The Photophysics of Pyridine‐Derivatized ortho‐, meta‐, and para‐Dibutylamino Cruciforms

Hinderer, Florian; Bunz, Uwe H. F.

doi:10.1002/chem.201300211

Cited by 11 publications

(5 citation statements)

References 38 publications

(25 reference statements)

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“…Red shift of emission spectra in molecules of this type is associated with lowering the energy of the LUMO and possibly the introduction of low-lying (perhaps twisted) CT states from which emission occurs. 53 Spectroelectrochemistry. Compounds 1 and 3 were investigated by IR and UV−vis−NIR spectroelectrochemical methods in order to explore the influence of oxidation on the physical and electronic structure of the cross-conjugated backbone.…”

Section: ■ Results and Discussionsupporting

confidence: 59%

“…However, the emission profiles are red-shifted such that the emission maxima fall in the order λ em 4 < 3 < 5 (Table , Figure ). Red shift of emission spectra in molecules of this type is associated with lowering the energy of the LUMO and possibly the introduction of low-lying (perhaps twisted) CT states from which emission occurs …”

Section: Results and Discussionmentioning

confidence: 99%

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Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations

Gluyas¹,

Manici

Gückel

et al. 2015

J. Org. Chem.

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A series of cross-conjugated compounds based on an (E)-4,4'-(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skeleton (1-6) have been synthesized. The linear optical absorption properties can be tuned by modification of the substituents at the 1 and 5 positions of the hexa-3-en-1,5-diynyl backbone (1: Si(CH(CH3)2)3, 2: C6H4C≡CSi(CH3)3, 3: C6H4COOCH3, 4: C6H4CF3, 5: C6H4C≡N, 6: C6H4C≡CC5H4N), although attempts to introduce electron-donating (C6H4CH3, C6H4OCH3, C6H4Si(CH3)3) substituents at these positions were hampered by the ensuing decreased stability of the compounds. Spectroelectrochemical investigations of selected examples, supported by DFT-based computational studies, have shown that one- and two-electron oxidation of the 1,2-bis(triarylamine)ethene fragment also results in electronic changes to the perpendicular π-system in the hexa-3-en-1,5-diynyl branch of the molecule. These properties suggest that (E)-hexa-3-en-1,5-diynyl-based compounds could have applications in molecular sensing and molecular electronics.

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Section: ■ Results and Discussionsupporting

confidence: 59%

Section: Results and Discussionmentioning

confidence: 99%

Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations

Gluyas¹,

Manici

Gückel

et al. 2015

J. Org. Chem.

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“…The known 2-aminobenzaldehydes were synthesised by the literature procedure based on the work of Rabong, 3 involving the SNAr reaction between the requisite fluorobenzaldehydes and amines to give the known precursor benzaldehydes to nitroalkenes 1, 3 3, 16 6, 4 9, 23 10, 24 12, 25 13, 25 14, 26 15, 27 and 16. 28 General procedure B for the Pd catalysed synthesis of aminobenzaldehydes.…”

Section: Synthesis Of Nitroalkenesmentioning

confidence: 99%

“…The requisite aldehyde 25 (14). The requisite aldehyde 26 (700 mg, 3.00 mmol), prepared by General procedure A, was subjected to General procedure C and gave after purification by column chromatography (0-2% EtOAc/hexane), (15). (17).…”

Section: (E)-4-(2-(2-nitrovinyl)phenyl)thiomorpholine (11)mentioning

confidence: 99%

Investigation of the [1,5]-hydride shift as a route to nitro-Mannich cyclisations

et al. 2019

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Conditions were found for the [1,5]-hydride shift nitro-Mannich reaction that led to the synthesis of 2,3-disubstituted tetrahydroquinolines. Two simple cyclic amine substrates gave diastereomerically pure rearranged products in 65 and 90% yields by refluxing in HFIP. A more general procedure used Gd(OTf)3 as a catalyst and successfully rearranged other cyclic and acyclic amines in 42-84% yield with diastereomeric ratios of 75:25 to >95:5 in favour of the antidiastereoisomer (9 examples). Two examples of sulfur containing heterocycles gave lower yields of 9 and 25%. Electron withdrawing substituents were shown to have a deleterious effect on the success of the reaction. The results indicated the limitation of the [1,5]-hydride shift nitro-Mannich reaction with respect to the stability of the intermediate iminium ion.

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“…In the case of the non-fluorescent PBI 9, we have investigated the ICT characteristics of the system, as well as its perturbation by the rotational motion of the dimethylamino group. Because the CT transition from the dimethylamino group to the PBI unit might be blocked under acidic conditions, [27] we have performed a spectrophotometric titration of PBI 9 in toluene with trifluoroacetic acid (TFA). Upon protonation, the broad absorption band (l = 550-750 nm) of PBI 9 became diminished and a new absorption structure similar to that of typical PBI dyes with an intense transition at l = 547 nm appeared (Figure 3 a; Figure S3 in the Supporting Information).…”

Section: Solvent Dependence Of the Pbi Systemsmentioning

confidence: 99%

Tuning the Electronic Nature of Mono‐Bay Alkynyl–Phenyl‐Substituted Perylene Bisimides: Synthesis, Structure, and Photophysical Properties

Mishra¹,

Lim²,

Son³

et al. 2014

Chemistry A European J

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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.

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The Photophysics of Pyridine‐Derivatized ortho‐, meta‐, and para‐Dibutylamino Cruciforms

Cited by 11 publications

References 38 publications

Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations

Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations

Investigation of the [1,5]-hydride shift as a route to nitro-Mannich cyclisations

Tuning the Electronic Nature of Mono‐Bay Alkynyl–Phenyl‐Substituted Perylene Bisimides: Synthesis, Structure, and Photophysical Properties

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