meso-Nitromethyl-Substituted BODIPYs – A new type of water switchable fluorogenic dyes useful for further core modifications

Didukh, Natalia O.; Yakubovskyi, Viktor P.; Zatsikha, Yuriy V.; Nemykin, Victor N.; Kovtun, Yuriy P.

doi:10.1016/j.dyepig.2017.11.037

Cited by 16 publications

(10 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2 Recently, we have developed a convenient synthetic methodology to the preparation of mesonitromethyl-substituted BODIPYs that is based on the addition of nitromethane to the meso-unsubstituted boron dipyrromethene in the presence of base followed by the further oxidation of the corresponding intermediate. 3 The meso-nitromethyl group in these BODIPYs was then used for further modification of the chromophore core via reduction or condensation reactions. In particular, sterically nonhindered BODIPY (1) can be easily benzoylated using anizoyl chloride in the presence of DIPEA to form BODIPY 2.…”

mentioning

confidence: 99%

“…Because properties of this chromophore can be tuned via functionalization of the α-, β-, or meso -positions of the BODIPY core, it is not surprising to see an extensive array of well-developed synthetic procedures reported on chemical modification of these dyes . Recently, we have developed a convenient synthetic methodology to the preparation of meso -nitromethyl-substituted BODIPYs that is based on the addition of nitromethane to the meso -unsubstituted boron dipyrromethene in the presence of base followed by the further oxidation of the corresponding intermediate . The meso -nitromethyl group in these BODIPYs was then used for further modification of the chromophore core via reduction or condensation reactions.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Preparation of Viscosity-Sensitive Isoxazoline/Isoxazolyl-Based Molecular Rotors and Directly Linked BODIPY–Fulleroisoxazoline from the Stable meso-(Nitrile Oxide)-Substituted BODIPY

et al. 2019

Self Cite

View full text Add to dashboard Cite

We developed a simple methodology for the preparation of stable meso-(nitrile oxide)-substituted BODI-PYs, which were characterized by spectroscopic methods and X-ray crystallography. These compounds were used for the preparation of isoxazoline− or isoxazolyl−BODIPYs by 1,3dipolar cycloaddition reaction with dipolarophiles. Several BODIPYs possess molecular rotor behavior, including viscosity-dependent fluorescence. Transient absorption spectroscopy and time-resolved fluorescence are indicative of a 3 orders of magnitude difference in the excited-state lifetime for dichloromethane and glycerol solutions.

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

Preparation of Viscosity-Sensitive Isoxazoline/Isoxazolyl-Based Molecular Rotors and Directly Linked BODIPY–Fulleroisoxazoline from the Stable meso-(Nitrile Oxide)-Substituted BODIPY

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…The initial rationale for using tetramethyl-containing BODIPY 1 was to explore and compare the reactivity of the methyl groups at the 1,7- versus 3,5-positions. Although 1,3,5,7-tetramethyl-2,6-dicarbethoxy-BODIPY 1 has been known since 1968, to our surprise, this platform was mentioned only in four publications to date. − Moreover, while the chemical transformations of the diphenyl-analogue V are quite well-explored, only a single paper on BODIPY 1 discussed direct nitromethylation of its meso -position and thus the reactivity of the four methyl groups in 1 remains completely unexplored . This is even more surprising taking into consideration commercial availability and ease of preparation of the 2,4-dimethyl-3-carbethoxypyrrole, which is a key precursor for synthesis of BODIPY 1 .…”

Section: Resultsmentioning

confidence: 99%

Flexible BODIPY Platform That Offers an Unexpected Regioselective Heterocyclization Reaction toward Preparation of 2-Pyridone[a]-Fused BODIPYs

et al. 2019

Self Cite

View full text Add to dashboard Cite

We have explored the synthetic routes for regioselective formation of 2-pyridone[a]- and 2-pyridone[b]-fused BODIPYs using 1,3,5,7-tetramethyl-2,6-dicarbethoxy-BODIPY as the universal starting platform. While heterocyclization of the 3-(dimethylaminovinyl)-BODIPY and 3,5-bis(dimethylaminovinyl)-BODIPY results in the formation of mono-2-pyridone- and bis-2-pyridone[b]-fused BODIPYs, respectively, similar heterocyclization of the 1,3-bis(dimethylaminovinyl)-BODIPY leads to the regioselective formation of the 2-pyridone[a]-fused BODIPY core, which is the first example of heterocycle[a]-fused BODIPYs. The regioselective formation of the 2-pyridone[a]-fused BODIPY was further confirmed by X-ray crystallography and explained on the basis of the DFT and TDDFT calculations that are suggestive of the energy-favorable out-of-plane rotation of the dimethylaminovinyl group located at first position, which accelerates the reaction with n-butylamine. Trends in the UV–vis and fluorescence spectra of the BODIPYs 1–17 were discussed on the basis of DFT and TDDFT calculations.

show abstract

“…BODIPY, derived from 4,4-difluoro-4-bora-3a,4a-diazas-indacene, a class of boron chelates with dipyrromethene, was first discovered by Treibs and Kreuzer in 1968 [17]. Subsequently, there has been rising interest in BODIPY dyes due to their fascinating photophysical properties like excellent photostability, high fluorescent quantum yield, intense absorption profile and lager extinction coefficient [18][19][20][21][22]. Over the past three decades, because of these remarkable properties, BODIPY derivatives were widely used as chemosensors [23,24], biological imaging, [25] fluorescent probes [26], photodynamic therapy [27], NLO materials [28][29][30], etc.…”

Section: Introductionmentioning

confidence: 99%

DFT study of effect of substituents on second-order NLO response of novel BODIPY dyes

Kang

Wang

et al. 2021

Theor Chem Acc

View full text Add to dashboard Cite

Based on molecular structural design of boron-dipyrromethene (BODIPY), nine BODIPY derivatives decorated with vinyl, phenyl, dimethylamino, nitro and aldehyde group substituents, respectively, have been systematically investigated by the density function theory (DFT) method. The purposes of this paper are to study the effect of various substituents and their positions on geometric structures, electronic structures and second-order nonlinear optical (NLO) properties. In addition, the effects of polarizable environment and electric fields on the first hyperpolarizabilities (β tot ) values have been investigated. It is found that the incorporation of strong electron-donating dimethylamino could induce a significant enhancement of the β tot values, and the β tot values of the bilateral α-position substitution are much larger with respect to the unilateral α-position substitution, because those substituents are able to expend the BODIPYs' delocalized π-electron system to different extents. Time-dependent DFT results suggest that the increasement of the β tot values is related to the intramolecular charge transfer from substituents to BODIPY core. Thus, forming a D-π-A model is favorable for increasing the β tot values, where BODIPY was used as electron accepting. Hence, we hope this work will be beneficial to further investigating versatile and novel NLO materials.

show abstract

meso-Nitromethyl-Substituted BODIPYs – A new type of water switchable fluorogenic dyes useful for further core modifications

Cited by 16 publications

References 45 publications

Preparation of Viscosity-Sensitive Isoxazoline/Isoxazolyl-Based Molecular Rotors and Directly Linked BODIPY–Fulleroisoxazoline from the Stable meso-(Nitrile Oxide)-Substituted BODIPY

Preparation of Viscosity-Sensitive Isoxazoline/Isoxazolyl-Based Molecular Rotors and Directly Linked BODIPY–Fulleroisoxazoline from the Stable meso-(Nitrile Oxide)-Substituted BODIPY

Flexible BODIPY Platform That Offers an Unexpected Regioselective Heterocyclization Reaction toward Preparation of 2-Pyridone[a]-Fused BODIPYs

DFT study of effect of substituents on second-order NLO response of novel BODIPY dyes

Contact Info

Product

Resources

About