Tuning the electronic nature of mono-bay alkynyl-phenyl-substituted perylene bisimides

Synthesis, structure, and photophysical properties

Ruchika Mishra, Jong Min Lim, Minjung Son, Piyush Panini, Dongho Kim, Jeyaraman Sankar

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

Perylene bisimide (PBI) derivatives with various alkynyl-phenyl substituents at a single bay position have been synthesised by Sonogashira coupling. NMR spectroscopic studies reveal the unsymmetric nature of the dyads. All of the dyads undergo two reversible reductions, which demonstrates their structural and electrochemical rigidity. The synthesised dyads show a remarkable redshift in their absorption maxima and sharp vibronic progression. Electron-rich substituents facilitate efficient charge transfer from the substituent HOMO to the electron-deficient PBI core. The most interesting spectral signatures were exhibited by a PBI with a strongly electron-donating ethynyl(dimethylaminophenyl) substituent. The steady-state features of this PBI showed a broad absorption that covered almost the whole visible region with no emission. A twisted intramolecular charge-transfer (TICT) process, related to the rotational motion of ethynyl(dimethylaminophenyl) PBI, was also demonstrated. Computational investigations shed light on the coplanarity of the various substituents with respect to the PBI core; the PBI core itself remains flat without any noticeable deformation even after mono-functionalisation. This illustrates that mono-functionalisation exerts meagre steric hindrance on the bay positions relative to disubstituted analogues. Despite several previous reports on the structural characterisation of 1,7-disubstituted PBI derivatives, we present the first structural characterisation of a mono-bay ethynyl-phenyl substituted PBI. The solid-state structure of the phenyl derivative has a flat PBI core without any noticeable steric constraints from the substituents, as predicted. In contrast, single-crystal X-ray analysis for the mono-bromo bay-substituted PBI shows that the bromine substituent is not in the plane of the PBI core. Single minded: Perylene bisimide derivatives that contain various alkynyl-phenyl substituents at a single-bay position have been synthesized and characterized (see scheme). Detailed studies on the electrochemical and the photophysical properties were explored.

Original languageEnglish
Pages (from-to)5776-5786
Number of pages11
JournalChemistry - A European Journal
Volume20
Issue number19
DOIs
Publication statusPublished - 2014 May 5

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Tuning
Derivatives
Electrons
Charge transfer
Bromine
X ray analysis
Rigidity
Nuclear magnetic resonance
Single crystals
perylene bisimide

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Mishra, Ruchika ; Lim, Jong Min ; Son, Minjung ; Panini, Piyush ; Kim, Dongho ; Sankar, Jeyaraman. / Tuning the electronic nature of mono-bay alkynyl-phenyl-substituted perylene bisimides : Synthesis, structure, and photophysical properties. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 19. pp. 5776-5786.
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abstract = "Perylene bisimide (PBI) derivatives with various alkynyl-phenyl substituents at a single bay position have been synthesised by Sonogashira coupling. NMR spectroscopic studies reveal the unsymmetric nature of the dyads. All of the dyads undergo two reversible reductions, which demonstrates their structural and electrochemical rigidity. The synthesised dyads show a remarkable redshift in their absorption maxima and sharp vibronic progression. Electron-rich substituents facilitate efficient charge transfer from the substituent HOMO to the electron-deficient PBI core. The most interesting spectral signatures were exhibited by a PBI with a strongly electron-donating ethynyl(dimethylaminophenyl) substituent. The steady-state features of this PBI showed a broad absorption that covered almost the whole visible region with no emission. A twisted intramolecular charge-transfer (TICT) process, related to the rotational motion of ethynyl(dimethylaminophenyl) PBI, was also demonstrated. Computational investigations shed light on the coplanarity of the various substituents with respect to the PBI core; the PBI core itself remains flat without any noticeable deformation even after mono-functionalisation. This illustrates that mono-functionalisation exerts meagre steric hindrance on the bay positions relative to disubstituted analogues. Despite several previous reports on the structural characterisation of 1,7-disubstituted PBI derivatives, we present the first structural characterisation of a mono-bay ethynyl-phenyl substituted PBI. The solid-state structure of the phenyl derivative has a flat PBI core without any noticeable steric constraints from the substituents, as predicted. In contrast, single-crystal X-ray analysis for the mono-bromo bay-substituted PBI shows that the bromine substituent is not in the plane of the PBI core. Single minded: Perylene bisimide derivatives that contain various alkynyl-phenyl substituents at a single-bay position have been synthesized and characterized (see scheme). Detailed studies on the electrochemical and the photophysical properties were explored.",
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Tuning the electronic nature of mono-bay alkynyl-phenyl-substituted perylene bisimides : Synthesis, structure, and photophysical properties. / Mishra, Ruchika; Lim, Jong Min; Son, Minjung; Panini, Piyush; Kim, Dongho; Sankar, Jeyaraman.

In: Chemistry - A European Journal, Vol. 20, No. 19, 05.05.2014, p. 5776-5786.

Research output: Contribution to journalArticle

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T1 - Tuning the electronic nature of mono-bay alkynyl-phenyl-substituted perylene bisimides

T2 - Synthesis, structure, and photophysical properties

AU - Mishra, Ruchika

AU - Lim, Jong Min

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AU - Panini, Piyush

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AU - Sankar, Jeyaraman

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AB - Perylene bisimide (PBI) derivatives with various alkynyl-phenyl substituents at a single bay position have been synthesised by Sonogashira coupling. NMR spectroscopic studies reveal the unsymmetric nature of the dyads. All of the dyads undergo two reversible reductions, which demonstrates their structural and electrochemical rigidity. The synthesised dyads show a remarkable redshift in their absorption maxima and sharp vibronic progression. Electron-rich substituents facilitate efficient charge transfer from the substituent HOMO to the electron-deficient PBI core. The most interesting spectral signatures were exhibited by a PBI with a strongly electron-donating ethynyl(dimethylaminophenyl) substituent. The steady-state features of this PBI showed a broad absorption that covered almost the whole visible region with no emission. A twisted intramolecular charge-transfer (TICT) process, related to the rotational motion of ethynyl(dimethylaminophenyl) PBI, was also demonstrated. Computational investigations shed light on the coplanarity of the various substituents with respect to the PBI core; the PBI core itself remains flat without any noticeable deformation even after mono-functionalisation. This illustrates that mono-functionalisation exerts meagre steric hindrance on the bay positions relative to disubstituted analogues. Despite several previous reports on the structural characterisation of 1,7-disubstituted PBI derivatives, we present the first structural characterisation of a mono-bay ethynyl-phenyl substituted PBI. The solid-state structure of the phenyl derivative has a flat PBI core without any noticeable steric constraints from the substituents, as predicted. In contrast, single-crystal X-ray analysis for the mono-bromo bay-substituted PBI shows that the bromine substituent is not in the plane of the PBI core. Single minded: Perylene bisimide derivatives that contain various alkynyl-phenyl substituents at a single-bay position have been synthesized and characterized (see scheme). Detailed studies on the electrochemical and the photophysical properties were explored.

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