A detailed theoretical study on the excited‐state hydrogen‐bonding dynamics and the proton transfer mechanism for a novel white‐light fluorophore

Gao, Haiyan; Yang, Guang; Jia, Min; Song, Xiaoyan; Zhang, Chenglong; Yang, Dapeng

doi:10.1002/jccs.201800045

Cited by 5 publications

(2 citation statements)

References 65 publications

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“…The geometric structures of reactants (R), transition states (TSs), and products (P) in the gas and solution phase at the DFT-B3LYP [42] level was optimized using basis set 6-311++G (d, p) [43] and Gaussian 09 software. [44] The accuracy of the B3LYP method for studies with interactions such as hydrogen bonding (HB) and proton transfer has previously been proved [45][46][47] and CAM-B3LYP single point energy was performed to confirm the energetic results from the B3LYP. Frequency calculations were also performed at the same computational level to determine harmonic frequencies, thermodynamic functions, and TSs imaginary frequencies.…”

Section: Calculationsmentioning

confidence: 99%

Solvent effects on direct and indirect tautomerism of pyrimidin‐2(1H)‐one/pyrimidin‐2‐ol

Hosseini

2022

J of Physical Organic Chem

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A theoretical study at the B3LYP/6‐311++G(d,p) level on tautomeric conversion of pyrimidin‐2(1H)‐one (PYH) to pyrimidin‐2‐ol (PY) was performed. Two mechanisms have been considered for this processes: (i) one in which the hydrogen is directly transferred, mechanisms A, through TS12 and (ii) another one in which a double hydrogen transfer takes place via TS1122, by formation of the corresponding dimer, mechanisms B. The results associated with the gas phase reveal that overcame to TS12 needs high activation free energies of 34.47 kcal/mol, as a consequence of the strain associated with the formation of the four‐membered transition state, while overcame to TS1122 requires much lower activation free energies, 4.97 kcal/mol. The effect of solvent on the studied tautomerization in implicit, explicit, and a combination of both implicit and explicit solvation models in various media (protic and aprotic polar solvents) has been considered. The results show that the use of a protic polar solvent reduces the energy barrier of the corresponding transition states in a very significant amount.

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Section: Calculationsmentioning

confidence: 99%

Solvent effects on direct and indirect tautomerism of pyrimidin‐2(1H)‐one/pyrimidin‐2‐ol

Hosseini

2022

J of Physical Organic Chem

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“…Even though the fluoride anion plays significant roles in nature, the excessive fluoride could lead to environmental pollution, kidney damage, immune system disruption, and even cancer . Because of the own apparent advantages (i.e., high sensitivity, low cost, high selectivity, rapid implementation, and so on) of the fluorescent sensors, the developing of novel fluoride anion chemosensors attracts lots of attention in recent years. In fact, most of the current fluoride anion sensors have been developed using tert‐butyldimethylsilyl (TBDMS) or tert‐butyldiphenylsilyl (TBDPS) groups.…”

Section: Introductionmentioning

confidence: 99%

The investigation of proton transfer and fluorescence‐sensing mechanisms of [2‐(2‐hydroxy‐phenyl)‐1H‐benzoimidazol‐5‐yl]‐phenyl‐methanone

Yang

Zhao

Jia

et al. 2019

J Chinese Chemical Soc

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Given the tremendous potential of fluorescence sensors in recent years, in this present work, we theoretically explore a novel fluorescence chemosensor [2-(2-Hydroxy-phenyl)-1H-benzoimidazol-5-yl]-phenyl-methanone (HBPM) about its excited state behaviors and probe-response mechanism. Using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, we explore the S 0 -state and S 1 -state hydrogen bond dynamical behaviors and confirm that the strengthening intramolecular hydrogen bond in the S 1 state may promote the excited state intramolecular proton transfer (ESIPT) reaction. In view of the photoexcitation process, we find that the charge redistribution around the hydroxyl moiety plays important roles in providing driving force for ESIPT. And the constructed potential energy curves further verify that the ESIPT process of HBPM should be ultrafast. That is the reason why the normal HBPM fluorescence cannot be detected in previous experiment. Furthermore, with the addition of fluoride anions, the exothermal deprotonation process occurs spontaneously along with the intermolecular hydrogen bond O-HÁ Á ÁF. It reveals the uniqueness of detecting fluoride anions using HBPM molecules. As a whole, the fluoride anions inhibit the initial ESIPT process of HBPM, which results in different fluorescence behaviors. This work presents the clear ESIPT process and fluoride anion-sensing mechanism of a novel HBPM chemosensor. K E Y W O R D Sdeprotonation, fluoride-triggered fluorescence response, intra and interhydrogen bonds, potential energy curves

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Fluorescent Terpolymers via In Situ Allocation of Aliphatic Fluorophore Monomers: Fe(III) Sensor, High‐Performance Removals, and Bioimaging

Mahapatra

Dutta

Roy

et al. 2019

Adv Healthcare Materials

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Herein, purely aliphatic intrinsically fluorescent terpolymers, i.e., 1 and 2, are synthesized through one-pot solution polymerization via N-H functionalized and multi C-C/C-N coupled in situ protrusion of fluorescent monomers using two nonemissive monomers. These scalable terpolymers are suitable for highly selective Fe(III) sensing, high-performance exclusion of Fe(III), logic function and the imaging of normal mammalian Madin-Darby canine kidney and human osteosarcoma cancer cell lines. The structures of terpolymers, in situ attachment of fluorescent monomers, clusteroluminescence, adsorption-mechanism, and cell-imaging abilities are understood via unadsorbed and/or adsorbed microstructural analyses using 1 H/ 13 C NMR, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy, atomic absorption spectroscopy, thermogravimetric analysis, high-resolution transmission electron microscopy, dynamic light scattering, fluorescence imaging, and fluorescence lifetime. The geometries, electronic structures, location of fluorophores, and singlet-singlet absorption and emission of terpolymers are examined using density functional theory (DFT) and time-dependent DFT. For the precise identification of fluorophores, transition from occupied natural transition orbitals (NTOs) to unoccupied NTOs is computed. For 1/2, limit of detection (LOD) values and adsorption capacities are 6.0 × 10 −7 /8.0 × 10 −7 m and 147.82/120.56 mg g −1 at pH i = 7.0 and 303 K, respectively. The overall properties of 1 are more advantageous compared to 2 in sensing, cell imaging, and adsorptive exclusion of Fe(III).

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A detailed theoretical study on the excited‐state hydrogen‐bonding dynamics and the proton transfer mechanism for a novel white‐light fluorophore

Cited by 5 publications

References 65 publications

Solvent effects on direct and indirect tautomerism of pyrimidin‐2(1H)‐one/pyrimidin‐2‐ol

Solvent effects on direct and indirect tautomerism of pyrimidin‐2(1H)‐one/pyrimidin‐2‐ol

The investigation of proton transfer and fluorescence‐sensing mechanisms of [2‐(2‐hydroxy‐phenyl)‐1H‐benzoimidazol‐5‐yl]‐phenyl‐methanone

Fluorescent Terpolymers via In Situ Allocation of Aliphatic Fluorophore Monomers: Fe(III) Sensor, High‐Performance Removals, and Bioimaging

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