High Stokes Shift Anilido‐Pyridine Boron Difluoride Dyes

Araneda, Juan F.; Piers, Warren E.; Heyne, Belinda; Parvez, Masood; McDonald, Robert

doi:10.1002/anie.201105228

Cited by 265 publications

(171 citation statements)

References 43 publications

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“…It is surprising and exciting that such primitive aromatic amines as BDAAs can achieve a large Stokes shift comparable to highly designed donor-acceptor systems. [44][45]50 …”

Section: Calculated Stokes Shiftmentioning

confidence: 99%

Highly Twisted N,N-Dialkylamines as a Design Strategy to Tune Simple Aromatic Hydrocarbons as Steric Environment-Sensitive Fluorophores

et al. 2016

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The steric-environment sensitivity of fluorescence of 9,10-bis(N,N-dialkylamino)anthracenes (BDAAs) was studied experimentally and theoretically. A new design strategy to tune simple aromatic hydrocarbons as efficient aggregation-induced emission (AIE) luminogens and molecular rotors is proposed. For a variety of BDAAs, prominent Stokes shifts and efficient solid-state fluorescence were observed. Calculations on BDAA-methyl suggested that in the ground state (S0) conformations, the pyramidal amine groups are highly twisted, so that their lone-pair orbitals cannot conjugate with the anthracene π orbitals. Fluorescence takes place from the S1 minima, in which one or both amine groups are planarized. The stability of the S1 excited state minima as well as destabilization of the S0 state is the origin of large Stokes shift. Experimental measurement of the nonadiabatic transition rate suggests that para disubstitution by dialkylamino (or strongly electron-donating) groups is a key for fast internal conversion. Minimum energy conical intersection (MECI) between S1 and S0 states was found to have a Dewar-benzene like structure. Although this can be reached efficiently in liquid phase for fast internal conversion, a large amplitude motion is required to reach this MECI, which is prohibited in the solid state and caused efficient AIE. This strategy is used to find experimentally that naphthalene analogues are also efficient AIE luminogens. The flexibility of alkyl chains on amino groups is also found to be important for allowed charge-transfer transition. Thus, three points [(1) highly twisted N,N-dialkylamines, (2) substitution at the para positions, (3) with flexible alkyl groups] were proposed for activation of small aromatic hydrocarbons.

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“…It is surprising and exciting that such primitive aromatic amines as BDAAs can achieve a large Stokes shift comparable to highly designed donor-acceptor systems. [44][45]50 …”

Section: Calculated Stokes Shiftmentioning

confidence: 99%

Highly Twisted N,N-Dialkylamines as a Design Strategy to Tune Simple Aromatic Hydrocarbons as Steric Environment-Sensitive Fluorophores

et al. 2016

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“…11,12 These fluorescent dyes use the difluoroboron (BF 2 ) unit to restrict intramolecular rotation and vibrational freedom of the β-diketonate ligand, producing bright and efficient fluorescence. 13,14 Various types of BF 2 fluorescent materials have been prepared, including β-diketiminate (NBN), 15,16 β-ketoiminate (NBO), 17–21 and β-diketonate (OBO) complexes. 22–24 Difluoroboron can also act as an electron-accepting group, inducing a strong dipole upon excitation, making the dyes sensitive to solvent and media polarity.…”

Section: Introductionmentioning

confidence: 99%

Oxygen Sensing Difluoroboron Dinaphthoylmethane Polylactide

et al. 2015

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Dual emissive luminescence properties of solid-state difluoroboron β-diketonate-poly(lactic acid) (BF2bdk-PLA) materials have been utilized as biological oxygen sensors. Dyes with red-shifted absorption and emission are important for multiplexing and in vivo imaging, thus hydroxyl-functionalized dinaphthoylmethane initiators and dye-PLA conjugates BF2dnm(X)PLA (X = H, Br, I) with extended conjugation were synthesized. The luminescent materials show red-shifted absorbance (~435 nm) and fluorescence tunability by molecular weight. Fluorescence colors range from yellow (~530 nm) in 10 – 12 kDa polymers to green (~490 nm) in 20 – 30 kDa polymers. Room-temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) are present under a nitrogen atmosphere. For the iodine-substituted derivative, BF2dnm(I)PLA, clearly distinguishable fluorescence (green) and phosphorescence (orange) peaks are present, making it ideal for ratiometric oxygen-sensing and imaging. Bromide and hydrogen analogues with weaker relative phosphorescence intensities and longer phosphorescence lifetimes can be used as highly sensitive, concentration independent, lifetime-based oxygen sensors or for gated emission detection. BF2dnm(I)PLA nanoparticles were taken up by T41 mouse mammary cells and successfully demonstrated differences in vitro ratiometric measurement of oxygen.

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“…The Stokes shift of compounds 1-4 are ranging from 70 to 84 nm which are larger than that of common BODIPY dyes (7-15 nm). [10] Fluorescence lifetimes of about 500 ps are observed for 1-4, with only minor differences among these compounds (Figure S15 b and Table S3), ruling out a possible decay mechanism through triplet states.…”

Section: Resultsmentioning

confidence: 94%

“…[10] The colors of 1-4 are blue, red, yellow and orange, respectively. Notably, for ligand 7, only the proton at the nitrogen atom of the indole ring was deprotonated after reaction with BF 3 .…”

Section: Resultsmentioning

confidence: 99%

Geometric and Electronic Structures of Boron(III)‐Cored Dyes Tailored by Incorporation of Heteroatoms into Ligands

Sun

Zhang

Wang

et al. 2015

Chemistry An Asian Journal

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Complexation of a boron atom with a series of bidentate heterocyclic ligands successfully gives rise to corresponding BF2-chelated heteroarenes, which could be considered as novel boron(III)-cored dyes. These dye molecules exhibit planar structures and expanded π-conjugated backbones due to the locked conformation with a boron center. The geometric and electronic structures of these BF2 complexes can be tailored by embedding heteroatoms in the unique modes to form positional isomer and isoelectronic structures. The structure-property relationship is further elucidated by studying the photophysical properties, electrochemical behavior and quantum-chemical calculations.

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High Stokes Shift Anilido‐Pyridine Boron Difluoride Dyes

Cited by 265 publications

References 43 publications

Highly Twisted N,N-Dialkylamines as a Design Strategy to Tune Simple Aromatic Hydrocarbons as Steric Environment-Sensitive Fluorophores

Highly Twisted N,N-Dialkylamines as a Design Strategy to Tune Simple Aromatic Hydrocarbons as Steric Environment-Sensitive Fluorophores

Oxygen Sensing Difluoroboron Dinaphthoylmethane Polylactide

Geometric and Electronic Structures of Boron(III)‐Cored Dyes Tailored by Incorporation of Heteroatoms into Ligands

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