TY  - JOUR
A1  - Hattori, Yohei
A1  - Michail, Evripidis
A1  - Schmiedel, Alexander
A1  - Moos, Michael
A1  - Holzapfel, Marco
A1  - Krummenacher, Ivo
A1  - Braunschweig, Holger
A1  - Müller, Ulrich
A1  - Pflaum, Jens
A1  - Lambert, Christoph
T1  - Luminescent Mono-, Di-, and Tri-radicals: Bridging Polychlorinated Triarylmethyl Radicals by Triarylamines and Triarylboranes
JF  - Chemistry - A European Journal
N2  - Up to three polychlorinated pyridyldiphenylmethyl radicals bridged by a triphenylamine carrying electron withdrawing (CN), neutral (Me), or donating (OMe) groups were synthesized and analogous radicals bridged by tris(2,6‐dimethylphenyl)borane were prepared for comparison. All compounds were as stable as common closed‐shell organic compounds and showed significant fluorescence upon excitation. Electronic, magnetic, absorption, and emission properties were examined in detail, and experimental results were interpreted using DFT calculations. Oxidation potentials, absorption and emission energies could be tuned depending on the electron density of the bridges. The triphenylamine bridges mediated intramolecular weak antiferromagnetic interactions between the radical spins, and the energy difference between the high spin and low spin states was determined by temperature dependent ESR spectroscopy and DFT calculations. The fluorescent properties of all radicals were examined in detail and revealed no difference for high and low spin states which facilitates application of these dyes in two‐photon absorption spectroscopy and OLED devices.
KW  - density functional calculations
KW  - fluorescence
KW  - NIR OLED
KW  - radical
KW  - two-photon absorption
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-208162
VL  - 25
IS  - 68
ER  - 
TY  - JOUR
A1  - Belaidi, Houmam
A1  - Rauch, Florian
A1  - Zhang, Zuolun
A1  - Latouche, Camille
A1  - Boucekkine, Abdou
A1  - Marder, Todd B.
A1  - Halet, Jean-Francois
T1  - Insights into the optical properties of triarylboranes with strongly electron-accepting bis(fluoromesityl)boryl groups: when theory meets experiment
JF  - ChemPhotoChem
N2  - The photophysical properties (absorption, fluorescence and phosphorescence) of a series of triarylboranes of the form 4-D-C\(_6\)H\(_4\)-B(Ar)\(_2\) (D=\(^t\)Bu or NPh\(_2\); Ar=mesityl (Mes) or 2,4,6-tris(trifluoromethylphenyl (Fmes)) were analyzed theoretically using state-of-the-art DFT and TD-DFT methods. Simulated emission spectra and computed decay rate constants are in very good agreement with the experimental data. Unrestricted electronic computations including vibronic contributions explain the unusual optical behavior of 4-\(^t\)Bu-C\(_6\)H\(_4\)-B(Fmes)\(_2\) 2, which shows both fluorescence and phosphorescence at nearly identical energies (at 77 K in a frozen glass). Analysis of the main normal modes responsible for the phosphorescence vibrational fine structure indicates that the bulky tert-butyl group tethered to the phenyl ring is strongly involved. Interestingly, in THF solvent, the computed energies of the singlet and triplet excited states are very similar for compound 2 only, which may explain why 2 shows phosphorescence in contrast to the other members of the series.
KW  - boron
KW  - density functional calculations
KW  - luminescence
KW  - phosphorescence
KW  - photophysics
KW  - activated delayes flourescence
KW  - 3-coordinate organoboron compounds
KW  - light-emitting-diodes
KW  - phosphorescene spectra
KW  - molecular structures
KW  - high efficiency
KW  - pi-conjugation
KW  - trivalent boron
KW  - single photon
KW  - donor
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-205600
VL  - 4
IS  - 3
ER  -