Azadipyrromethene-based near-IR dyes with styryl substituents at the pyrrolic positions for organic photovoltaic applications

Fernando, Roshan; Pejić, Sandra; Thomsen, Anna M; Wang, Chunlai; Sauvé, Geneviève

doi:10.1016/j.dyepig.2019.04.067

Cited by 8 publications

(4 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We therefore wondered if its replacement by a metal could allow us to modify advantageously the photophysical properties of the fluorophore. AzaMetalDIPYs, or more simply azaMDIPYs, have already been synthesized over the last decade. − Homoleptic complexes are relatively stable, but most of azaMDIPYs involving a single aza-DIPY ligand display limited stability. Moreover, their very low luminescence did not allow their use for fluorescence imaging.…”

Section: Introductionmentioning

confidence: 99%

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N₂O₂” Complexes as Efficient NIR-Fluorophores

et al. 2022

View full text Add to dashboard Cite

Aza-boron-dipyrromethenes (Aza-BODIPYs) are an increasingly studied class of fluorophores. They can be seen as an azadipyrromethene (“aza-DIPY”) ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. The impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined, and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) makes them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this redshift seems to be more due to the geometry around the boron/metal than to the nature of the metal.

show abstract

Section: Introductionmentioning

confidence: 99%

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N₂O₂” Complexes as Efficient NIR-Fluorophores

et al. 2022

View full text Add to dashboard Cite

show abstract

“…AzaMetalDIPYs, or more simply azaMDIPYs, have already been synthesized over the last decade. [31][32][33][34][35][36][37] Homoleptic complexes are relatively stable, but most of azaMDIPY involving a single aza-DIPY ligand display limited stability. Moreover, their very low luminescence did not allow their use for fluorescence imaging.…”

Section: Introductionmentioning

confidence: 99%

"N2O2" Metal-azaDIPY complexes: a new class of NIR-fluorophores

Godard

Galán

Rouillon

et al. 2022

Preprint

View full text Add to dashboard Cite

Aza-BODIPYs are an increasingly studied class of fluorophores. They can be seen as an "aza-DIPY" ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. Impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) make them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this red shift seems to be more due to the geometry around the boron/metal than to the nature of the metal.

show abstract

“…We have established that the presence of arylethynyl groups at the pyrrolic positions is essential to increase the conjugation of the complex and obtain favorable phase separation from P3HT . Replacing the triple bond with a double bond, on the other hand, increases the energy levels and lowers the performance . Fluorination at the para position of the phenylethynyl improves the performance and electron mobility .…”

Section: Introductionmentioning

confidence: 99%

“…11 Replacing the triple bond with a double bond, on the other hand, increases the energy levels and lowers the performance. 14 Fluorination at the para position of the phenylethynyl improves the performance and electron mobility. 15 These complexes tend to be amorphous, making it hard to obtain a crystal structure.…”

Section: ■ Introductionmentioning

confidence: 99%

Structure–Property Study of Homoleptic Zinc(II) Complexes of Di(arylethynyl) Azadipyrromethene as Nonfullerene Acceptors for Organic Photovoltaics: Effect of the Aryl Group

et al. 2020

Self Cite

View full text Add to dashboard Cite

Azadipyrromethene-based zinc(II) complexes were demonstrated to be promising molecular organic semiconductors for electronic applications due to their easy preparation, tunable structures, and high electron affinity. The first successful such complex incorporated phenylethynyl groups at the pyrrolic positions, which red-shifted the absorption spectra of zinc(II) bis(tetraphenyl azadipyrromethene) and improved the morphology in blends with poly(3-hexylthiophene) (P3HT). We recently discovered that replacing the phenyl group in the pyrrolic positions with the larger 1-naphthyl group [Zn(L2) 2 ] increases the crystallinity and improves the organic photovoltaic (OPV) performance. In this work, two more aryl groups were explored to further investigate the relationship between the aryl groups in the pyrrolic position and electronic properties: naphthyl with a different anchoring site, 2-naphthyl [Zn(L3) 2 ], and a larger aryl group, 9phenanthrenyl [Zn(L4) 2 ]. The larger aryl group slightly improved the absorptivity, red-shifted the absorption spectra, and led to different packing modes in crystals with most intermolecular π−π stacking interactions being of T-shaped-type involving the pyrrolic aryl group of one complex. Of the series, 1-naphthyl gave the highest crystallinity. The organic photovoltaic (OPV) power conversion efficiency (PCE) of Zn(L3) 2 and Zn(L4) 2 when blended with P3HT was 3.7 and 3.4%, respectively, both lower than that of Zn(L2) 2 (PCE of 5.5%) due to the higher trap-assisted recombination and less favorable morphology. The charge carrier mobility in these complexes was also relatively low, also limiting the performance. Single-point energy calculations point to low overlap integrals as a cause for the low mobility. The aryl group anchoring position and size, therefore, have a large effect on the properties in these systems, but do not appear to significantly enhance intermolecular interactions.

show abstract

Azadipyrromethene-based near-IR dyes with styryl substituents at the pyrrolic positions for organic photovoltaic applications

Cited by 8 publications

References 20 publications

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N₂O₂” Complexes as Efficient NIR-Fluorophores

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N₂O₂” Complexes as Efficient NIR-Fluorophores

"N2O2" Metal-azaDIPY complexes: a new class of NIR-fluorophores

Structure–Property Study of Homoleptic Zinc(II) Complexes of Di(arylethynyl) Azadipyrromethene as Nonfullerene Acceptors for Organic Photovoltaics: Effect of the Aryl Group

Contact Info

Product

Resources

About

Azadipyrromethene-based near-IR dyes with styryl substituents at the pyrrolic positions for organic photovoltaic applications

Cited by 8 publications

References 20 publications

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N2O2” Complexes as Efficient NIR-Fluorophores

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N2O2” Complexes as Efficient NIR-Fluorophores

"N2O2" Metal-azaDIPY complexes: a new class of NIR-fluorophores

Structure–Property Study of Homoleptic Zinc(II) Complexes of Di(arylethynyl) Azadipyrromethene as Nonfullerene Acceptors for Organic Photovoltaics: Effect of the Aryl Group

Contact Info

Product

Resources

About

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N₂O₂” Complexes as Efficient NIR-Fluorophores

Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N₂O₂” Complexes as Efficient NIR-Fluorophores