Influence of Substituent and Benzoannulation on Photophysical Properties of 1-Benzoylmethyleneisoquinoline Difluoroborates

Ośmiałowski, Borys; Zakrzewska, Anna; Jędrzejewska, Beata; Grabarz, Anna; Zaleśny, Robert; Bartkowiak, Wojciech; Kolehmainen, Erkki

doi:10.1021/jo502244j

Cited by 49 publications

(56 citation statements)

References 78 publications

(113 reference statements)

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“…Furthermore, it was implied that the nitrogen atom could contribute to suppressing ACQ by partially disordering π‐stacking at the boron complex moiety. Based on these results, we designed ketoiminate complexes by employing fused structures in order to realize constant emission efficiencies in the solid state, such as the amorphous and crystal forms, as well as in solution. By introducing the fused structure at the nitrogen atom in the ketoiminate ligand, molecular motions should be effectively suppressed.…”

Section: Resultsmentioning

confidence: 99%

Design and Luminescence Chromism of Fused Boron Complexes Having Constant Emission Efficiencies in Solution and in the Amorphous and Crystalline States

2017

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Mechanochromic luminescent molecules often suffer from critical loss of luminescence intensity during phase transitions in the solid state. In this study, we present mechanochromic luminescent molecules that can provide clear color changes with constant emission intensity during phase transitions. It was reported that the class of aggregation‐induced emission (AIE)‐active boron complexes can present intense emission by freezing intramolecular motions. According to this mechanism, we designed a complex with a fused ligand to preserve the enhanced emission in the aggregated state in the AIE during phase transitions between the solution, amorphous, and crystalline states. From optical measurements, it was shown that the synthesized boron complexes present bright emission in various phases. In particular, as we expected, the luminescence color was clearly altered during phase transition, whereas the emission intensity changed only slightly. Finally, we also found that diverse luminescence colors were obtained from each polymorph and for various substituents as induced by the substituent effect. The results in the series of mechanistic studies show that electronic interactions and π–π interactions can modulate the electronic conjugation system of the complexes without causing loss of emission efficiency.

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Section: Resultsmentioning

confidence: 99%

Design and Luminescence Chromism of Fused Boron Complexes Having Constant Emission Efficiencies in Solution and in the Amorphous and Crystalline States

2017

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“…The situation changes when one considers a boron atom chelated between two differently substituted nitrogen atoms or, in a more extreme example, between two different atoms, such as nitrogen and oxygen. These structures are known as ketoiminates or boranils . Their properties, with an emphasis on electron distribution in the light of electronic absorption, were studied by using theoretical methods by Jacquemin et al., whereas the first review publication that focused on difluoroborates with the exception of BODIPYs was published by Ziessel et al …”

Section: Introductionmentioning

confidence: 99%

Tuning the Electronic Properties of the Dative N−B Bond with Associated O−B Interaction: Electron Localizability Indicator from X‐Ray Wavefunction Refinement

et al. 2016

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Despite the immense growth in interest in difluoroborate dyes, the nature of the interactions of the boron atom within the N-BF2 -O kernel is not yet fully understood. Herein, a set of real-space bonding indicators is used to quantify the electronic characteristics of the dative N-B bond in difluoroborate derivatives. The atoms-in-molecules (AIM) partitioning scheme is complemented by the electron localizability indicator (ELI-D) approach, and both were applied to experimental and theoretical electron-density distributions (X-ray constrained wavefunction fitting vs. DFT calculations). Additionally, Fermi orbital analysis was introduced for small DFT models to support and extend the findings for structures that contain BF2 .

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“…However, the numerous efforts devoted to reproducing the key spectroscopic features of fluoroborates have found mixed successes [14][15][16][17][18][19][20][21], a result in part related to the different protocols used: gas-phase or solution calculations, accounting for vibronic effects or neglecting them, using single-reference or multi-reference methods, etc. Timedependent density functional theory (TD-DFT) the most widely used approach to model electronically excited states has been shown to yield too large transition energies in BODIPYs, as well as in other cyanine-like dyes [22].…”

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confidence: 99%

Theoretical spectroscopy of BASHY dyes

2016

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International audienceThis works constitutes an ab initio investigation of a recently disclosed class of fluorophores, BASHY (Santos et al. in Chem Eur J 22:1631-1637, 2016). We use state-of-the-art approaches including an electronic structure method partially accounting for the contributions of double excitations and a solvent model dependent of the change of dipole moment between the states, to provide accurate estimates of all key optical signatures, including 0-0 energies and, for a prototype structure, the topology of the absorption and emission bands. Besides comparing the pros and cons of several theoretical models and showing that theory adequately reproduces the experimental trends, our calculations demonstrate that despite significant displacement of the electron density from the ground- to the excited-state, typical of charge-transfer states, a cyanine-like character partly pertains in the transition of BASHY. We also rationalize why the most planar structure has one of the smallest quantum yields of emission

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Influence of Substituent and Benzoannulation on Photophysical Properties of 1-Benzoylmethyleneisoquinoline Difluoroborates

Cited by 49 publications

References 78 publications

Design and Luminescence Chromism of Fused Boron Complexes Having Constant Emission Efficiencies in Solution and in the Amorphous and Crystalline States

Design and Luminescence Chromism of Fused Boron Complexes Having Constant Emission Efficiencies in Solution and in the Amorphous and Crystalline States

Tuning the Electronic Properties of the Dative N−B Bond with Associated O−B Interaction: Electron Localizability Indicator from X‐Ray Wavefunction Refinement

Theoretical spectroscopy of BASHY dyes

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