Tuning the aromatic backbone twist in dipyrrolonaphthyridinediones

Sadowski, Bartłomiej; Mierzwa, Dominik; Kang, Seongsoo; Grzybowski, Marek; Poronik, Yevgen M.; Sobolewski, Andrzej L.; Kim, Dongho; Gryko, Daniel T.

doi:10.1039/d1cc06863f

Cited by 6 publications

(5 citation statements)

References 34 publications

(18 reference statements)

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“…From the above, it can be seen that the bending of the aromatic core by tethering leads to red-shifted absorption and PL spectra, smaller band gaps, larger Stokes shifts, and lower PL quantum yields. This is consistent with the observation in some previous studies. , …”

Section: Resultssupporting

confidence: 94%

“…This is consistent with the observation in some previous studies. 36,48 Next, we studied the chiroptical properties of the tethered aromatic lactams. P and M enantiomers of 2L-Me-C 10 , 4L-Me-C 12 , 4L-Bu-C 12 , and 6L-Bu-C 14 were successfully separated by using chiral HPLC.…”

Section: ■ Introductionmentioning

confidence: 99%

“…36 Gryko et al synthesized a family of tethered dipyrrolonaphthyridinedione (DPND) derivatives via the direct condensation of 1,4-di(1Hpyrrol-1-yl)butane-1,4-dione with aliphatic dicarboxylic acids. 48 They found that the large distortion of the DPND chromophore caused by tethering promoted the intersystem crossing process, leading to a considerable redshift of emission spectra and largely reduced quantum yield. Despite the above progress for TNAs, the synthetic methods and the types of aromatics are still quite limited.…”

Section: ■ Introductionmentioning

confidence: 99%

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Tethered Helical Ladder-Type Aromatic Lactams

Xie,

Xiao,

Song

et al. 2024

J. Am. Chem. Soc.

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Tethered nonplanar aromatics (TNAs) make up an important class of nonplanar aromatic compounds showing unique features. However, the knowledge on the synthesis, structures, and properties of TNAs remains insufficient. In this work, a new type of TNAs, the tethered aromatic lactams, is synthesized via Pd-catalyzed consecutive intramolecular direct arylations. These molecules possess a helical ladder-type conjugated system of up to 13 fused rings. The overall yields ranged from 3.4 to 4.3%. The largest of the tethered aromatic lactams, 6L-Bu-C 14 , demonstrates a guest-adaptive hosting capability of TNAs for the first time. When binding fullerene guests, the cavity of 6L-Bu-C 14 became more circular to better accommodate spherical fullerene molecules. The host–guest interaction is thoroughly studied by X-ray crystallography, theoretical calculations, fluorescence titration, and nuclear magnetic resonance (NMR) titration experiments. 6L-Bu-C 14 shows stronger binding with C70 than with C60 due to the better convex–concave π–π interaction. P and M enantiomers of all tethered aromatic lactams show distinct and persistent chiroptical properties and demonstrate the potential of chiral TNAs as circularly polarized luminescence (CPL) emitters.

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Section: Resultssupporting

confidence: 94%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Tethered Helical Ladder-Type Aromatic Lactams

Xie,

Xiao,

Song

et al. 2024

J. Am. Chem. Soc.

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“…DFT calculations for some arylated DPNDs revealed that the expected deviation from the core plane mainly caused by the presence of arene rings at position 3 and 9 should be no greater that 8°. 30 a In order to test how high distortion influences of the photophysical aspects, we assembled three analogues of cyclophanes based on the DPND core (1o–r) 20 that differ in a length of an alkane bridge. X-ray analysis of 1p revealed that the distortion from the planarity reaches 28° ( Fig.…”

Section: The Optoelectronic Properties Of Dipyrrolonaphthyridinedione...mentioning

confidence: 99%

“…Another tested strategy towards 1a involved dipyrroyl derivative 4 as a source of pyrrole rings. Compound 4 can be easily synthesized from either 2,5-dimethoxytetrahydrofurane and succinamide 18,20 or pyrrole and 3. 21 Indeed, subjecting 4 to the typical Vilsmeier-Haack reaction conditions (DMF/POCl 3 ) resulted in the formation of 1a, but still with low efficiency (Scheme 2).…”

Section: Synthesis Of Dipyrrolonaphthiridinedionesmentioning

confidence: 99%

Dipyrrolonaphthyridinedione – (still) a mysterious cross-conjugated chromophore

Sadowski,

Gryko

2023

Chem. Sci.

Self Cite

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Strain‐Driven Formal [1,3]‐Aryl Shift within Molecular Bows

Jiang,

Peng,

Liang

et al. 2023

Angewandte Chemie

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Delving into the influence of strain on organic reactions in small molecules at the molecular level can unveil valuable insight into developing innovative synthetic strategies and structuring molecules with superior properties. Herein, we present a molecular‐strain engineering approach to facilitate the consecutive [1,2]‐aryl shift (formal [1,3]‐aryl shift) in molecular bows (MBs) that integrate 1,4‐dimethoxy‐2,5‐cyclohexadiene moieties. By introducing ring strain into MB through tethering the bow‐limb, we can harness the intrinsic mechanical forces to drive multistep aryl shifts from para‐ to meta‐ to ortho‐position.Through exercise of precise intramolecular strain, the seemingly impractical [1,3]‐aryl shift was realized, resulting in the formation of ortho‐disubstituted products. The solvent and temperature play a crucial role in the occurrence of the [1,3]‐aryl shift.The free energy calculations with inclusion of solvation support a feasible mechanism, which entails multistep carbocation rearrangements, for the formal [1,3]‐aryl shift. By exploring the application of molecular strain in synthetic chemistry, this research offers a promising direction for developing new tools and strategies towards precision organic synthesis.

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Tuning the aromatic backbone twist in dipyrrolonaphthyridinediones

Abstract: This communication describes the photophysical behavior of three analogs of cyclophane bearing the dipyrrolonaphthyridinedione (DPND) core. In these molecules, intersystem crossing (ISC) can be successfully induced by distinct changes in...

Cited by 6 publications

References 34 publications

Tethered Helical Ladder-Type Aromatic Lactams

Tethered Helical Ladder-Type Aromatic Lactams

Dipyrrolonaphthyridinedione – (still) a mysterious cross-conjugated chromophore

Strain‐Driven Formal [1,3]‐Aryl Shift within Molecular Bows

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