Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers

Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)₄(2,2′-bipyridine)]²⁻ (1), [Fe(CN)₄(2,3-bis(2-pyridyl)pyrazine)]²⁻ (2) and [Fe(CN)₄(2,2′-bipyrimidine)]²⁻ (3) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the ¹MLCT vertical energy to be varied from 1.64 eV to 2.64 eV and the ³MLCT lifetime to range from 180 fs to 67 ps. The ³MLCT lifetimes in 1 and 2 decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred (³MC) excited state, as established by the Tanabe–Sugano analysis of the Fe 2p3d RIXS data. In contrast, the ³MLCT lifetime in 3 changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing ³MLCT → ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The ³MLCT → GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (hν = 1530 cm⁻¹), which is most displaced for complex 3, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the ³MLCT and the ³MC states and suppression of the intramolecular distortion of the acceptor ligand in the ³MLCT excited state.

Photoinduced intramolecular electron transfer in Fe tetracyano-polypyridyl complexes was investigated with static and time-resolved UV-visible absorption and resonant inelastic X-ray scattering which revealed a competition of two relaxation pathways.     

Studies on State-to-State Energy Transfer of Electronically Excited Atoms and Molecules

Rotationally inelastic collisions of NH₂( òA₁), ∑(0,9,0), 3₀₃, 1₀₁ have been studied by measuring the dispersed fluorescence spectra at molecular beam conditions. The results show that the angular momentum transfer rule is much more successful than is that predicted by energy gap law for fitting the rotational energy transfer rate. For ΔN < 2 the transfer rates are getting slow down. Downward transfer rates are faster than those of upward transfer. With same angular momentum transferred, the transfer rates for Δk_a = 0 process are larger than those for Δk_a≠0. It is also found that rotation transfer process is a very efficient way for decaying of the initially pumped levels. About 60% of the initially pumped 3₀₃ is colliding into other rotational levels. Energy transfer reactions of metastable rare gas atoms (R_g*) with N₂, NH₃, CS₂ were investigated by measuring the emission spectra. The preferential population of n(A″) of NH(c¹II) was found in He(2³S) + NH₃ reaction, the experimental data shows II(A″)/II(A′) = 1.2 at J′ < 13. A high vibrational excitation and low rotational excitation of N₂(C³n) were observed in Ne(³P₀₂) + N₂ reaction comparing with Ar(³P_0.2) + N₂ reaction. The detailed vibrational populations of CS₂⁺ (Ã, B?) achieved by He(2³S)/Ne(³P_0.2) + CS₂ reaction are different from those obtained by PES. The vibrational distributions of CH(A²Δ) obtained by He(2³S) + CHC1₃ (CH₃NO₂) reactions were discussed based on statistical theory, special attention was paid to reveal the role played by tie angular momentum restriction in this process. The result on energy transfer between N₂(a¹ Π) and CO(X¹ ∑) was firstly presented by VUV emission spectra at single collision condition. The mechanisms of energy transfer related to some of the reactions mentioned above were also discussed in the text.     

Experimental evidence for impulsive energy transfer in electronically adiabatic low-energy collison of Na+ with CF4

Time-of-flight measurement of the inelastic scattering of Na⁺ ions from CF₄ reveal two energy-loss mechanisms which have been observed at center-of-mass collison energies between 4 and 24 eV. At small angles θ_1ab?20° a single energy transfer peak is observed and attributed to normal mode excitation. At larger angles an additional sharp peak is observed out to θ_lab = 70° with nearly double the energy transfer. the final velocities and angular dependence agree with an impulsive interaction involving only one of the F atoms with an effective mass which approaches that of the F atoms with increasing collison energy. This is the first evidence for an impulsive mechanism in inelastic collisons at energies below the threshold for electonic excitation.     

Single nucleon transfer reactions near Coulomb barrier on <Superscript>197</Superscript>Au

Summary Single neutron transfer reactions on ¹⁹⁷Au induced by ¹²C and ¹⁶O at near Coulomb barrier energies have been studied using radiochemical and off-line gamma-ray spectrometric techniques. High spin yield fraction (HSF = σ_m/(σ_m+σ_g)) for ^196m,gAu and formation cross section ratio (σ₁₉₈/σ₁₉₆) of ¹⁹⁸Au and ¹⁹⁶Au have been determined for both ¹⁹⁷Au+¹²C and ¹⁹⁷Au+¹⁶O reactions at different excitation energies near the Coulomb barrier. The HSF of ^196m,gAu and σ₁₉₈/σ₁₉₆ values in both reactions are seen to sharply increase with increasing excitation energy near the Coulomb barrier and then slowly increase reaching a constant value at high projectile energy. These observations have been analyzed in terms of nuclear structural and kinematic parameters. A comparison the effects of Coulomb excitation and nucleon transfer process during heavy-ion interactions indicates a predominant effect of the latter process in the background of the Coulomb excitation. Observed reaction systematics seem to follow the quasi-elastic transfer process.     

The effect of vibrational bond stretching on rotational inelastic electron-molecule scattering

Differential cross sections for state-to-state rotationally inelastic electron-Na₂ scattering, with the molecule being in the vibrational levelv′'=31, are measured at a collision energy of 150 eV. Angular momentum transfer of up to Δj=26 is observed, which is even more than previously obtained for the vibrational ground statev′'=0. Good agreement is found with theoretical results from a spectator scattering model. This work, in general, elucidates the role of vibrational excitation in collision dynamics under vibrationally sudden conditions.     

Effect of rotation on vibrational excitation of H2 by Li impact

Coupled channel calculations of integral cross sections for rotational and vibrational excitation of H₂(X¹Σ⁺_g by collision with Li⁺ are reported for 1.2 eV in the c.m. system employing an ab initio potential energy surface and numerical vibration—rotation functions of the Koo?s—Wolniewicz potential function including adiabatic correction. Pure rotational excitation is found to strongly dominate the inelastic scattering occurring at this energy. Preparation of H₂ in various allowed non-zero rotational states is seen to enhance the 0 → 1 vibrational cross section by approximately an order of magnitude.     

Inner shell excitation of SF6 by 2.5 keV electron impact

The S 2p, S 2s and F 1s inner shell excitation spectra of SF₆ have been examined by small angle, inelastic scattering of 2.5 keV electrons. While the main features of the spectra are in agreement with previous photoabsorption spectra, a number of new features have been observed. A detailed investigation of the S 2p spectrum below the ionization limit has been performed. The weak Rydberg structure in this region has been interpreted on the basis of a comparison of the present electron energy loss results with previous photoabsorption studies. Part of the Rydberg structure in the electron impact spectrum has been identified as arising from electric quadrupole transitions.     

Alkylation Effects on the Energy Transfer of Highly Vibrationally Excited Naphthalene

The energy transfer of highly vibrationally excited isomers of dimethylnaphthalene and 2‐ethylnaphthalene in collisions with krypton were investigated using crossed molecular beam/time‐of‐flight mass spectrometer/time‐sliced velocity map ion imaging techniques at a collision energy of approximately 300 cm^?1. Angular‐resolved energy‐transfer distribution functions were obtained directly from the images of inelastic scattering. The results show that alkyl‐substituted naphthalenes transfer more vibrational energy to translational energy than unsubstituted naphthalene. Alkylation enhances the V→T energy transfer in the range ?ΔE_d=?100～?1500 cm^?1 by approximately a factor of 2. However, the maximum values of V→T energy transfer for alkyl‐substituted naphthalenes are about 1500～2000 cm^?1, which is similar to that of naphthalene. The lack of rotation‐like wide‐angle motion of the aromatic ring and no enhancement in very large V→T energy transfer, like supercollisions, indicates that very large V→T energy transfer requires special vibrational motions. This transfer cannot be achieved by the low‐frequency vibrational motions of alkyl groups.     

Speciation of sulfur in individual aerosol particles from work places by wavelength-dispersive electron-probe microanalysis

The oxidation state of sulfur has been determined by measuring the energy shift of the S K line by wavelength-dispersive electron-probe microanalysis. On flat polished samples the energy shift between sulfate (S⁺⁶) and sulfide (S^-2) was 1.3 eV, in good agreement with previous literature data. The observed energy shift of the S K line is dominated by the change of the valence state of sulfur—the effects of co-ordination geometry and nearest neighbours are small. The relationship between the energy shift of the S K line and the oxidation number of sulfur is linear, to a first approximation. The effect of particle geometry on the position of the S K line is usually small and introduces an error of approximately half an oxidation number. The apparent sulfur valence states observed for individual aerosol particles from work places in a nickel refinery are highly variable and most probably result from different mixtures of the two end-members sulfide and sulfate.     

Study of kinetics and mechanism of the acid dissociation of copper(II) complex of novel C-functionalized macrocyclic dioxotetraamines

The kinetics of the acid dissociation of copper(II) complexes of novel C-functionalized macrocyclic dioxotetraamines has been studied by means of a stopped-flow spectrophotometer. The acid dissociation rate follows the law V_d = C_comkK₁K₂H ²/(1+K₁H+K₁K₂H ²). From the experimental facts we have obtained, the dissociation kinetics are interpreted by a mechanism involving the negatively charged carbonyl oxygen of the complex being rapidly protonated in a pre-equilibrium step, the rate-determining step being intramolecular hydrogen (enolic tautomer) migration (to imine nitrogen). The dissociation rate reached a plateau in the strongly acidic solution. By means of temperature coefficient method, ΔH ^φ, ΔS ^φ of the pre-equilibrium step and ΔH ^≠, ΔS^≠ of the rate-determining step were obtained. The results of 13-membered macrocyclic dioxotetraamines have been discussed. The influence of the substituents to the acid dissociation rates has also been discussed. The Bronsted type linear free energy relationships do also exist in these C-functionalized dioxotetraamine copper(II) complexes.     

Evidence for a long-lived excited state of CH4+ from a beam scattering study of the collision-induced dissociation of CH4+ to CH2+ at low energy

A crossed-beam study of the collision-induced dissociation of CH₄⁺ by Ar was carried out at a center-of-mass (c.m.) collision energy of 5.5 eV. The scattering shows three patterns for the formation of CH₂⁺, (1) large-angle scattering at preferred impact parameters with little internal excitation of the products, (2) scattering near the c.m. with nearly all collision energy transferred into products internal energy and (3) superelastic scattering, i.e. conversion of internal energy to translational energy, implying the reaction is initiated by a long-lived excited state of CH₄⁺ generated by electron impact ionization of methane. No previous evidence exists, to our knowledge, that excited states of CH₄⁺ thus generated may have microsecond lifetimes.     

Kinetics and mechanism of the oxidation of a ternary complex involving nitrilotriacetatocobaltate(II) and malonic acid by N-bromosuccinimide

The kinetics of oxidation of [Co^IINM(H₂O)]^3– (N = nitrilotriacetate, M = malonate) by N-bromosuccinimide (NBS) in aqueous solution have been found to obey the equation: d[Co^III]/dt = k ₁ K ₂[NBS][Co^II]_T/{1 + K₂[NBS] + (H⁺/K₁)} where k ₁ is the rate constant for the electron transfer process, K ₁ the equilibrium constant for dissociation of [Co^IINM(H₂O)]^3– to [Co^IINM(OH)]^4– + H⁺, and K ₂ the pre-equilibrium formation constant. Values of k ₁ = 1.07 × 10^–3 s^–1, K ₁ = 4.74 × 10^–8 mol dm^–3 and K ₂ = 472 dm³ mol^–1 have been obtained at 30 °C and I = 0.2 mol dm^–3. The thermodynamic activation parameters have been calculated. The experimental rate law is consistent with a mechanism in which the deprotonated [Co^IINM(OH)]^4– is considered to be the most reactive species compared to its conjugate acid. It is assumed that electron transfer takes place via an inner-sphere mechanism.     

Specific heat and phase transition of (Li1−xKx)2SO4 single crystals

A specific heat study of (Li_1–xK_x)₂SO₄ — LKS — mixed crystals has been made in a wide concentration rangex covering the temperature range 300–800 K. The phase diagram was determined. It is shown that a variation of the Li⁺:K⁺ concentration changes the critical behaviour of the specific heat. The results are discussed in terms of scattering mechanisms of energy carriers.

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Zusammenfassung Bei Temperaturen zwischen 300 und 800 K wurde für einen breiten Konzentrationsbereich für x die spezifische Wärme von (Li_1–xK_x)₂SO₄-Mischkristallen untersucht und das entsprechende Phasendiagramm erstellt. Es wurde gezeigt, daß eine Änderung des Verhältnisses Li⁺:K⁺ auch das kritische Verhalten der spezifischen Wärme verändert. Die Ergebnisse werden hinsichtlich von Sreuungsmechanismen der Energieträger diskutiert.

     

Inner-sphere oxidation of ethylenediaminetetraacetatocobaltate(II) by N-bromosuccinimide

Summary The kinetics of oxidation of [Co^II(EDTA)]^2- (EDTA = ethylenediaminetetraacetate) by N-bromosuccinimide (NBS) in aqueous solution obey the equation: Rate = k ₂ K ₃[Co^II]_T[NBS]/{1 + [H⁺]/K ₂ + K ₃[NBS]} where k ₂ is the rate constant for the electron-transfer process, K ₂ the equilibrium constant for the dissociation of [Co^II(EDTAH)(H₂O)]^– to [Co^II(EDTA)(OH)]^3– and K ₃ the pre-equilibrium formation constant. The activation parameters are reported. It is proposed that electron transfer proceeds via an inner-sphere mechanism with the formation of an intermediate which slowly generates hexadentate[Co^III(EDTA)]^–.Abstracted from the M.Sc. thesis of Eman S. H. Khaled.     

Theoretical study of stereodynamics for the O(D) + D2 → OD + D reaction

A quasi-classical trajectory method (QCT) running on the ¹A′ and ¹A″ potential energy surfaces (PESs) given by Dobbyn and Knowles [A.J. Dobbyn, P.J. Knowles, Mol. Phys. 91 (1997) 1107] has been employed to study the dynamical stereochemistry of the chemical reaction O(¹D) + D₂ → OD + D, especially the vector correlations between products and reagents. The results indicate that product rotational angular momentum j′ is not only aligned, but also oriented along the direction perpendicular to the scattering plane on both PESs, with different rotational polarization behaviors of product OD for the two PESs and for different collision energies. Calculations show that the alignment effect of products become weaker with an increase of the collision energy on the ¹A′ PES but is not sensitive to the collision energy on the ¹A″ PES. When the collision energy increases, the product OD mainly tends to the forward scattering on the ¹A′ PES and displays a switch from the backward scattering to the forward one on the ¹A″ PES. These differences are probably attributed to the different characteristics of the two PESs.     

Selectivity in resonant vibrational excitation by e− impact (0.3–4.5 eV) on formaldehyde,acetaldehyde and acetone

Vibrational excitation by e⁻ impact via low-energy resonances has been investigated in acetaldehyde and acetone and compared with similar results in formaldehyde. Despite the large number of vibrational modes involved, the three systems exhibit a selective excitation of only several modes. Besides an important excitation of the CO stretch modes (dominant in H₂CO), excitation of CH stretch, CH₃ stretch and CH₃ deformation are also observed in CH₃CHO and (CH₃)₂CO. Interpretation of the energy loss spectra is given in terms of recently developed symmetry considerations together with the character of the LUMO occupied by the extra electron to form the transitory negative ion (resonance). Differential cross sections versus electron energy are presented for elastic and several inelastic processes. Weak oscillations (of the “boomerang” type) are observed on the inelastic cross sections for acetaldehyde, whereas no structure appears for acetone. This is in contrast with the pronounced oscillations observed for H₂CO, and reveals a shorter lifetime for the CH₃CHO⁻ and (CH₃)₂CO⁻ resonant states, compared to H₂CO⁻.     

Low power threshold photochemical upconversion using a zirconium(iv) LMCT photosensitizer

The current investigation demonstrates highly efficient photochemical upconversion (UC) where a long-lived Zr(iv) ligand-to-metal charge transfer (LMCT) complex serves as a triplet photosensitizer in concert with well-established 9,10-diphenylanthracene (DPA) along with newly conceived DPA–carbazole based acceptors/annihilators in THF solutions. The initial dynamic triplet–triplet energy transfer (TTET) processes (ΔG ∼ −0.19 eV) featured very large Stern–Volmer quenching constants (K_SV) approaching or achieving 10⁵ M⁻¹ with bimolecular rate constants between 2 and 3 × 10⁸ M⁻¹ s⁻¹ as ascertained using static and transient spectroscopic techniques. Both the TTET and subsequent triplet–triplet annihilation (TTA) processes were verified and throughly investigated using transient absorption spectroscopy. The Stern–Volmer metrics support 95% quenching of the Zr(iv) photosensitizer using modest concentrations (0.25 mM) of the various acceptor/annihilators, where no aggregation took place between any of the chromophores in THF. Each of the upconverting formulations operated with continuous-wave linear incident power dependence (λ_ex = 514.5 nm) down to ultralow excitation power densities under optimized experimental conditions. Impressive record-setting η_UC values ranging from 31.7% to 42.7% were achieved under excitation conditions (13 mW cm⁻²) below that of solar flux integrated across the Zr(iv) photosensitizer''s absorption band (26.7 mW cm⁻²). This study illustrates the importance of supporting the continued development and discovery of molecular-based triplet photosensitizers based on earth-abundant metals.

The LMCT photosensitizer Zr(^MesPDP^Ph)₂ paired with DPA-based acceptors enabled low power threshold photochemical upconversion with record-setting quantum efficiencies.     

Photochemical Reactivity of Naphthol-Naphthalimide Conjugates and Their Biological Activity

Quinone methide precursors 1a–e, with different alkyl linkers between the naphthol and the naphthalimide chromophore, were synthesized. Their photophysical properties and photochemical reactivity were investigated and connected with biological activity. Upon excitation of the naphthol, Förster resonance energy transfer (FRET) to the naphthalimide takes place and the quantum yields of fluorescence are low (Φ_F ≈ 10⁻²). Due to FRET, photodehydration of naphthols to QMs takes place inefficiently (Φ_R ≈ 10⁻⁵). However, the formation of QMs can also be initiated upon excitation of naphthalimide, the lower energy chromophore, in a process that involves photoinduced electron transfer (PET) from the naphthol to the naphthalimide. Fluorescence titrations revealed that 1a and 1e form complexes with ct-DNA with moderate association constants K_a ≈ 10⁵–10⁶ M⁻¹, as well as with bovine serum albumin (BSA) K_a ≈ 10⁵ M⁻¹ (1:1 complex). The irradiation of the complex 1e@BSA resulted in the alkylation of the protein, probably via QM. The antiproliferative activity of 1a–e against two human cancer cell lines (H460 and MCF 7) was investigated with the cells kept in the dark or irradiated at 350 nm, whereupon cytotoxicity increased, particularly for 1e (>100 times). Although the enhancement of this activity upon UV irradiation has no imminent therapeutic application, the results presented have importance in the rational design of new generations of anticancer phototherapeutics that absorb visible light.     

Non-adiabatic collisions in H+ + O2 system: An ab initio study

An ab initio study on the low-lying potential energy surfaces of H⁺ + O₂ system for different orientations (γ) of H⁺ have been undertaken employing the multi-reference configuration interaction (MRCI) method and Dunning’s cc-pVTZ basis set to examine their role in influencing the collision dynamics. Nonadiabatic interactions have been analysed for the 2 × 2 case in two dimensions for γ = 0°, 45° and 90°, and the corresponding diabatic potential energy surfaces have been obtained using the diabatic wavefunctions and their CI coefficients. The characteristics of the collision dynamics have been analysed in terms of vibrational coupling matrix elements for both inelastic and charge transfer processes in the restricted geometries. The strengths of coupling matrix elements reflect the vibrational excitation patterns observed in the state-to-state beam experiments.     

Kinetics and mechanisms of the catalyzed decomposition of hydrogen peroxide by ethylenebis(oxyethylenedinitrilo)tetracetate complex of iron(III)

The rate of decomposition of H₂O₂ in the presence of Fe(III)-y complex (y is ethylenebis(oxyethylenedinitrilo)tetraacetic acid (EGTA) anion) was investigated under variable conditions of pH and temperature, various water-miscible solvents, and different concentrations of H₂O₂, [Fe-y]⁻, and acetate ions. The following rate law holds: Rate = (k₁K₃K₄/[H⁺]) [Fe-y(OH)]²⁻ [H₂O₂] at pH less than 9.80, and Rate = (k₂K₅[H⁺]/K₃) [Fe-y(OH)₂]³⁻[OOH]⁻ at pH above 9.80. The values of k₁K₄and k₂K₅ at 25 °C were found to be 1523 and 0.747 M⁻¹ S⁻¹, respectively. Activation enthalpy and activation entropy for this reaction were determined from Arrhenius plots and found to be ΔH^* = 34.38 K J mol⁻¹ and ΔS^* = −167.2 J K⁻¹ mol⁻¹.