The synthesis and crystal structure of unsubstituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)

Tram, Kha; Yan, Hongbin; Jenkins, Hilary A.; Vassiliev, S.; Bruce, Doug

doi:10.1016/j.dyepig.2009.03.001

Cited by 115 publications

(65 citation statements)

References 20 publications

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“…BÀN bond lengths equal 1.569(2) and 1.565 (2) and are similar to distances typically reported for BODIPY complexes. [54][55][56] Distances between the hydrogen atoms H (26) and H(30) and the proximate F atom equal 2.23 and 2.20 , respectively, and are slightly shorter than the mean C-H···F distance reported for intermolecular interactions (2.45 ). [57] The fused pentaphyrin 7 b-H 2…”

Section: Resultsmentioning

confidence: 75%

Hückel and Möbius Expanded para‐Benziporphyrins: Synthesis and Aromaticity Switching

Szyszko

Sprutta

Chwalisz

et al. 2014

Chemistry A European J

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The four expanded p-benziporphyrins A,C-di-p-benzi[24]pentaphyrin(1.1.1.1.1), N-fused A-p-benzi[24]pentaphyrin, A,D-di-p-benzi[28]hexaphyrin(1.1.1.1.1.1), and A,C-di-p-benzi[28]hexaphyrin(1.1.1.1.1.1) were obtained in three-component Lindsey-type macrocyclizations. These compounds were explored as macrocyclic ligands and as potential aromaticity switches. A BODIPY-like difluoroboron complex was obtained from the A,C-di-p-benzi[24]pentaphyrin, whereas A,C-di-p-benzi[28]hexaphyrin yielded a Möbius-aromatic Pd(II) complex containing fused pyrrole and phenylene subunits. Conformational behavior, tautomerism, and acid-base chemistry of the new macrocycles were characterized by means of NMR spectroscopy and DFT calculations. Free base N-fused A-p-benzi[24]pentaphyrin showed temperature-dependent Hückel-Möbius aromaticity switching, whereas the A,C-di-p-benzi[28]hexaphyrin formed a Möbius-aromatic dication.

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Section: Resultsmentioning

confidence: 75%

Hückel and Möbius Expanded para‐Benziporphyrins: Synthesis and Aromaticity Switching

Szyszko

Sprutta

Chwalisz

et al. 2014

Chemistry A European J

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“…The rich variety of groups introducible at the 8‐position leads to a set of dyes with absorption and fluorescence emission spectra covering the major part of the visible spectrum 102. The dyes with 8‐ N (8‐phenylamino, 8‐benzylamino; Scheme , i) and 8‐ O (8‐methoxy, 8‐phenoxy; Scheme , iv–v) substituents have blue‐shifted absorption and fluorescence emission spectra and larger Stokes shifts with respect to unsubstituted BODIPY 103,104. This hypsochromic shift is related to the electron‐donating character of the heteroatom and is markedly larger in the N case than in the O case.…”

Section: Functionalization At the 8‐positionmentioning

confidence: 99%

Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

2015

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In this review we describe the various new methodologies for synthetic postmodification of the BODIPY core designed and developed by our research groups, as well as their electronic spectroscopic properties. We discuss the different strategies created for functionalization of the BODIPY framework at the pyrrole C‐ring positions and the meso‐position. Halogenated boron dipyrrins are substrates for nucleophilic substitution or Pd‐catalyzed cross‐coupling reactions. α‐Unsubstituted BODIPYs can be functionalized with N and C nucleophiles through oxidative or vicarious nucleophilic substitution (VNS) of the α‐hydrogen atoms. Combining this methodology with reversible Michael addition onto nitrostyrenes provides a route to 3‐styrylated BODIPYs. Furthermore, the one‐step, Pd‐catalyzed C–H arylation of 3,5‐unsubstituted BODIPYs leads to 3‐ and 3,5‐arylated dyes. Finally, radical C–H arylation at the 3,5‐positions of α‐unsubstituted BODIPYs provides an additional synthesis route to arylated dyes.

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“…We show now that BODIPYs( Scheme1)a re able to generate the T 1 state based on ad ifferent mechanism.B ODIPY and its derivatives are well-known highlyf luorescent materials for various applications, [13][14][15][16][17] but these dyes lack the ability to produce the T 1 state upon photo excitation. [12,18,19] Unsubstituted BODIPY,f or example, shows fluorescencee fficiency near unity (0.97 AE 0.03) and al ong fluorescence lifetime of 6.89 ns in methanol, [20] which leaves it little space to form the T 1 state. The heavy atom effect with iodine or bromine substitution and dimerization are often used to make BODIPYefficient in T 1 formation.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Electron Transfer‐based Halogen‐free Photosensitizers: Covalent meso‐Aryl (Phenyl, Naphthyl, Anthryl, and Pyrenyl) as Electron Donors to Effectively Induce the Formation of the Excited Triplet State and Singlet Oxygen for BODIPY Compounds

Zhang

Feng

2017

Chemistry An Asian Journal

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Pristine BODIPY compounds have negligible efficiency to generate the excited triplet state and singlet oxygen. In this report, we show that attaching a good electron donor to the BODIPY core can lead to singlet oxygen formation with up to 58 % quantum efficiency. For this purpose, BODIPYs with meso-aryl groups (phenyl, naphthyl, anthryl, and pyrenyl) were synthesized and characterized. The fluorescence, excited triplet state, and singlet oxygen formation properties for these compounds were measured in various solvents by UV/Vis absorption, steady-state and time-resolved fluorescence methods, as well as laser flash photolysis technique. In particular, the presence of anthryl and pyrenyl showed substantial enhancement on the singlet oxygen formation ability of BODIPY with up to 58 % and 34 % quantum efficiency, respectively, owing to their stronger electron-donating ability. Upon the increase in singlet oxygen formation, the fluorescence quantum yield and lifetime values of the aryl-BODIPY showed a concomitant decrease. The increase in solvent polarity enhances the singlet oxygen generation but decreases the fluorescence quantum yield. The results are explained by the presence of intramolecular photoinduced electron transfer from the aryl moiety to BODIPY core. This method of promoting T formation is very different from the traditional heavy atom effect by I, Br, or transition metal atoms. This type of novel photosensitizers may find important applications in organic oxygenation reactions and photodynamic therapy of tumors.

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The synthesis and crystal structure of unsubstituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)

Cited by 115 publications

References 20 publications

Hückel and Möbius Expanded para‐Benziporphyrins: Synthesis and Aromaticity Switching

Hückel and Möbius Expanded para‐Benziporphyrins: Synthesis and Aromaticity Switching

Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

Photoinduced Electron Transfer‐based Halogen‐free Photosensitizers: Covalent meso‐Aryl (Phenyl, Naphthyl, Anthryl, and Pyrenyl) as Electron Donors to Effectively Induce the Formation of the Excited Triplet State and Singlet Oxygen for BODIPY Compounds

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