Optical signatures of borico dyes: a TD-DFT analysis

Charaf-Eddin, Azzam; Guennic, Boris Le; Jacquemin, Denis

doi:10.1007/s00214-014-1456-y

Cited by 10 publications

(16 citation statements)

References 52 publications

(73 reference statements)

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“…For this purpose, the recent time-dependent density functional theory (TD-DFT) study on "Borico" dyes published by Charaf-Eddin et al will be av aluabler esource, because these authors have demonstrated that adding an electron acceptor on the coumarin sidea nd as trong electron-donating group on the 3-heteroaryl moiety is the most efficient strategy for obtaining al arge red-shift. [35] Experimental Section General Flash column chromatography purifications were performed on Kieselgel 60 Si 60 silica gel (40-63 mmo r6 3-200 mm) from Macherey-Nagel. TLC analyses were carried out on Merck DC Kieselgel 60 F-254 coated aluminum sheets.…”

Section: Resultsmentioning

confidence: 99%

New 3‐(Heteroaryl)‐2‐iminocoumarin‐based Borate Complexes: Synthesis, Photophysical Properties, and Rational Functionalization for Biosensing/Biolabeling Applications

Roubinet

Massif

Moreau

et al. 2015

Chemistry A European J

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Members of a series of boron difluoride complexes with 3-(heteroaryl)-2-iminocoumarin ligands bearing both a phenolic hydroxyl group (acting as a fluorogenic center) and an N-aryl substituent (acting as a stabilizing moiety) have been synthesized in good yields by applying a straightforward two-step method. These novel fluorogenic dyes belong to the family of "Boricos" (D. Frath et al., Chem. Commun.- 2013, 49, 4908-4910) and are the first examples of phenol-based fluorophores of which the photophysical properties in the green-yellow spectral range are dramatically improved by N,N-chelation of a boron atom. Modulation of their fluorescence properties through reversible chemical modification of their phenol moieties has been demonstrated by the preparation of the corresponding 2,4-dinitrophenyl (DNP) ethers, which led to a dramatic "OFF-ON" fluorescence response upon reaction with thiols. Additionally, to expand the scope of these "7-hydroxy-Borico" derivatives, particularly in biolabeling, amine or carboxylic acid functionalities amenable to (bio)conjugation have been introduced within their scaffold. Their utility has been demonstrated in the preparation of fluorescent bovine serum albumin (BSA) conjugates and "Borico"-DOTA-like scaffolds in an effort to design novel monomolecular multimodal fluorescence- radioisotope imaging agents.

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Section: Resultsmentioning

confidence: 99%

New 3‐(Heteroaryl)‐2‐iminocoumarin‐based Borate Complexes: Synthesis, Photophysical Properties, and Rational Functionalization for Biosensing/Biolabeling Applications

Roubinet

Massif

Moreau

et al. 2015

Chemistry A European J

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“…In previous works dealing with the modeling of spectroscopic properties of BODIPY derivatives, the PCM-TD-DFT protocol enabled to obtain theoretical results in good qualitative agreement with experimental data, but generally too large on the absolute energy scale [18][19][20][21] . Here, 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Next, we carried out the same study by TD-DFT methodologies incorporating the solvent effects via the state specific (SS-TD Figure 2, one clearly sees that TD-DFT overestimates the experimental AFCP energies, irrespective of the selected solvent models, which was, as stated above, expected from previous simulations of fluoroborates 19,21 .…”

Section: Discussionmentioning

confidence: 99%

“…E 0-0 can be defined as the difference of the excited-state (ES) and ground-state (GS) energies taken at their respective optimal geometries and corrected for the difference of zero-point vibrational effects between the two states. E 0-0 can be accessed computationally and compared to the experimental absorption and fluorescence crossing point (AFCP, see Computational Details) 18 . Second, we simulate the vibrationally resolved spectra within the harmonic approximation on the basis of vibrational signatures.…”

Section: Introductionmentioning

confidence: 99%

“…E 0‑0 can be accessed computationally and compared to the experimental absorption and fluorescence crossing point (AFCP; see Computational Details). Second, we simulate the vibrationally resolved spectra within the harmonic approximation on the basis of vibrational signatures. In this context, we note that vibronic TD-DFT calculations have been previously successfully employed to obtain the band shapes of (aza-)BODIPYs, BODIPY–cyanines, and ladder-type-π-conjugated dyes .…”

Section: Introductionmentioning

confidence: 99%

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Combined TD-DFT-SOS-CIS(D) Study of BOPHY Derivatives with Potential Application in Biosensing

et al. 2017

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A set of 13 bis(difluoroboron)-1,2-bis((pyrrol-2-yl)methylene)hydrazine (BOPHY) dyes is studied through a hybrid time-dependent density functional theory (TD-DFT)-scaled opposite spin-configuration interaction singles with a double correction [SOS-CIS(D)] approach accounting for solvent effects, to shed light onto the structure-property relationships of these recently developed chromophores. In the first step, we calculate the absorption-fluorescence crossing points with refined TD-DFT models considering the influences of both vibrational and solvent contributions. We found that the systematic overestimation of the 0-0 energies is effectively reduced by combining polarizable continuum model-TD-DFT with a scaled opposite spin-configuration interaction singles with a double correction [SOS-CIS(D)]. Next, for a representative system, the vibrationally resolved spectrum within the harmonic approximation is computed on the basis of TD-DFT vibrational signatures and an excellent match with experiment is found. Finally, the influence of different lateral groups on the spectroscopic properties is rationalized by investigating charge transfer parameters and examining electronic density difference maps. It is found that one can tune the position of the absorption/emission maxima by a judicious choice of the lateral substituents or by using π-extended segments. The largest absorption and emission wavelengths as well as the largest Stokes shifts are obtained for BOPHYs containing strong electron-donor dimethylaminophenyl groups attached to the α-positions of the pyrrole units through vinyl linkers, making these chromophores promising candidates for bioluminescence applications.

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“…[24][25][26][27] In turn, these allow researchers to efficiently explore the potential energy surface of the excited states, to obtain uorescence wavelengths and Stokes shis, as well as to rapidly account for the most important vibronic couplings. Whilst these methodologies have already found applications for "real-life" structures, [28][29][30][31][32][33][34][35][36][37][38][39][40] they remain oen unused by non-specialists. In the present work, we illustrate the applications of these new approaches taking as working examples several structures that have appeared in organic chemistry journals.…”

Section: Introductionmentioning

confidence: 99%