A Diradical Approach towards BODIPY‐Based Dyes with Intense Near‐Infrared Absorption around <i>λ</i>=1100 nm

Ni, Yong; Lee, Sangsu; Son, Minjung; Aratani, Naoki; Ishida, Masatoshi; Samanta, Animesh; Yamada, Hiroko; Chang, Young‐Tae; Furuta, Hiroyuki; Kim, Dongho; Wu, Jishan

doi:10.1002/anie.201511151

Cited by 103 publications

(59 citation statements)

References 52 publications

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“…The para-and meta-QDM bridged BODIPY dimers 74 and 75 with small diradical character (y 0 = 0.069 and 0.26, respectively) were reported by us to be very stable compounds. 35 These BODIPY-based diradicaloids exhibit very intense absorption at 1088 nm ( = 6.65 × 10 5 (mol/L) −1 cm −1 ) and 1136 nm ( = 6.44 × 10 5 (mol/L) −1 cm −1 ), respectively. Therefore, diradical approach provides an alternative strategy to design organic dyes with intense absorption in the NIR region.…”

Section: Zethrene Analogues As Stable Near-infrared Dyesmentioning

confidence: 99%

Modern zethrene chemistry

Pan

2017

Can. J. Chem.

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This paper gives a brief summary of zethrene chemistry after the pioneering works by Clar, Mitchell, Sondheimer, and Staab et al. In the past a few years, various synthetic methods and stabilizing strategies have been developed, which have made the synthesis of stable, vertically and laterally extended zethrenes practically achievable. One of the most important discoveries for this type of molecule is their open-shell diradical character, which is the origin of their unique optical, electronic, and magnetic properties. The fundamental structure-diradical character-physical property relationships were investigated, and these studies form the basis for the tailored design of more general open-shell singlet diradicaloids with controllable diradical character and physical properties.Key words: zethrene, polycyclic aromatic hydrocarbons, diradicaloid, polyradical.Résumé : Cet article présente un résumé de la chimie du zéthrène fondé sur les premiers travaux exploratoires de Clar, Mitchell, Sondheimer et Staab, ainsi que leurs collaborateurs. Au cours des dernières années, diverses méthodes de synthèse et stratégies de stabilisations ont été mises au point, rendant possible du point de vue pratique la synthèse de zéthrènes stables étendus sur les plans vertical et latéral. L'une des découvertes les plus importantes concernant ce type de molécules consiste en leur caractère de diradical à couches ouvertes, qui est à l'origine de leurs propriétés optiques, électroniques et magnétiques particulières. Nous avons étudié les relations entre la structure fondamentale, le caractère diradicalaire et les propriétés physiques. Ces études forment la base d'une conception généralisée aux diradicaloïdes singulets à couches ouvertes dont le caractère diradicalaire et les propriétés physiques seraient réglables. [Traduit par la Rédaction]

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Section: Zethrene Analogues As Stable Near-infrared Dyesmentioning

confidence: 99%

Modern zethrene chemistry

Pan

2017

Can. J. Chem.

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“…Many BODIPY‐based NIR dyes have been isolated, but their absorption bands are mostly around λ =700–900 nm. Recently, two stable BODIPY‐based organic dyes with diradical character were reported to exhibit intense absorption around 1100 nm …”

Section: Introductionmentioning

confidence: 99%

The Diradical‐Dication Strategy for BODIPY‐ and Porphyrin‐Based Dyes with Near‐Infrared Absorption Maxima from 1070 to 2040 nm

Wei

Feng

Fang

et al. 2018

Chemistry A European J

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Four stable boron dipyrromethene (BODIPY)‐ and porphyrin‐based bis‐arylamine diradical dications were synthesized by two‐electron oxidation of their neutral molecules. The two BODIPY‐based dications have open‐shell singlet ground states. UV/Vis absorption spectra of all four dications showed large redshifts in the NIR region compared to their neutral precursors with absorption maxima at 1274 and 1068 nm for the two BODIPY‐based dications and 1746 and 2037 nm for the two porphyrin‐based dications. Thus, two new types of NIR dyes with longer wavelengths are provided by the diradical‐dication strategy, which can be applied for the generation of other NIR dyes with a range of different chromophores and auxochromes.

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“…In particular, because the decrease of energy gap between the lowest excited state and the open‐shell ground state by the formation of (di)radical species induces an acceleration of the non‐radiative internal conversion processes, we observed ultrafast excited‐state lifetimes in NDI‐1 . (0.35 ps) and NDI‐2 .. (1.5 ps) …”

Section: Methodsmentioning

confidence: 99%

“…These short excited-state lifetimes are in good agreement with their non-fluorescent behaviors.I n particular, because the decreaseo fe nergy gap between the loweste xcited state and the open-shell ground state by the formation of (di)radical species induces an acceleration of the non-radiative internal conversion processes, we observed ultrafast excited-state lifetimes in NDI-1C (0.35 ps) and NDI-2CC (1.5 ps). [37,45] In summary,w edemonstrated the formationo f( di)anion and (di)radicali nt he NDI derivatives, NDI-1 and NDI-2,b yd eprotonation and simple chemicalo xidation using Bu 4 NOH and PbO 2 ,r espectively.M oreover,t he characterizationo fg enerated (di)radical throughv arious optical, magnetic spectroscopies, and theoretical calculations revealed their strong nonlinear optical properties, short excited-state lifetimes, small singlet-triplet energy gap, and weak interactions originated from localized spin characters. In particular,w es uccessfully synthesized, for the first time, an NDI diradical with relatively large singlet diradical character (y = 0.69).…”

mentioning

confidence: 95%

Radical and Diradical Formation in Naphthalene Diimides through Simple Chemical Oxidation

et al. 2017

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We successfully synthesized, for the first time, a naphthalene diimide (NDI) radical and diradical by simple chemical oxidation using lead(IV) dioxide. The formation of the (di)radical is confirmed by UV/Vis/NIR absorption, H NMR, and electron paramagnetic resonance (EPR) measurements. In particular, temperature-dependent EPR, SQUID (superconducting quantum interference device) measurements, and quantum calculations demonstrated that the generated NDI diradical has a singlet diradical character of y=0.69 in the ground state. Subsequent characterization of this (di)radical revealed its stabilities, large two-photon absorption cross-section, and short excited-state lifetime.

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A Diradical Approach towards BODIPY‐Based Dyes with Intense Near‐Infrared Absorption around λ=1100 nm

Cited by 103 publications

References 52 publications

Modern zethrene chemistry

Modern zethrene chemistry

The Diradical‐Dication Strategy for BODIPY‐ and Porphyrin‐Based Dyes with Near‐Infrared Absorption Maxima from 1070 to 2040 nm

Radical and Diradical Formation in Naphthalene Diimides through Simple Chemical Oxidation

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