Synthesis and Reversible Control of the Fluorescent Properties of a Divalent Tin Dipyrromethene

Kobayashi, Junji; Kushida, Tomokatsu; Kawashima, Takayuki

doi:10.1021/ja904470m

Cited by 55 publications

(75 citation statements)

References 21 publications

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“…39,40 However, in spite of the increasing number of reported metallodipyrrins, 37,41−51 their photophysics are not well-understood. Unlike the highly fluorescent bDIPs, 36,37 homoleptic complexes MD n (D = dipyrrin or π-extended dipyrrin ligands) 43,44,46,47,49 generally exhibit low to moderate fluorescent quantum yields.…”

Section: Introductionmentioning

confidence: 99%

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Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins

et al. 2014

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Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450–550 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16–0.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10–3, in acetonitrile). The low quantum efficiencies in polar solvents are attributed to the formation of a nonemissive symmetry-breaking charge transfer (SBCT) state, which is not formed in nonpolar solvents. Analysis using ultrafast spectroscopy shows that in polar solvents the singlet excited state relaxes to the SBCT state in 1.0–5.5 ps and then decays via recombination to the triplet or ground states in 0.9–3.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11–22 ps.

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Section: Introductionmentioning

confidence: 99%

“…In contrast, the heteroleptic complexes MDX n (X is an ancillary ligand) were shown to have quite high luminescent efficiencies (up to 80%). 41−45,50,51 …”

Section: Introductionmentioning

confidence: 99%

Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins

et al. 2014

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“…PODIPY and aza-PODIPY are watersoluble, and aza-PODIPY is suited for labeling living Hep-2 cells for imaging assays in the near-infrared region. Moreover,d ipyrromethene compounds with group 14 elements (germanium, [7] silicon [8] and tin [9] )h ave been successfully synthesized. [1] Dipyrromethenes or azadipyrromethenes have also been explored as ligands to complex with different metals to form metallodipyrrin or metalloazadipyrrin complexes,w hiche xhibit av ariety of coordination geometriesa nd architectures.…”

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confidence: 99%

A New Water‐Soluble Phosphorus‐Dipyrromethene and Phosphorus‐Azadipyrromethene Dye: PODIPY/aza‐PODIPY

Jiang

Zhao

et al. 2015

Chemistry A European J

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PODIPY and aza-PODIPY have been successfully prepared by the treatment of dipyrromethene and azadipyrromethene with POCl3 in the presence of Et3 N. The new PODIPY and aza-PODIPY dyes are found to have photophysical properties. PODIPY and aza-PODIPY are water-soluble, and aza-PODIPY is suited for labeling living Hep-2 cells for imaging assays in the near-infrared region. Molecular orbital calculations show that the increase in the HOMO-LUMO band gap for the lowest energy absorption bands is observed in the new phosphorus-containing aza-PODIPY, and the HOMO and LUMO energies of aza-PODIPY are found to be higher than those of aza-BODIPY.

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“…For example, Holten, Lindsey et al showed that by increasing the size of the meso -aryl group in Zn bis -aryldipyrrins, the non-radiative decay could be diminished, affording considerable gain in emission 6a. On the other hand, some recently reported heteroleptic Al 3+ and Sn 2+ mono -dipyrrinates (MLX n ) exhibit bright fluorescence,7,8 suggesting that the emissivity of metallodipyrrins could in part be related to the mode of metal coordination. Overall, the interplay between the structure and photophysics of metallodipyrrins is not well understood; and generally metallodipyrrins are considered poorly emissive species 1a…”

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confidence: 99%

π-Extended Dipyrrins Capable of Highly Fluorogenic Complexation with Metal Ions

et al. 2010

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Synthesis and properties of a new family of π-extended dipyrrins, capable of forming brightly fluorescent complexes with metal ions, are reported. The metal complexes posses tunable spectral bands and exhibit different emission properties depending on the mode of metal coordination.Boron dipyrrins (BODIPY) form a popular group of fluorophores due to their high emission quantum yields, excellent photostability and versatile chemistry.1 While boron complexes of dipyrrins are by far the most recognized, dipyrrins have also long been known to form stable adducts with metal ions.2 , 3 , 4 Metallodipyrrins are typically isolated as homoleptic biscomplexes (ML 2 , L=dipyrrin), which mainly find use as building blocks for construction of various supramolecular assemblies.5 Curiously, unlike BODIPY, homoleptic metallodipyrrins practically do not fluoresce, although there are several important exemptions.6 For example, Holten, Lindsey et al showed that by increasing the size of the meso-aryl group in Zn bis-aryldipyrrins, the non-radiative decay could be diminished, affording considerable gain in emission.6a On the other hand, some recently reported heteroleptic Al 3+ and Sn 2+ mono-dipyrrinates (MLX n ) exhibit bright fluorescence,7 , 8 suggesting that the emissivity of metallodipyrrins could in part be related to the mode of metal coordination. Overall, the interplay between the structure and photophysics of metallodipyrrins is not well understood; and generally metallodipyrrins are considered poorly emissive species.1aHere we report a new family of aromatically π-extended dipyrrin molecules capable of forming bright fluorescent complexes with metal ions and exhibiting a unique fluorescence modulation effect mediated by exciton coupling.9 A recently described approach to π-extended porphyrins, based on 4,7-dihydroisoindole and its derivatives (Scheme 1),10 paved a new way to π-extended oligopyrroles, including 2,2′-alkoxycarbonyl-dibenzo-(BDP) and dinaphtho [2,3] condensation of 2-substituted 4,7-dihydroisoindole 1 with aldehydes,10c followed by the oxidation of dipyrromethanes with DDQ. Similarly, dinaphthodipyrrins can be synthesized from the corresponding pyrrole-esters reported previously (Scheme 1).10aAll the synthesized dipyrrins exhibit broad absorption bands (ε~4-7×10 4 M −1 cm −1 ) ranging from 550-570 nm for BDP's (2a-f) to 660-700 nm for NDP (3). Taken as free-bases, BDP's and NDP's fluoresce very weakly (φ fl~0 .01-0.02 at 22°C); however, upon addition of metal salts (e.g. Zn(OAc) 2 , Ca(OAc) 2 , YCl 3 , LaCl 3 , GdCl 3 ) their solutions instantly become fluorescent. For example, upon addition of Zn(OAc) 2 , purple solutions of BDP's in DMF immediately change color to deep blue with appearance of bright red fluorescence (Fig. 1b). In contrast, metallation of regular dipyrrins typically requires heating and/or presence of bases and leads to non-emissive products.The optical transitions of the new π-extended dipyrrinates span the entire red spectral range (Fig. 1a), resembling in shape the bands of BOD...

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Synthesis and Reversible Control of the Fluorescent Properties of a Divalent Tin Dipyrromethene

Cited by 55 publications

References 21 publications

Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins

Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins

A New Water‐Soluble Phosphorus‐Dipyrromethene and Phosphorus‐Azadipyrromethene Dye: PODIPY/aza‐PODIPY

π-Extended Dipyrrins Capable of Highly Fluorogenic Complexation with Metal Ions

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