfer from an iridium-based water-oxidation catalyst to perylene diimide derivatives

A photochromic diarylethene dyad based on perylene diimide

Green Perylene Bisimide Dyes: Synthesis, Photophysical and Electrochemical Properties

Contact Info

Product

Resources

About