Influence of the Nature of the Amino Group in Highly Fluorescent Difluoroborates Exhibiting Intramolecular Charge Transfer

Jędrzejewska, Beata; Skotnicka, Agnieszka; Laurent, Adèle D.; Pietrzak, Marek; Jacquemin, Denis; Ośmiałowski, Borys

doi:10.1021/acs.joc.8b00664

Cited by 27 publications

(18 citation statements)

References 47 publications

(96 reference statements)

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“…Quantum chemistry can answer some of these questions by exploring the chemical and photochemical properties of BODIPY dyes, such as their luminescence spectra or the fluorescence/phosphorescence ratio. − However, the most commonly used functionals applied within the framework of time-dependent density functional theory (TD-DFT) are not able to reproduce the photophysical properties of BODIPY dyes. , Several groups have overcome this difficulty by using other methods like SOS-CIS(D) and CASPT2 , or using purpose-specific functionals. , These solutions are unfortunately not a panacea as SOS-CIS(D) results rely on the quality of the underlying CIS calculation while CASPT2 requires an active space and suffers from the intruder state problem. Thus, an accurate theoretical method which is capable of delivering results of a uniform quality in a black box fashion and without such deficiencies is much desired for the study of larger molecules such as BODIPY compounds.…”

Section: Introductionmentioning

confidence: 99%

Unveiling the Photophysical Properties of Boron-dipyrromethene Dyes Using a New Accurate Excited State Coupled Cluster Method

Berraud-Pache

Neese

Bistoni

et al. 2019

J. Chem. Theory Comput.

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Boron-dipyrromethene (BODIPY) molecules form a class of fluorescent dyes known for their exceptional photoluminescence properties. Today, they are used extensively in various applications from fluorescent imaging to optoelectronics. The ease of altering the BODIPY core has allowed scientists to synthesize dozens of analogues by exploring chemical substitutions of various kinds or by increasing the length of conjugated groups. However, predicting the impact of any chemical change accurately is still a challenge, especially as most computational methods fail to describe correctly the photophysical properties of BODIPY derivatives. In this study, the recently developed coupled cluster method called "domain-based local pair natural orbital similarity transformed equation of motion-coupled cluster singles and doubles" (DLPNO-STEOM-CCSD) is employed to compute the lowest vertical excitation energies of more than 50 BODIPY molecules. The method performs remarkably well yielding an accuracy of about 0.06 eV compared to the experimental absorption maxima. We also provide an estimate to the error made by neglecting vibronic effects in the computed spectra. The dyes selected for investigation here span a large range of molecular sizes and chemical functionalities and are embedded in solvents with different polarities. We have also investigated if the method is able to correctly reproduce the impact of a single chemical modification on the absorption energy. To characterize the method in more specific terms, we have studied four large BODIPY analogues used in real-life applications due to their interesting chemical properties. These examples should illustrate the capacity of the DLPNO-STEOM-CCSD procedure to become a method of choice for the study of photophysical properties of medium to large organic compounds.

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Section: Introductionmentioning

confidence: 99%

Unveiling the Photophysical Properties of Boron-dipyrromethene Dyes Using a New Accurate Excited State Coupled Cluster Method

Berraud-Pache

Neese

Bistoni

et al. 2019

J. Chem. Theory Comput.

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“…The effect of the twist may be used in bioimaging as a tool to change the properties of the fluorophore, making it responsive due to the PICT (planar intramolecular charge transfer) mechanism. 52 It is also worth recalling that alkyl groups (Et in this case) are electron donating substituents. Thus, the overall electron accepting properties of the BF 2 core are decreased and so is the effectiveness of the charge transfer.…”

Section: Resultsmentioning

confidence: 99%

“…17° and 6° for core CH and CHC 6 H 4 single bonds, respectively). The effect of the twist may be used in bioimaging as a tool to change the properties of the fluorophore, making it responsive due to the PICT (planar intramolecular charge transfer) mechanism . It is also worth recalling that alkyl groups (Et in this case) are electron donating substituents.…”

Section: Resultsmentioning

confidence: 99%

Two-Photon Absorption Activity of BOPHY Derivatives: Insights from Theory

et al. 2021

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We present a theoretical study of a two-photon absorption (2PA) process in dipolar and quadrupolar systems containing two BF 2 units. For this purpose, we considered 13 systems studied by Ponce-Vargas et al. [ 29136383 J. Phys. Chem. B 2017 121 10850 10858 ] and performed linear and quadratic response theory calculations based on the RI-CC2 method to obtain the 2PA parameters. Furthermore, using the recently developed generalized few-state model, we provided an in-depth view of the changes in 2PA properties in the molecules considered. Our results clearly indicate that suitable electron-donating group substitution to the core BF 2 units results in a large red-shift of the two-photon absorption wavelength, thereby entering into the desired biological window. Furthermore, the corresponding 2PA strength also increases significantly (up to 30-fold). This makes the substituted systems a potential candidate for biological imaging.

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“…The introduction of electrondonating groups or additional conjugated fragments into such molecules shifts the spectral maxima to an even longer wavelengths. [13][14][15][16][17] However, such derivatives require multistep synthesis based on lithiation of 2-alkyl pyridines. In this work, we demonstrate that similar highly fluorescent derivatives can be synthesized starting from pyridineacetic acids just in two steps (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Fluorescent 2‐Hydroxy‐3‐(pyridin‐2‐yl)‐4H‐quinolizin‐4‐ones through Dimerization of Pyridineacetic Acids

Соколов¹,

Sycheva²,

Farkhutdinova

et al. 2022

Eur J Org Chem

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Influence of the Nature of the Amino Group in Highly Fluorescent Difluoroborates Exhibiting Intramolecular Charge Transfer

Cited by 27 publications

References 47 publications

Unveiling the Photophysical Properties of Boron-dipyrromethene Dyes Using a New Accurate Excited State Coupled Cluster Method

Unveiling the Photophysical Properties of Boron-dipyrromethene Dyes Using a New Accurate Excited State Coupled Cluster Method

Two-Photon Absorption Activity of BOPHY Derivatives: Insights from Theory

Fluorescent 2‐Hydroxy‐3‐(pyridin‐2‐yl)‐4H‐quinolizin‐4‐ones through Dimerization of Pyridineacetic Acids

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