Theoretical Study on the Substituent Effect on the Excited‐State Proton Transfer in the 7‐Azaindole‐Water Derivatives

The first excited‐state proton transfer (ESPT ) in 7AI ‐H₂O complex and its derivatives, in which the hydrogen atom at the C₂ position in pyrrole ring was replaced by halogen atom X (X = F, Cl, Br), were studied at the TD ‐M06‐2X/6‐31 + G(d, p) level. The double proton transfer took place in a concerted but asynchronous protolysis pathway. The vibrational‐mode selectivity of excited‐state double proton transfer in the model system was confirmed. The specific vibrational‐mode could shorten the reaction path and accelerate the reaction rate. The substituent effects on the excited‐state proton transfer process were discussed. When the H atom at C₂ position in 7AI ‐H₂O complex was replaced by halogen atom, some geometrical parameters changed obviously, the barrier height of ESDPT reduced, and the asynchronicity of proton transfer enlarged. The above changes correlated with the Pauling electronegativity of halogen atom.     

Theoretical insights into the excited‐state process of 4‐tert‐butyl‐2‐(5‐(5‐tert‐butyl‐2‐methoxyphenyl)thiazolo[5,4‐d]thiazol‐2‐yl)‐phenol

In this paper, we theoretically explore the motivation and behaviors of the excited‐state intramolecular proton transfer (ESIPT) reaction for a novel white organic light‐emitting diode (WOLED) material 4‐tert‐butyl‐2‐(5‐(5‐tert‐butyl‐2‐methoxyphenyl)thiazolo[5,4‐d]thiazol‐2‐yl)‐phenol (t‐MTTH). The “atoms in molecules” (AIM) method is adopted to verify the formation and existence of the hydrogen bond O? H···N. By analyzing the excited‐state hydrogen bonding behaviors via changes in the chemical bonding and infrared (IR) vibrational spectra, we confirm that the intramolecular hydrogen bond O? H···N should be getting strengthened in the first excited state in four kinds of solvents, thus revealing the tendency of ESIPT reaction. Further, the role of charge‐transfer interaction is addressed under the frontier molecular orbitals (MOs), which depicts the nature of the electronic excited state and supports the ESIPT reaction. Also, the electron distribution confirms the ESIPT tendency once again. The scanned and optimized potential energy curves according to variational O? H coordinate in the solvents demonstrate that the proton transfer reaction should occur in the S₁ state, and the potential energy barriers along with ESIPT direction support this reaction. Based on the excited‐state behaviors reported in this work, the experimental spectral phenomenon has been reasonably explained.     

On the Mechanisms of Hydrogen‐Atom Transfer from Water to the Heteronuclear Oxide Cluster [Ga2Mg2O5].+: Remarkable Electronic Structure Effects

Mechanistic insight into the homolytic cleavage of the O? H bond of water by the heteronuclear oxide cluster [Ga₂Mg₂O₅]^.+ has been derived from state‐of‐the‐art gas‐phase experiments in conjunction with quantum chemical calculations. Three pathways have been identified computationally. In addition to the conventional hydrogen‐atom transfer (HAT) to the radical center of a bridging oxygen atom, two mechanistically distinct proton‐coupled electron‐transfer (PCET) processes have been identified. The energetically most favored path involves initial coordination of the incoming water ligand to a magnesium atom followed by an intramolecular proton transfer to the lone‐pair of the bridging oxygen atom. This step, which is accomplished by an electronic reorganization, generates two structurally equivalent OH groups either of which can be liberated, in agreement with labeling experiments.     

Computational studies on electron and proton transfer in phenol‐imidazole‐base triads

The electron and proton transfer in phenol‐imidazole‐base systems (base = NH₂^? or OH^?) were investigated by density‐functional theory calculations. In particular, the role of bridge imidazole on the electron and proton transfer was discussed in comparison with the phenol‐base systems (base = imidazole, H₂O, NH₃, OH^?, and NH₂^?). In the gas phase phenol‐imidazole‐base system, the hydrogen bonding between the phenol and the imidazole is classified as short strong hydrogen bonding, whereas that between the imidazole and the base is a conventional hydrogen bonding. The n value in spⁿ hybridization of the oxygen and carbon atoms of the phenolic CO sigma bond was found to be closely related to the CO bond length. From the potential energy surfaces without and with zero point energy correction, it can be concluded that the separated electron and proton transfer mechanism is suitable for the gas‐phase phenol‐imidazole‐base triads, in which the low‐barrier hydrogen bond is found and the delocalized phenolic proton can move freely in the single‐well potential. For the gas‐phase oxidized systems and all of the triads in water solvent, the homogeneous proton‐coupled electron transfer mechanism prevails. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

UV/Vis Action Spectroscopy and Structures of Tyrosine Peptide Cation Radicals in the Gas Phase

We report the first application of UV/Vis photodissociation action spectroscopy for the structure elucidation of tyrosine peptide cation radicals produced by oxidative intramolecular electron transfer in gas‐phase metal complexes. Oxidation of Tyr‐Ala‐Ala‐Ala‐Arg (YAAAR) produces Tyr‐O radicals by combined electron and proton transfer involving the phenol and carboxyl groups. Oxidation of Ala‐Ala‐Ala‐Tyr‐Arg (AAAYR) produces a mixture of cation radicals involving electron abstraction from the Tyr phenol ring and N‐terminal amino group in combination with hydrogen‐atom transfer from the C_α positions of the peptide backbone.     

Electrospun Nanofibers from a Tricyanofuran‐Based Molecular Switch for Colorimetric Recognition of Ammonia Gas

A chromophore based on tricyanofuran (TCF) with a hydrazone (H) recognition moiety was developed. Its molecular‐switching performance is reversible and has differential sensitivity towards aqueous ammonia at comparable concentrations. Nanofibers were fabricated from the TCF–H chromophore by electrospinning. The film fabricated from these nanofibers functions as a solid‐state optical chemosensor for probing ammonia vapor. Recognition of ammonia vapor occurs by proton transfer from the hydrazone fragment of the chromophore to the ammonia nitrogen atom and is facilitated by the strongly electron withdrawing TCF fragment. The TCF–H chromophore was added to a solution of poly(acrylic acid), which was electrospun to obtain a nanofibrous sensor device. The morphology of the nanofibrous sensor was determined by SEM, which showed that nanofibers with a diameter range of 200–450 nm formed a nonwoven mat. The resultant nanofibrous sensor showed very good sensitivity in ammonia‐vapor detection. Furthermore, very good reversibility and short response time were also observed.     

Electron Transfer between Hydrogen‐Bonded Pyridylphenols and a Photoexcited Rhenium(I) Complex

Two pyridylphenols with intramolecular hydrogen bonds between the phenol and pyridine units have been synthesized, characterized crystallographically, and investigated by cyclic voltammetry and UV/Vis spectroscopy. Reductive quenching of the triplet metal‐to‐ligand charge‐transfer excited state of the [Re(CO)₃(phen)(py)]⁺ complex (phen=1,10‐phenanthroline, py=pyridine) by the two pyridylphenols and two reference phenol molecules is investigated by steady‐state and time‐resolved luminescence spectroscopy, as well as by transient absorption spectroscopy. Stern–Volmer analysis of the luminescence quenching data provides rate constants for the bimolecular excited‐state quenching reactions. H/D kinetic isotope effects for the pyridylphenols are on the order of 2.0, and the bimolecular quenching reactions are up to 100 times faster with the pyridylphenols than with the reference phenols. This observation is attributed to the markedly less positive oxidation potentials of the pyridylphenols with respect to the reference phenols (≈0.5 V), which in turn is caused by proton coupling of the phenol oxidation process. Transient absorption spectroscopy provides unambiguous evidence for the photogeneration of phenoxyl radicals, that is, the overall photoreaction is clearly a proton‐coupled electron‐transfer process.     

Competing Excited-State Hydrogen and Proton-Transfer Processes in 6-Azaindole-S3,4 and 2,6-Diazaindole-S3,4 Clusters (S=H2O,NH3)

Excited state hydrogen (ESHT) and proton (ESPT) transfer reaction pathways in the three and four solvent clusters of 6-azaindole (6AI-S_3,4) and 2,6-diazaindole (26DAI-S_3,4)(S=H₂O, NH₃) were computationally investigated to understand the fate of photo-excited biomolecules. The ESHT energy barriers in (H₂O)₃ complexes (39.6–41.3 kJmol⁻¹) were decreased in (H₂O)₄ complexes (23.1–20.2 kJmol⁻¹). Lengthening the solvent chain lowered the barrier because of the relaxed transition states geometries with reduced angular strains. Replacing the water molecule with ammonia drastically decreased the energy barriers to 21.4–21.3 kJmol⁻¹ in (NH₃)₃ complexes and 8.1–9.5 kJ mol⁻¹ in (NH₃)₄ complexes. The transition states were identified as H_a atom attached to the first solvent molecule. The formation of stronger hydrogen bonds in (NH₃)_3,4 complexes resulted in facile ESHT reaction than that in the (H₂O)_3,4 complexes. The ESPT energy barriers in 6AI-S_3,4 and 26DAI-S_3,4 were found to range between 40–73 kJmol⁻¹. The above values were significantly higher than that of the ESHT processes and hence are considered as a minor channel in the process. The effect of N(2) insertion was explored for the very first time in the isolated solvent clusters using local vibrational mode analysis. In DAI-S₄, the higher K_a(H_a⋯S_a) values depicted the increased photoacidity of the N(1)-H_a group which may facilitate the hydrogen transfer reaction. However, the increased N(6)⋯H_b bond length elevated the reaction barriers. Therefore, in the ESHT reaction channel, the co-existence of two competing factors led to a marginal/no change in the overall energy barriers due to the N(2) insertion. In the ESPT reaction pathway, the energy barriers showed notable increase upon N(2) insertion because of the increased N(6)⋯H_b bond length.     

Water Molecules Gating a Photoinduced One‐Electron Two‐Protons Transfer in a Tyrosine/Histidine (Tyr/His) Model of Photosystem II

We investigate a biomimetic model of a Tyr_Z/His₁₉₀ pair, a hydrogen‐bonded phenol/imidazole covalently attached to a porphyrin sensitizer. Laser flash photolysis in the presence of an external electron acceptor reveals the need for water molecules to unlock the light‐induced oxidation of the phenol through an intramolecular pathway. Kinetics monitoring encompasses two fast phases with distinct spectral properties. The first phase is related to a one‐electron transfer from the phenol to the porphyrin radical cation coupled with a domino two‐proton transfer leading to the ejection of a proton from the imidazole–phenol pair. The second phase concerns conveying the released proton to the porphyrin N₄ coordinating cavity. Our study provides an unprecedented example of a light‐induced electron‐transfer process in a Tyr_Z/His₁₉₀ model of photosystem II, evidencing the movement of both the phenol and imidazole protons along an isoenergetic pathway.     

Regioselective Long‐Range Proton Transfer in New Rifamycin Antibiotics: A Process in which Crown Ethers Act as Stronger Brønsted Bases than Amines

Water‐mediated proton transfer in six new derivatives of 3‐formylrifamycin SV that contain crown, aza‐crown, and benzo‐crown ether rings were investigated by FTIR and NMR spectroscopy. ¹H–¹H COSY couplings provide evidence for the formation of zwitterionic structures of the aza‐crown and crown ether derivatives of rifamycin, in which a proton from one of the phenolic groups is transferred to tertiary and secondary nitrogen atoms. The increased intensity of the continuous absorption in the mid‐infrared region together with the NMR data indicate proton transfer from the phenol group of the rifamycin core to the cavity of the benzo‐crown ether ring. This proton transfer is achieved by formation of hydronium (H₃O⁺) or Zundel ions (H₅O₂⁺), which form intermolecular hydrogen bonds with the oxygen atoms of the crown ether. DFT calculations are in agreement with the spectroscopic data and allow visualization of the structures of all new rifamycin derivatives, characterized by different intramolecular protonation sites.     

Mechanism for the Nonadiabatic Photooxidation of Benzene to Phenol: Orientation‐Dependent Proton‐Coupled Electron Transfer

An efficient catalytic one‐step conversion of benzene to phenol was achieved recently by selective photooxidation under mild conditions with 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) as the photocatalyst. Herein, high‐level electronic structure calculations in the gas phase and in acetonitrile solution are reported to explore the underlying mechanism. The initially populated ¹ππ* state of DDQ can relax efficiently through a nearby dark ¹nπ* doorway state to the ³ππ* state of DDQ, which is found to be the precursor state involved in the initial intermolecular electron transfer from benzene to DDQ. The subsequent triplet‐state reaction between DDQ radical anions, benzene radical cations, and water is computed to be facile. The formed DDQH and benzene‐OH radicals can undergo T₁→S₀ intersystem crossing and concomitant proton‐coupled electron transfer (PCET) to generate the products DDQH₂ and phenol. Two of the four considered nonadiabatic pathways involve an orientation‐dependent triplet PCET process, followed by intersystem crossing to the ground state (S₀). The other two first undergo a nonadiabatic T₁→S₀ transition to produce a zwitterionic S₀ complex, followed by a barrierless proton transfer. The present theoretical study identifies novel types of nonadiabatic PCET processes and provides detailed mechanistic insight into DDQ‐catalyzed photooxidation.     

Proton transfer in phenol–amine complexes: Phenol electronic effects on free energy profile in solution

Free energy profiles for the proton transfer reactions in hydrogen‐bonded complex of phenol with trimethylamine in methyl chloride solvent are studied with the reference interaction site model self‐consistent field method. The reactions in both the electronic ground and excited states are considered. The second‐order Møller‐Plesset perturbation (MP) theory or the second‐order multireference MP theory is used to evaluate the effect of the dynamical electron correlation on the free energy profiles. The free energy surface in the ground state shows a discrepancy with the experimental results for the related hydrogen‐bonded complexes. To resolve this discrepancy, the effects of chloro‐substitutions in phenol are examined, and its importance in stabilizing the ionic form is discussed. The temperature effect is also studied. In contrast to the ground state, the ππ^* excited state of phenol–trimethylamine complex exhibits the proton transfer reaction with a low barrier. The reaction is almost thermoneutral. This is attributed to the reduction of proton affinity of phenol by the ππ^* electronic excitation. We further examine the possibility of the electron–proton–coupled transfer in the ππ^* state through the surface crossing with the charge transfer type πσ^* state. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Enzymatic and catalytic reduction of dinitrogen to ammonia: Density functional theory characterization of alternative molybdenum active sites

We used density functional calculations to model dinitrogen reduction by a FeMo cofactor containing a central nitrogen atom and by a Mo‐based catalyst. Plausible intermediates, reaction pathways, and relative energetics in the enzymatic and catalytic reduction of N₂ to ammonia at a single Mo center are explored. Calculations indicate that the binding of N₂ to the Mo atom and the subsequent multiple proton–electron transfer to dinitrogen and its protonated species involved in the conversion of N₂ are feasible energetically. In the reduction of N₂ the Mo atom experiences a cycled oxidation state from Mo(IV) to Mo(VI) by nitrogenase and from Mo(III) to Mo(VI) by the molybdenum catalyst, respectively, tuning the gradual reduction of N₂. Such a wide range of oxidation states exhibited by the Mo center is crucial for the gradual reduction process via successive proton–electron transfer. Present results suggest that the Mo atom in the N‐centered FeMo cofactor is a likely alternative active site for dinitrogen binding and reduction under mild conditions once there is an empty site available at the Mo site. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Control over Excited State Intramolecular Proton Transfer and Photoinduced Tautomerization: Influence of the Hydrogen‐Bond Geometry

The influence of H‐bond geometry on the dynamics of excited state intramolecular proton transfer (ESIPT) and photoinduced tautomerization in a series of phenol‐quinoline compounds is investigated. Control over the proton donor–acceptor distance (d_DA) and dihedral angle between the proton donor–acceptor subunits is achieved by introducing methylene backbone straps of increasing lengths to link the phenol and quinoline. We demonstrate that a long d_DA correlates with a higher barrier for ESIPT, while a large dihedral angle opens highly efficient deactivation channels after ESIPT, preventing the formation of the fully relaxed tautomer photoproduct.     

Mass spectrometric studies on 17β-estradiol-17-fatty acid esters: Evidence for the formation of anion-dipole intermediates

The behaviour towards low collision energy processes (eV range) of [M  H]⁻ prepared under negative ion chemical ionization (NICI) ammonia conditions from 17β-estradiol-17-fatty acid esters has been investigated. From such bifunctional compounds containing two acidic sites (i.e. phenol and ester groups), two isomeric forms (i.e. phenoxide and enolate forms) characterize the [M  H]⁻ ion structures, whose distribution depends on the ion preparation mode. Here NICI (ammonia) provides both phenoxide and enolate forms as the [M  H]⁻ species. This behaviour contrasts with the regioselectivity observed for proton abstraction from phenol under NICI (N₂O) and fast atom bombardment conditions. Production of both phenoxide and enolate forms in NICI (ammonia) is demonstrated under NICI (ND₃) conditions in which DO-labelled [M_d  H]⁻ enolate ions are produced in a similar yield to unlabelled [M_d  D]⁻ phenoxide ions. Collisionally activated dissociation (CAD) spectra of both isomeric deprotonated molecules differ strongly by the presence of two different pairs of complementary daughter ions, suggesting that these ionic species are unconvertible. This is due to a steric hindrance effect on the long-distance proton transfer. A mechanistic investigation on the formation of fragment ion pairs produced under CAD was performed with various deuterium-labelled molecules. From these experiments, evidence is provided for molecular isomerizations into ion-dipole complexes (prior to dissociation) which are structurally dependent on the initial charge location. Direct dissociation of these intermediates competes with the occurrence of exothermic proton transfer(s) yielding the formation of other isomeric intermediate forms. The orientation of these proton transfers is dictated by the relative acidities of both moieties of the complex.     

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

In this work, density functional theory (DFT) and time‐dependent DFT (TDDFT) methods were used to investigate the excited‐state dynamics of the excited‐state hydrogen‐bonding variations and proton transfer mechanism for a novel white‐light fluorophore 2‐(4‐[dimethylamino]phenyl)‐7‐hyroxy‐6‐(3‐phenylpropanoyl)‐4H‐chromen‐4‐one ( 1 ). The methods we adopted could successfully reproduce the experimental electronic spectra, which shows the appropriateness of the theoretical level in this work. Using molecular electrostatic potential (MEP) as well as the reduced density gradient (RDG) versus the product of the sign of the second largest eigenvalue of the electron density Hessian matrix and electron density (sign[λ₂]ρ), we demonstrate that an intramolecular hydrogen bond O1–H2···O3 should be formed spontaneously in the S₀ state. By analyzing the chemical structures, infrared vibrational spectra, and hydrogen‐bonding energies, we confirm that O1–H2·O3 should be strengthened in the S₁ state, which reveals the possibility of an excited‐state intramolecular proton transfer (ESIPT) process. On investigating the excitation process, we find the S₀ → S₁ transition corresponding to the charge transfer, which provides the driving force for ESIPT. By constructing the potential energy curves, we show that the ESIPT reaction results in a dynamic equilibrium in the S₁ state between the forward and backward processes, which facilitates the emission of white light.     

Proton Transfer Influence on Geometry and Electron Density in Benzoic Acid–Pyridine Complexes

The influence of the proton transfer on the geometry of donor and acceptor molecule in benzoic acid–pyridine complexes is investigated by theoretical calculations at the B3LYP/6‐311++G** level of theory. Systematic shifts of the H‐atom in the H‐bond are reflected in the geometry of the COOH group and the lengths of aromatic ring bond lengths of the proton acceptor. Changes in electron densities have been studied by atoms in molecules analysis. A systematic natural bond orbital analysis has been performed to study the proton transfer mechanism. Two donor orbitals are engaged in the proton transfer process which is accompanied by a change in orbital delocalization of H‐atom that can switch between two donor orbitals so the path of proton transfer in intermolecular H‐bond is not determined by the orbital shape. Theoretical results have been confirmed by experimental results published previously.     

Cysteine SH and Glutamate COOH Contributions to [NiFe] Hydrogenase Proton Transfer Revealed by Highly Sensitive FTIR Spectroscopy

A [NiFe] hydrogenase (H₂ase) is a proton‐coupled electron transfer enzyme that catalyses reversible H₂ oxidation; however, its fundamental proton transfer pathway remains unknown. Herein, we observed the protonation of Cys546‐SH and Glu34‐COOH near the Ni–Fe site with high‐sensitivity infrared difference spectra by utilizing Ni‐C‐to‐Ni‐L and Ni‐C‐to‐Ni‐SI_a photoconversions. Protonated Cys546‐SH in the Ni‐L state was verified by the observed SH stretching frequency (2505 cm^?1), whereas Cys546 was deprotonated in the Ni‐C and Ni‐SI_a states. Glu34‐COOH was double H‐bonded in the Ni‐L state, as determined by the COOH stretching frequency (1700 cm^?1), and single H‐bonded in the Ni‐C and Ni‐SI_a states. Additionally, a stretching mode of an ordered water molecule was observed in the Ni‐L and Ni‐C states. These results elucidate the organized proton transfer pathway during the catalytic reaction of a [NiFe] H₂ase, which is regulated by the H‐bond network of Cys546, Glu34, and an ordered water molecule.     

Proton‐Coupled Electron Transfer of Unsaturated Fatty Acids and Mechanistic Insight into Lipoxygenase

A proton‐coupled electron transfer (PCET) process plays an important role in the initial step of lipoxygenases to produce lipid radicals which can be oxygenated by reaction with O₂ to yield the hydroperoxides stereoselectively. The EPR spectroscopic detection of free lipid radicals and the oxygenated radicals (peroxyl radicals) together with the analysis of the EPR spectra has revealed the origin of the stereo‐ and regiochemistry of the reaction between O₂ and linoleyl (= (2Z)‐10‐carboxy‐1‐[(1Z)‐hept‐1‐enyl]dec‐2‐enyl) radical in lipoxygenases. The direct determination of the absolute rates of H‐atom‐transfer reactions from a series of unsaturated fatty acids to the cumylperoxyl (= (1‐methyl‐1‐phenylethyl)dioxy) radical by use of time‐resolved EPR at low temperatures together with detailed kinetic investigations on both photoinduced and thermal electron‐transfer oxidation of unsaturated fatty acids provides the solid energetic basis for the postulated PCET process in lipoxygenases. A strong interaction between linoleic acid (= (9Z,12Z)‐octadeca‐9,12‐dienoic acid) and the reactive center of the lipoxygenases (Fe^III? OH) is suggested to be involved to make a PCET process to occur efficiently, when an inner‐sphere electron transfer from linoleic acid to the Fe^III state is strongly coupled with the proton transfer to the OH group.