Fluoride anion sensing mechanism of a BODIPY-linked hydrogen-bonding probe.

The sensing mechanism of a fluoride-anion probe BODIPY-amidothiourea (1c) has been elucidated through the density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The theoretical study indicates that in the DMSO/water mixtures the fluorescent sensing has been regulated by the fluoride complex that formed between the probe 1c/two water molecules and the fluoride anion, and the excited-state intermolecular hydrogen bond (H-B) plays an important role in the fluoride sensing mechanism. In the first excited state, the H-Bs of the fluoride complex 1cFH2 are overall strengthened, which induces the weak fluorescence emission. In addition, molecular orbital analysis demonstrates that 1cFH2 has more obvious intramolecular charge transfer (ICT) character in the S1 state than 1cH2 formed between the probe 1c and two water molecules, which also gives reason to the weaker fluorescence intensity of 1cFH2 . Further, our calculated UV-vis absorbance and fluorescence spectra are in accordance with the experimental measurements. © 2018 Wiley Periodicals, Inc.

DFT/TDDFT Study on the Sensing Mechanism of a Fluorescent Probe for Hydrogen Sulfide: Excited State Intramolecular Proton Transfer Coupled Twisted Intramolecular Charge Transfer.

By using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, the sensing mechanism of a fluorescent probe 2-(2-hydroxyphenyl) benzothiazole (HBT) derivative HBTPP-S for hydrogen sulfide has been thoroughly studied. The thiolysis reaction has a moderate reaction barrier of 18.40 kcal mol-1, which indicates that the hydrogen sulfide sensing process has a favorable response speed. Because of the nonradiative donor-excited photoinduced electron transfer (d-PET, fluorophore as the electron donor) from the excited HBTPP group to the electron-withdrawing 2,4-dinitrophenyl group, as well as the inhibition of the proton transfer (PT) and the excited state intramolecular proton transfer (ESIPT) process by 2,4-dinitrophenyl group, the probe HBTPP-S is essentially nonfluorescent. On the other hand, the added hydrogen sulfide induces the thiolysis of the 2,4-dinitrophenyl ether bond, and then the thiolysis product HBTPP comes into existence. The theoretically simulated potential energy surface demonstrates that without the electron-withdrawing 2,4-dinitrophenyl group, the thiolysis product HBTPP undergoes the excited state intramolecular proton transfer (ESIPT) coupled twisted intramolecular charge transfer (TICT) processes in the first excited state. The absence of the d-PET and the process mentioned above may explain the significant fluorescent turn-on response and large Stokes shift of the thiolysis product HBTPP.

Photoinduced hydrogen-bonding dynamics.

Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bonding formed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water.

Reversibly monitoring oxidation and reduction events in living biological systems: Recent development of redox-responsive reversible NIR biosensors and their applications in in vitro/in vivo fluorescence imaging.

Reactive oxygen species (ROS) and changes in their redox cycles have great therapeutic potential for treating serious redox-related human diseases such as acute and chronic inflammation, diabetes, cancer and neurodegenerative disorders. This article presents a survey of the recently (2011-2016) developed NIR small-molecule biosensors for reversibly monitoring oxidation and reduction events in living cells and small animals through in vitro/in vivo fluorescence imaging. Emission and absorption profile, design strategy and fluorescence sensing mechanism, ROS selectivity and sensitivity, reversibility, ability of subcellular location and cytotoxicity are discussed for the NIR small-molecule biosensors capable of quantitatively, continuously and reversibly detecting transient ROS burst and redox changes at cellular level.

Sensing mechanism for biothiols chemosensor DCO: roles of excited-state hydrogen-bonding and intramolecular charge transfer.

The biothiols sensing mechanism of (E)-7-(diethylamino)-3-(2-nitrovinyl)-2H-chromen-2-one (DCO) has been investigated using the density functional theory (DFT) and time-dependent DFT methods. The theoretical results indicate that the excited-state intermolecular hydrogen bonding (H-B) plays an important role for the biothiols sensing mechanism of the fluorescence sensor DCO. Multiple H-B interaction sites exist in DCO and in its Michael addition product DCOT, which then induce the formation of the H-B complexes with water molecules, DCOH2 and DCOTH4. In the first excited state, the intermolecular H-Bs between water molecule and DCO in DCOH2 are cooperatively and generally strengthened and thus induced the weak fluorescence emission of DCO, while the cooperative H-Bs between water molecule and DCOT in DCOTH4 are overall weakened and thus responsible for the enhanced fluorescence emission of DCOT. Moreover, the theoretical results suggest that the blue shift of the UV-Vis absorption spectrum of DCOT can be attributed to the relatively weak excited-state intramolecular charge transfer in DCOT compared to DCO.

Sensing mechanism for a fluoride chemosensor: invalidity of excited-state proton transfer mechanism.

Our density functional theory (DFT)/time-dependent DFT calculations for the fluoride anion sensor, 5,7-dibromo-8-tert-butyldimethylsilyloxy-2-methylquinoline (DBM), suggested a different sensing mechanism from the experimentally proposed one (Chem. Commun., 2011, 47, 7098). Instead of the formation of fluoride-hydrogen-bond complex (DBMOHF) and excited-state proton transfer mechanism, the theoretical results predicted a sensing mechanism based on desilylation reaction and intramolecular charge transfer (ICT). The fluoride anion reacted with DBM and formed an anion (DBMO), with the ICT causing a red shift in the absorbance and emission spectra of the latter. The calculated vertical excitation energies in the ground and first excited states of both DBM and DBMO, as well as the calculated (1)H NMR spectra, significantly reproduced the experimental measurements, providing additional proofs for our proposed sensing mechanism for DBM.

A highly luminescent terbium-organic framework for reversible detection of mercury ions in aqueous solution.

A new organic-lanthanide framework [TbL1.5(H2O)2]·H2O (1) [H2L = 5-(3'-carboxylphenyl)nicotinic acid] was synthesized. Its structure was determined by single crystal X-ray diffraction. The complex was characterized by PXRD, FT-IR, fluorescence as well as TGA, and features a 3D framework with a 1D channel and exhibits exceptionally high thermal stability up to 440 °C in air. Furthermore, it displays highly sensitive and selective luminescence quenching to Hg(2+) in aqueous solution. The result of a reversible sensing experiment showed complex 1 could be reusable at least 5 times.

Fluoride anion sensing mechanism of 2-ureido-4[1H]-pyrimidinone quadruple hydrogen-bonded supramolecular assembly: photoinduced electron transfer and partial configuration change.

The fluoride anion sensing mechanism of 6-methyl-5-(9-methylene-anthracene)-(2-butylureido-4[1H]-pyrimidinone) (AnUP) has been investigated using the DFT/TDDFT method. The theoretical results indicate that the proton of the N3-H3 group in pyrimidine moiety is captured by the added fluoride anion and then deprotonated. The calculated vertical excitation energies of AnUP-dimer and its deprotonated form agree well with the experimental results. The molecular orbital analysis demonstrates that the first excited state (S1) of AnUP-dimer is a local excited state with a π-π* transition, whereas for the deprotonated form, S1 is a completely charge-separation state and is responsible for the photoinduced electron transfer (PET) process. The PET process from anthracene to the pyrimidine moiety leads to the fluorescence quenching.

Quantum dynamical study of the electronic nonadiabaticity in the D + DBr → Br(Br*) + D2 reaction on new diabatic potential energy surfaces.

A set of diabatic potential energy surfaces, that describe the D + DBr → Br(P(1/2,3/2)) + D(2) reaction, is constructed based on MRCI/aug-cc-pV5Z calculations at 29,526 grid points. Time-dependent wave packet calculations are performed for ground-state DBr initially with collision energies up to 2.0 eV to investigate possible electronic nonadiabaticity in this reaction. Reaction probabilities and integral cross sections are calculated. The results show negligible nonadiabatic effects for the title reaction in the energy range considered here, confirming experimental work of Zare and co-workers. In addition, the calculated thermal rate constants are in good agreement with experimental ones.

TD-DFT study on the excited-state proton transfer in the fluoride sensing of a turn-off type fluorescent chemosensor based on anthracene derivatives.

The sensing mechanism for fluoride chemosensor based on anthracene structure has been investigated by DFT and TDDFT methods. The results show that the similar geometries in S(0) and S(1) states in the absence of the fluoride anion induce the local excited (LE) state over the anthracene moiety, which is responsible for the strong fluorescence. The fluorescence quenching phenomenon for F-coordinated complex can be explained by the photoinduced electron transfer (PET) process from benzylic amide to anthracene moiety. Moreover, the strong electronegativity for fluoride anion in the F-complex constructs the intermolecular hydrogen bond of N-H…F in the ground state. In contrast, the upper proton in the urea group close to phenyl group prefers to bind fluoride anion in S(1) state of the F-complex, and it presents excited-state proton transfer (ESPT) to form another hydrogen bond like N…H-F, which has been confirmed by natural bond orbital (NBO) analysis and the potential energy curve of S(1) state for the function of N-H bond. In this novel and efficient fluoride fluorescent chemosensor based on anthracene, the anthracene moiety is regarded as not only the fluorescent source, but the template for introducing the binding sites for fluoride anion.

Intensity enhancement in the molecular ionization and dissociation dynamics in the presence of noise.

The ionization and the dissociation of the diatomic molecular ion H(2)(+) have been investigated within a scheme where a noise field is added to an intense infrared laser field. The results show that both the ionization and the dissociation probabilities are enhanced with the introduction of the additional noise (the Gaussian white noise or the color noise) field. Further, by tuning the noise intensity and the delay time between the laser and the noise, a stochastic resonancelike curve is observed for the ionization or the dissociation dynamics, showing the existence of an optimal noise intensity and delay time for the given laser field.

Theoretical study on photoisomerization effect with a reversible nonlinear optical switch for dithiazolylarylene.

DFT and TDDFT methods have been performed to investigate the photoisomerization effect for dithiazolylarylene on solution. The weak S···N interaction and CH···N hydrogen bond restrain the rotation of the side-chain thiazolyl ring in open-isomer 1a, the higher stability of which prefers to show a high quantum yield of photoisomerization. The calculated UV-Vis spectrum at around 320 nm for open-isomer 1a is bathochromically shifted to 647 nm for closed-isomer 1b, in excellent agreement with the experimental photochromic phenomenon. The electron transition in ECD (electron circular dichroism) spectra for closed-isomer 1b with two chiral carbon atoms is dominated by ICT (intramolecular charge transition) and LE (local excitation) corresponding to one positive (440 nm) and one negative Cotton effect (650 nm), respectively, where the two chiral carbon atoms play a slight role in these transitions. The PES in the S(1) and S(0) states, respectively, indicates that the cyclization reaction from open-isomer 1a to closed-isomer 1b is allowed in the photoexcited state with high-conversion quantum efficiency, while it is forbidden in the thermodynamic process. In addition, the second-order nonlinear optical response for closed-isomer 1b is nearly six times larger than that for open-isomer 1a. It is also confirmed that the photoirradiation evokes the photoisomerization character to show dramatic difference in the second-order NLO response, which can be applied to designing photochromic materials and reversible NLO switches.

A new luminescent terbium 4-methylsalicylate complex as a novel sensor for detecting the purity of methanol.

A new dinuclear terbium complex [Tb(2)(4-msal)(6)(H(2)O)(4)]·6H(2)O (1) (4-msal = 4-methylsalcylate) was synthesized. Its structure was determined by single crystal X-ray diffraction, and the complex was characterized by PXRD, FT-IR, fluorescence, TGA and DTA. Complex 1 exists as discrete molecules that are linked by extensive O-H … O hydrogen bonds into a 3D network. The luminescence lifetimes of 3 µM methanol solution and solid sample of 1 are 1.321 and 1.009 ms, respectively. The quantum yield of solid sample is 6.0%. The luminescence quenched more than 50% when 3% (vol/vol) different impurities (acetone, acetonitrile, chloroform, dichloromethane, dioxane, DMF, DMSO, ethanol, ether, ethyl acetate, glycol, H(2)O, hexane, TEA, THF and toluene or their mixture) were added. The inverse linear relationship between the Lg value of fluorescence intensity and the volume ratio of the minor component (to a maximum of 20%) is interpreted in terms of LgI = a-bX (I: luminescence intensity; X: volume ratio of impurities in methanol; a, b are constants). So 1 is a potential luminescent sensor for analyzing the purity of methanol.

Reaction mechanism and chemoselectivity of intermolecular cycloaddition reactions between phenyl-substituted cyclopropenone ketal and methyl vinyl ketone.

In this paper, the mechanisms of the intermolecular [3+2] and [1+2] cycloaddition reactions of 1,1/1,3-dipolar π-delocalized singlet vinylcarbenes, which is obtained from cyclopropenone, with an electron-deficient C═O or C═C dipolarophile, to generate five-membered ring products are first disclosed by the density functional theory (DFT). Four reaction pathways, including two concerted [3+2] cycloaddition reaction pathways and two stepwise reaction pathways (an initial [1+2] cycloaddition and then a rearrangement from the [1+2] cycloadducts to the final [3+2] cycloadducts), are investigated at the B3LYP/6-31G(d,p) level of theory. The calculated results reveal that, in contrast to the concerted C═O [3+2] cycloaddition reaction pathway, which is 7.1 kcal/mol more energetically preferred compared with its stepwise reaction pathway, the C═C dipolarophile favors undergoing [1+2] cycloaddition rather than concerted [3+2] cycloaddition (difference of 5.3 kcal/mol). The lowest free energy barrier of the C═O concerted [3+2] cycloaddition reaction pathway shows that it predominates all other reaction pathways. This observation is consistent with the finding that the C═O [3 + 2] cycloadduct is the main product under experimental conditions. In addition, natural bond orbital second-order perturbation charge analyses are carried out to explain the preferred chemoselectivity of C═O to the C═C dipolarophile and the origins of cis-stereoselectivity for C═C [1+2] cycloaddition. Solvent effects are further considered at the B3LYP/6-31G(d,p) level in the solvents CH(3)CN, DMF, THF, CH(2)Cl(2), toluene, and benzene using the PCM model. The results indicate that the relative reaction trends and the main products are insensitive to the polarity of the reaction solvent.

Nonadiabatic quantum reactive scattering of the OH(A 2Σ+) + D2.

The seams of conical intersection exist between the ground (1 (2)A(')) and the first-excited (2 (2)A(')) electronic potential energy surfaces (PESs) of OH(A (2)Σ(+),X (2)Π) + H(2) system. This intersection induces the nonadiabatic quenching of OH(A (2)Σ(+)) by D(2). We present nonadiabatic quantum dynamics study for OH(A (2)Σ(+)) + D(2) on new five-dimensional coplanar PESs. The ab initio calculations of PESs are based on multireference configuration interaction (MRCI)/aug-cc-pVQZ level. A back-propagation neural network is utilized to fit the PESs and nonadiabatic coupling. High degrees of rotational excitation of quenched OH(X (2)Π) products are found in nonreactive quenching channel, and the quenched D(2) products are vibrationally excited up to quantum number v(2) (')=8. The theoretical results of nonadiabatic time-dependent wave-packet calculation are in good agreement with the existing experimental data.

Quenching of OH(A(2)Sigma(+)) by H(2) through conical intersections: highly excited products in nonreactive channel.

Nonadiabatic quantum scattering calculations have been carried out for the reactive and nonreactive quenching of OH(A(2)Sigma(+)) in collisions with molecular H(2) on two new potential energy surfaces of the 1A' and 2A' states. Integral cross sections of the reactive and nonreactive quenching channels and the quantum state distributions of the nonreactive channel have been obtained. The theory reveals a high degree of rotational excitation of the quenched OH(X(2)II) products and vibrational excitation of the H(2) products. The calculated results are in good agreement with the existing experimental data. The topography of the potential energy surfaces in the conical intersection regions is provided in order to discuss the origin of the internal excitations of nonreactive products and the branching of the reactive and nonreactive channels.

Non-Born-Oppenheimer dynamics calculations using the coherent switching with decay of mixing method.

A theoretical investigation of the nonadiabatic processes that are involved in the full three-dimensional D+H(2), H+D(2), D(+)+H(2), and H(+)+D(2) reaction systems has been performed using the method of coherence switching with decay of mixing (CSDM) developed by Truhlar and coworkers. The electronic density matrix for each trajectory is fully coherent in the CSDM method, and a switching algorithm different to the original "decay of mixing" method is used to determine the pure state toward which the decoherent force drives the system. By solving the equations for the evolution of the electronic state populations along the semiclassical trajectory, the ensemble can present effective physical insight into nonadiabatic dynamics. The calculations for the D+H(2) and H+D(2) systems is based on the double many body expansion potential energy surface. The potential energy surface constructed by Kamisaka et al. is employed in the calculation of D(+)+H(2) and H(+)+D(2) reactions. The cross sections and the reaction probabilities for the total angular momentum J = 0 are calculated for all of these systems. The calculated results from the CSDM method are in good agreement with exact quantum mechanical calculations and experimental measurements.

Nonadiabatic effects in the H + H2 exchange reaction: accurate quantum dynamics calculations at a state-to-state level.

Real wave packet propagations were carried out on both a single ground electronic state and two-coupled-electronic states of the title reaction to investigate the extent of nonadiabatic effects on the distinguishable-atom reaction cross sections. The latest diabatic potential matrix of Abrol and Kuppermann [J. Chem. Phys. 116, 1035 (2002)] was employed in the present nonadiabatic quantum state-to-state scattering calculations over a total energy range-from threshold (the zero point of the reagent H(2)) to 3.0 eV. Based on the assumption that the hydrogen atoms are distinguishable in the collisions where the inelastic and elastic ones are excluded, no significant nonadiabatic effects have been found in the calculations of the full state-to-state integral and differential cross sections up to a total energy of 3.0 eV for product vibrational levels v(')=0, 1, 2, 3. Our results therefore confirm the recent and the previous studies of the geometric phase effects in H+H(2) employing a different diabatic double many-body expansion potential matrix or a different BKMP2 potential energy surface.

Effect of Coriolis coupling in chemical reaction dynamics.

It is essential to evaluate the role of Coriolis coupling effect in molecular reaction dynamics. Here we consider Coriolis coupling effect in quantum reactive scattering calculations in the context of both adiabaticity and nonadiabaticity, with particular emphasis on examining the role of Coriolis coupling effect in reaction dynamics of triatomic molecular systems. We present the results of our own calculations by the time-dependent quantum wave packet approach for H + D2 and F(2P3/2,2P1/2) + H2 as well as for the ion-molecule collisions of He + H2 +, D(-) + H2, H(-) + D2, and D+ + H2, after reviewing in detail other related research efforts on this issue.

Full six-dimensional nonadiabatic quantum dynamics calculation for the energy pooling reaction O(2)(a (1)Delta)+O(2)(a (1)Delta)-->O(2)(b (1)Sigma)+O(2)(X (3)Sigma).

Six new potential energy surfaces of four singlet states and two triplet states for the title oxygen molecule reaction along with the spin-orbit coupling among them have been constructed from the complete active space second-order perturbation theory with a 6-311+G(d) basis. Accurate integral cross sections are calculated with a full six-dimensional nonadiabatic time-dependent quantum wave packet method. The thermal rate constant based on the integral cross sections agrees well with the result of the experimental measurements, and the intersystem crossing effects are also discussed in this electronic energy-transfer process.