Metal‐Bridging Cyclic Bilatriene Analogue Affords Stable π‐Radicaloid Dyes with Near‐Infrared II Absorption DOI Creative Commons
Anupam Ghosh, Shigeki Mori, Yuki Ide

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

Abstract Stable neutral metal radicaloid complexes have been synthesized from a modified tetrapyrrolic pigment, bilatriene, with iridium(I) and rhodium(I) cyclooctadiene (COD) synthons. The bilatriene skeleton contains α‐linked conjugated pyrrole units, whereas an N‐confused analogue used in this work possesses β‐linked moieties at the terminal, demonstrating unique binding capability. Unprecedentedly, metal‐COD cations are accommodated outer nitrogen sites, which induced formation of open‐shell metal‐radicaloid species. resulting compounds highly stable under ambient conditions demonstrated facile redox conversion to afford corresponding cation anion Furthermore, showed distinct second near‐infrared absorption (NIR‐II) capability extending up 1500 nm along high photostability. These features emphasized that can be potential NIR‐II light‐responsible photothermal photoacoustic imaging contrast agents based on dye platform.

Language: Английский

Ruthenocenoporphyrinoids─π-Conjugation Transmitted across 1,3-Substituted Ruthenocene DOI Creative Commons
Anna Berlicka, Aleksandra M. Walczak, Michał J. Białek

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

Synthesis of ruthenocenoporphyrinoids, wherein the [RuCp*]+ moiety coordinates to cyclopentadienyl π-surface 21-carba-23-selenaporphyrin macrocyclic platform, has been developed. The specific electronic ruthenocene-macrocycle communication is observed. ring current maintained despite strong π-conjugation in ruthenocene fragment. theoretical data are consistent with magnetic properties reflected by 1H NMR spectra. DFT-optimized molecular models were used evaluate NICS 2D maps and EDDB plots. These gave an insight into aromaticity effectiveness across 1,3-substituted obtained hybrid molecules.

Language: Английский

Citations

0
Bowl‐Shaped Anthracene‐Fused Antiaromatic Ni(II) Norcorrole: Synthesis, Structure, Assembly with C60, and Photothermal Conversion DOI Creative Commons
Kaisheng Wang, Anupam Ghosh, Daiki Shimizu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 31, 2024

The synthesis of bowl-shaped antiaromatic molecules is challenging because the molecular distortion further destabilizes these already inherently reactive molecules. Here, we report and properties fused anthrylnorcorroles that exhibit near-infrared (NIR) absorption reaching 1900 nm. oxidation meso-anthryldibromodipyrrin provides anthryldibromodipyrrin, which was converted to mono- bisanthrylnorcorroles through Ni(0)-mediated intramolecular coupling with a bis(dibromodipyrrin) Ni(II) complex. Single-crystal X-ray diffraction analyses revealed structures for bisanthrylnorcorroles, enables them act as suitable receptors C

Language: Английский

Citations

1
Metal‐Bridging Cyclic Bilatriene Analogue Affords Stable π‐Radicaloid Dyes with Near‐Infrared II Absorption DOI Creative Commons
Anupam Ghosh, Shigeki Mori, Yuki Ide

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

Stable neutral metal radicaloid complexes have been synthesized from a modified tetrapyrrolic pigment, bilatriene, with iridium(I) and rhodium(I) cyclooctadiene (COD) synthons. The bilatriene skeleton contains α-linked conjugated pyrrole units, whereas an N-confused analogue used in this work possesses β-linked moieties at the terminal, demonstrating unique binding capability. Unprecedentedly, metal-COD cations are accommodated outer nitrogen sites, which induced formation of open-shell metal-radicaloid species. resulting compounds highly stable under ambient conditions demonstrated facile redox conversion to afford corresponding cation anion Furthermore, showed distinct second near-infrared absorption (NIR-II) capability extending up 1500 nm along high photostability. These features emphasized that can be potential NIR-II light-responsible photothermal photoacoustic imaging contrast agents based on dye platform.

Language: Английский

Citations

1
A bis-aromatic MOF system constructed with a copper iodine cluster and porphyrinic ligand for enhancing near-infrared photothermal conversion DOI

Man Cao,

Qian‐You Wang,

R. LI

et al.

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(20), P. 7018 - 7025

Published: Jan. 1, 2024

An organic–inorganic bis-aromatic system achieves an NIR-II photothermal efficiency of up to 63.77%.

Language: Английский

Citations

0
Bowl‐Shaped Anthracene‐Fused Antiaromatic Ni(II) Norcorrole: Synthesis, Structure, Assembly with C60, and Photothermal Conversion DOI Creative Commons
Kaisheng Wang, Aryya Ghosh, Daiki Shimizu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 31, 2024

Abstract The synthesis of bowl‐shaped antiaromatic molecules is challenging because the molecular distortion further destabilizes these already inherently reactive molecules. Here, we report and properties fused anthrylnorcorroles that exhibit near‐infrared (NIR) absorption reaching 1900 nm. oxidation meso ‐anthryldibromodipyrrin provides anthryldibromodipyrrin, which was converted to mono‐ bisanthrylnorcorroles through Ni(0)‐mediated intramolecular coupling with a bis(dibromodipyrrin) Ni(II) complex. Single‐crystal X‐ray diffraction analyses revealed structures for bisanthrylnorcorroles, enables them act as suitable receptors C 60 bonding constants 2.89×10 3 M −1 1.59×10 , respectively. formation 1 : complex between monoanthrylnorcorrole confirmed by single‐crystal analysis. effective expansion π‐conjugation triple fusion norcorrole anthracene units substantially enhances bands, endows photothermal conversion.

Language: Английский

Citations

0
Metal‐Bridging Cyclic Bilatriene Analogue Affords Stable π‐Radicaloid Dyes with Near‐Infrared II Absorption DOI Creative Commons
Anupam Ghosh, Shigeki Mori, Yuki Ide

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

Abstract Stable neutral metal radicaloid complexes have been synthesized from a modified tetrapyrrolic pigment, bilatriene, with iridium(I) and rhodium(I) cyclooctadiene (COD) synthons. The bilatriene skeleton contains α‐linked conjugated pyrrole units, whereas an N‐confused analogue used in this work possesses β‐linked moieties at the terminal, demonstrating unique binding capability. Unprecedentedly, metal‐COD cations are accommodated outer nitrogen sites, which induced formation of open‐shell metal‐radicaloid species. resulting compounds highly stable under ambient conditions demonstrated facile redox conversion to afford corresponding cation anion Furthermore, showed distinct second near‐infrared absorption (NIR‐II) capability extending up 1500 nm along high photostability. These features emphasized that can be potential NIR‐II light‐responsible photothermal photoacoustic imaging contrast agents based on dye platform.

Language: Английский

Citations

0