Brønsted acid catalysis of photosensitized cycloadditions

Catalysis is central to contemporary synthetic chemistry. There has been a recent recognition that the rates of photochemical reactions can be profoundly impacted by the use of Lewis acid catalysts and co-catalysts. Herein, we show that Brønsted acids can also modulate the reactivity of excited-state organic reactions. Brønsted acids dramatically increase the rate of Ru(bpy)₃²⁺-sensitized [2 + 2] photocycloadditions between C-cinnamoyl imidazoles and a range of electron-rich alkene reaction partners. A combination of experimental and computational studies supports a mechanism in which the Brønsted acid co-catalyst accelerates triplet energy transfer from the excited-state [Ru*(bpy)₃]²⁺ chromophore to the Brønsted acid activated C-cinnamoyl imidazole. Computational evidence further suggests the importance of driving force as well as geometrical reorganization, in which the protonation of the imidazole decreases the reorganization penalty during the energy transfer event.

Brønsted acids can catalyze triplet energy transfer reactions, and DFT computations suggest the unexpected importance of reorganization energy for catalysis.     

Solution equilibria of zinc(II) and cadmium(II) complexes with 2,2′-bipyridine in N,N-dimethylacetamide at 25°C

Complexation of zinc(II) and cadmium(II) ions with 2,2-bipyridine (bpy) are studied in N,N-dimethylacetamide (DMA) by calorimetry. Formation constants, enthalpies, and entropies of five mononuclear complexes, [Zn(bpy)_n]²⁺ (n=1–3) and [Cd(bpy)_n]²⁺ (n=1,2), are determined, and compared with the corresponding values in an analogous but less bulky solvent, N,N-dimethylformamide (DMF). The zinc complexes are more stable and the formation is more exothermic in DMA than in DMF, whereas the solvent effect on the cadmium complexes are rather small. A largely positive value of the enthalpy of transfer of Zn²⁺ from DMF to DMA shows that the greater stability of the zinc complexes in DMA is due to the weaker solvation of the metal ion, which is caused by the steric hindrance of DMA molecules. The transfer enthalpies become smaller in the order Zn²⁺>[Zn(bpy)]²⁺>[Zn(bpy)₂]²⁺>[Zn(bpy)₃]²⁺ and dictate gradual relaxation of the steric effect in the complexes. On the other hand, the transfer enthalpies of Cd²⁺ and its complexes are all small, indicating that the hindrance is insignificant in the vicinity of this larger cation.     

Influence of dissociation of tris(2,2′-bipyridyl)iron(II) cations on the time dependence of currents in clay-modified electrodes

The time dependence of the voltammetric waves of [Fe(bpy)₃]²⁺ adsorbed in clay-modified electrodes (CMES) differed greatly from those of [Ru(bpy)₃]²⁺ and [Os(bpy)₃]²⁺. The currents obtained with the ruthenium and osmium cations were essentially constant in the first 2 h that the CME spent in the blank electrolyte. For [Fe(bpy)₃]²⁺, the maximum currents were twice as large. After a sharp rise in the first few scans, they decreased rapidly to less than half of their maximum values after 40 min. The decrease was more rapid when the potential was scanned continuously or when the pH of the electrolyte was increased. Coulometry shows that a larger fraction of the adsorbed [Fe(bpy)₃] ²⁺ cations were oxidized and that they were oxidized much more rapidly than the other two cations. The unique behaviour of [Fe(bpy)₃]²⁺ is attributed to its dissociation in the CME. UV—visible spectroscopy shows that significant dissociation of this cation occurred on the time-scale of the electrochemical measurements. Much larger currents were also found for CMEs containing cis- or trans-[Ru(bpy)₂(H₂O)₂] ²⁺, and these are attributed to the greater mobility of adsorbed bis-bipyridyl cations.     

Free Energy Relationships for the Outer-Sphere Anion–Anion and Anion–Cation Optical Electron Transitions Involving Common Cyanometalate (II) and (IV) Donors: Evidence for the Frequency-Distorted Reorganization Dynamics

This work is an extension of the research project on the outer-sphere optical charge transfer (CT) initiated by Prof. R.R. Dogonadze at the Laboratory founded by him in Tbilisi, Georgia. We report the band deconvolution procedures and accomplished free energy relationships for recently observed novel outer-sphere anion–anion and anion–cation optical electron transitions involving common cyanometalate II and IV ions, viz. [M(CN) _x ]^4–, M = Fe, Ru, Os (x = 6) and M = Mo, W (n = 8) as electron donors, and [Fe^III(CN)₆]^3– and [Ru^III(NH₃)₆]³⁺ as electron acceptors, respectively. The CT band maximum vs. the redox asymmetry free energy relationships, constructed through the consideration of spin-orbit splitting effects, exhibit linear character with slopes close to unity as predicted theoretically, and fully confirm the assignment of these transitions to outer-sphere optical electron transitions as outlined in the preceding works. The preliminary comparative analysis of presented relationships based on the contemporary charge transfer theory and recent differential DO-D stretching overtone data strongly suggests the essential redox asymmetry for the reorganization free energy increments attributed to first solvating shells of cyanometalate ions involved.     

Study of the Light‐Induced Spin Crossover Process of the [FeII(bpy)3]2+ Complex

Ab initio calculations have been performed on [Fe^II(bpy)₃]²⁺ (bpy=bipyridine) to establish the variation of the energy of the electronic states relevant to light‐induced excited‐state spin trapping as a function of the Fe? ligand distance. Light‐induced spin crossover takes place after excitation into the singlet metal‐to‐ligand charge‐transfer (MLCT) band. We found that the corresponding electronic states have their energy minimum in the same region as the low‐spin (LS) state and that the energy dependence of the triplet MLCT states are nearly identical to the ¹MLCT states. The high‐spin (HS) state is found to cross the MLCT band near the equilibrium geometry of the MLCT states. These findings give additional support to the hypothesis of a fast singlet–triplet interconversion in the MLCT manifold, followed by a ³MLCT–HS (⁵T₂) conversion accompanied by an elongation of the Fe? N distance.     

A novel cyano complex of tungsten(IV) with 2, 2′-bipyridyl

Summary (bpyH)₃(H₃O)[W(CN)₈]·H₂O reacts at high temperature to give the ionic species [W(bpy)(CN)₆]^2–. Tetraphenylphosphonium and tetraphenylarsonium salts were isolated as solids whereas the acid and its alkali metal salts were investigated in solution. The new complexes were characterized by u.v. and visible, i.r. and e.s.r. spectrometry, t.g. and d.t. analysis. The intensively coloured salts exhibit solvent—dependent absorption bands at low energy assigned to Wbpy transitions.     

Charge-Transfer and Spin-Flip States: Thriving as Complements

Transition metal complexes with photoactive charge-transfer excited states are pervasive throughout the literature. In particular, [Ru(bpy)₃]²⁺ (bpy=2,2′-bipyridine), with its metal-to-ligand charge-transfer emission, has been established as a key complex. Meanwhile, interest in so-called spin-flip metal-centered states has risen dramatically after the molecular ruby [Cr(ddpd)₂]³⁺ (ddpd=N,N′-dimethyl-N,N′-dipyridin-2-yl-pyridine-2,6-diamine) led to design principles to access strong, long-lived emission from photostable chromium(III) complexes. This Review contrasts the properties of emissive charge-transfer and spin-flip states by using [Ru(bpy)₃]²⁺ and [Cr(ddpd)₂]³⁺ as prototypical examples. We discuss the relevant excited states, the tunability of their energy and lifetimes, and their response to external stimuli. Finally, we identify strengths and weaknesses of charge-transfer and spin-flip states in applications such as photocatalysis and circularly polarized luminescence.     

Dielectric dispersion in optical electron transfer in solution

Dielectric dispersion causes the outer-sphere reorganization free energy to vary with photon energy in optical electron transfer. The resulting distortion of the spectral response for photoelectron emission may yield misleading evidence about the emission yield versus photon energy relationship. Dispersion is taken into account in the calculation of emission threshold energies and the correlation between optical and thermal electron transfer. Results are given for V²⁺, Cr²⁺, Mn²⁺, Fe²⁺, Co²⁺, Fe(CN)₆^4?.     

Measurement of the driving force dependence of interfacial charge-transfer rate constants in response to pH changes at n-ZnO/H2O interfaces

Changes in pH have been used to shift the band-edge positions of n-type ZnO electrodes relative to solution-based electron acceptors having pH-independent redox potentials. Differential capacitance vs. potential and current density vs. potential measurements using [Co(bpy)₃]^3+/2+ and [Ru(bpy)₂(MeIm)₂]^3+/2+ (where bpy = 2,2′-bipyridyl and MeIm = 1-methyl-imidazole) allowed investigation of the pH-induced driving-force dependence of the interfacial electron-transfer rate in the normal and inverted regions of electron transfer, respectively. All rate processes were observed to be kinetically first-order in the concentration of electrons at the ZnO surface and first-order in the concentration of dissolved redox acceptors. Measurements using [Co(bpy)₃]^3+/2+, which has a low driving force and a high reorganization energy in contact with ZnO electrodes, and measurements of [Ru(bpy)₂(MeIm)₂]^3+/2+, which has a high driving force and a low reorganization energy in contact with ZnO electrodes, allowed for the evaluation of both the normal and inverted regions of interfacial electron-transfer processes, respectively. The rate constant at optimum exoergicity was observed to be approximately 5 × 10⁻¹⁷ cm⁴ s⁻¹. The rate constant vs. driving-force dependence at n-type ZnO electrodes exhibited both normal and inverted regions, and the data were well-fitted by parabolas generated using classical electron-transfer theory.     

Partial molar volumes and partial molar adiabatic compressibilities of bipyridine and phenanthroline complexes with Fe(II), Co(II), Ni(II), and Cu(II) and chlorides of these metals

Densities and ultrasonic velocities were measured at 25°C for aqueous solutions of bipyridine and phenanthroline complexes [M(bpy)₃]Cl₂ and [M(phen)₃]Cl₂ (M=Fe, Co, Ni, and Cu, bpy=2,2-bipyridine, and phen=1,10-phenanthroline), and chlorides of these metals. The partial molar volumes V ₂ ^o and partial molar adiabatic compressibilities K _s ^o were calculated. For the complex ions, [M(bpy)₃]²⁺ and [M(phen)₃]²⁺, electrostatic interactions with the solvent are not nearly as important as effects due to the hydrophobic ligands bpy and phen. The relationship between V ₂ ^o and K _s ^o of the complex ions and common metal ions are examined.     

[M(bpy)3] (M = Fe,Ru, Os): New Crystalline Materials from the reductive electrocrystallization of [M(bpy)3](PF6)2

Reductive electrocrystallization at a constant current density (11.0–11.5 μA/cm²) of millimolar solutions of [M(bpy)₃](PF₆)₂, where M = Fe, Ru, or Os, and bpy = 2,2′-bipyridine in acetonitrile containing 0.1M Bu₄NPF₆ results in the formation of dark crystals on the Pt cathode. The crystals grow as long, thin, and shiny needles having a hexagonal cross section of 0.1–0.5 mm in diameter. Combustion microanalyses results are consistent with the composition for [Fe(bpy)₃], [Ru(bpy)₃], and [Os(bpy)₃]. In addition, the chromophores are conserved, as confirmed by recording both the electronic and the ¹H-NMR spectra after reoxidation of the electrocrystals in humid air. The spectra are identical to those for authentic samples of [Fe(bpy)₃]²⁺, [Ru(bpy)₃]²⁺, and [Os(bpy)₃]²⁺. A ratio of 2.0 ± 0.1 e^?/molecule is observed upon completion of the controlled potential electrolysis of a solution of [M(bpy)₃]²⁺, which results in the precipitation of a dark solid and the almost complete fading of the color of the original solution. Unexpectedly, the crystals do not exhibit an ESR signal. These data indicate the formation of novel materials, crystalline [Fe(bpy)₃], [Ru(bpy)₃], and [Os(bpy)₃].     

Formation of [Ru(bpy)3]2+‐Containing Microstructures Induced by Electrostatic Assembly and Their Application in Solid‐State Detection of Electrochemiluminescence

Tris(2,2′‐bipyridine)ruthenium(II) ([Ru(bpy)₃]²⁺) is one of the most extensively studied and used electrochemiluminescent (ECL) compounds owing to its superior properties, which include high sensitivity and stability under moderate conditions in aqueous solution. In this paper we present a simple method for the preparation of [Ru(bpy)₃]²⁺‐containing microstructures based on electrostatic assembly. The formation of such microstructures occurs in a single process by direct mixing of aqueous solutions of [Ru(bpy)₃]Cl₂ and K₃[Fe(CN)₆] at room temperature. The electrostatic interactions between [Ru(bpy)₃]²⁺ cations and [Fe(CN)₆]^3? anions cause them to assemble into the resulting microstructures. Both the molar ratio and concentration of reactants were found to have strong influences on the formation of these microstructures. Most importantly, the resulting [Ru(bpy)₃]²⁺‐containing microstructures exhibit excellent ECL behavior and, therefore, hold great promise for solid‐state ECL detection in capillary electrophoresis (CE) or CE microchips.     

Complexation of the zinc(II) ion with 2,2′-bipyridine and 1,10-phenanthroline in 4-methylpyridine and solvation structure of the manganese(II), cobalt(II), nickel(II), and zinc(II) ions in 4-methylpyridine and 3-methylpyridine

Complexation of the zinc(II) ion with 2,2-bipyridine (bpy) and 1,10-phenanthroline (phen) has been calorimetrically studied in 4-methylpyridine (4Me-py) containing 0.1 mol dm^–3 (n-C₄H₉)₄NClO₄ as a constant ionic medium at 25°C. The formation of [ZnL]²⁺, [ZnL₂]²⁺, and [ZnL₃]²⁺ (L=bpy, phen), and their formation constants, reaction enthalpies and entropies were determined. Our EXAFS (extended X-ray absorption fine structure) measurements showed that the solvation structure of the manganese(II), cobalt(II), and nickel(II) ions is six-coordinate octahedral in 4Me-py and 3-methylpyridine (3Me-py), while that of the zinc(II) ion is four-coordinate tetrahedral in 4Me-py. Since [ZnL₃]²⁺ is expected to have an octahedral structure, a tetrahedral-to-octahedral structural change should take place at a certain step of complexation. The thermodynamic parameters, especially reaction entropies, indicate that the structural change occurs at the formation of [Zn(bpy)₂]²⁺ and [Zn(phen)]²⁺.     

Correlation analysis of reactivity in the reduction of Co(en)2Br2+ by Fe(CN)64– in water–methanol/1,4-dioxane media

The reduction of [Co(en)₂Br₂]⁺ by [Fe(CN)₆]^4– in H₂O–MeOH and H₂O–1,4-dioxane mixtures has been studied over a range of solvent compositions [5–30% (v/v)]. The reduction of [Co(en)₂Br₂]⁺ was monitored under second order conditions and was found to be rapid in the various solvent compositions investigated. The favoured mechanism is an outer-sphere electron-transfer process consisting of elementary steps, ion-pair formation (K _IP), electron-transfer (k _et) and successor dissociation. Therefore, the overall rate constant, k ₂ = K _IP k _et[Co(en)₂- Br₂ ⁺][Fe(CN)₆ ^4–]. The rates increase as the proportion of organic cosolvent increases. The rates correlate with solvent properties, such as relative permittivity (_r) and the Grunwald–Winstein parameter, Y _GW, which are used to explain the non-specific interaction upon solvation of mixture of solvents on the incipient reactants and on the ion-pair. In addition, they are also subjected to multiparametric analysis employing Swain's solvent vectors A and B also with Kamlet–Taft's solvatochromic parameters , and *. The reduction rates show an excellent correlation with multiparametric equations and are susceptible to both specific and non-specific solvation effects. A quantitative estimation of the latter components has been attempted.     

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN₆] chromophore [Cr(tpe)₂]³⁺ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)₂]³⁺ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)₂]³⁺ are redox non‐innocent, leading to reversible reductive chemistry. The excited state redox potential and lifetime of [Cr(tpe)₂]³⁺ surpass those of the classical photosensitizer [Ru(bpy)₃]²⁺ (bpy=2,2′‐bipyridine) enabling energy transfer (to oxygen) and photoredox processes (with azulene and tri(n‐butyl)amine).     

Polychromatic femtosecond fluorescence studies of metal-polypyridine complexes in solution

Femtosecond-resolved broadband fluorescence studies are reported for[M(bpy)₃]²⁺ (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [Fe(bpy)₃]²⁺ and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the ¹MLCT fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in ?30-45 fs due to intersystem crossing to the ³MLCT states, but a longer lived component of ∼190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are characterized by internal conversion (IC) and intramolecular vibrational redistribution (IVR) processes on a time scale which we estimate to ?10 fs using the ¹MLCT lifetime as an internal clock.     

Electronic tuning of ruthenium complexes by 8-quinolate ligands

A series of Ru(II) complexes were synthesized with the deprotonated forms of the ligands 8-hydroxyquinoline (quo⁻) and 5-NO₂-8-hydroxyquinoline (5-NO₂-quo⁻) as analogs to the prototypical complex [Ru(bpy)₃]²⁺ (bpy = 2,2′-bipyridine). Electrochemistry, spectroscopy and density functional theory calculations were utilized to investigate the electronic tuning of the occupied t_2g-type orbitals of the metal center with variation in the ligation sphere. The maximum of the lowest energy absorption of complexes containing one, two and three 8-quinolate ligands progressively redshifts from 452 nm in [Ru(bpy)₃]²⁺ to 510 nm in [Ru(bpy)₂(quo)]⁺, 515 nm in [Ru(bpy)(quo)₂] and 540 nm in [Ru(quo)₃]⁻ in water. This bathochromic shift results from the increase in energy of the occupied t_2g-type orbital across the series afforded by coordination of each subsequent quo⁻ ligand to the Ru(II) center. Time-dependent density functional theory calculations along with electrochemical analysis reveals that the lowest energy transition has contributions in the highest occupied molecular orbital from both the quo⁻ ligand and the metal, such that the lowest energy transition is not from an orbital that is purely metal-centered in character as in [Ru(bpy)₃]²⁺.     

Theoretical study of vibration spectra of sensitizing dyes for photoelectrical converters based on ruthenium(II) and iridium(III) complexes

Quantum-chemical method of the density functional theory was employed to calculate, with the use of a B3LYP hybrid exchange-correlation functional, the IR absorption and Raman spectra of [Ru(bpy)₂(CN)₂] and [Ir(bpy)₂(CN)₂]⁺ complexes. All the normal vibrational frequencies were analyzed and new assignments of a number of bands in the IR absorption and Raman spectra were made. The role of vibrational motions of metal atoms and ligands in the vibronic deformation of electron shells in the course of electron transfer was discussed. This was done using data on surface-enhanced Raman spectra of [Fe(bpy)₂(CN)₂] and [Ru(bpy)₃]²⁺ complexes adsorbed on the surface of colloid silver.     

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.     

Photosensitized Generation of Singlet Oxygen from (Substituted Bipyridine)ruthenium(II) Complexes

Photophysical properties in dilute MeCN solution are reported for seven Ru^II complexes containing two 2,2′‐bipyridine (bpy) ligands and different third ligands, six of which contain a variety of 4,4′‐carboxamide‐disubstituted 2,2′‐bipyridines, for one complex containing no 2,2′‐bipyridine, but 2 of these different ligands, for three multinuclear Ru^II complexes containing 2 or 4 [Ru(bpy)₂] moieties and also coordinated via 4,4′‐carboxamide‐disubstituted 2,2′‐bipyridine ligands, and for the complex [(Ru(bpy)₂(L)]²⁺ where L is N,N′‐([2,2′‐bipyridine]‐4,4′‐diyl)bis[3‐methoxypropanamide]. Absorption maxima are red‐shifted with respect to [Ru(bpy)₃]²⁺, as are phosphorescence maxima which vary from 622 to 656 nm. The lifetimes of the lowest excited triplet metal‐to‐ligand charge transfer states ³MLCT in de‐aerated MeCN are equal to or longer than for [Ru(bpy)₃]²⁺ and vary considerably, i.e., from 0.86 to 1.71 μs. Rate constants k_q for quenching by O₂ of the ³MLCT states were measured and found to be well below diffusion‐controlled, ranging from 1.2 to 2.0⋅10⁹ dm³ mol⁻¹ s⁻¹. The efficiencies f of singlet‐oxygen formation during oxygen quenching of these ³MLCT states are relatively high, namely 0.53 – 0.89. The product of k_q and f gives the net rate constant k for quenching due to energy transfer to produce singlet oxygen, and k_q−k equals k, the net rate constant for quenching due to energy dissipation of the excited ³MLCT states without energy transfer. The quenching rate constants were both found to correlate with ΔG^CT, the free‐energy change for charge transfer from the excited Ru complex to oxygen, and the relative and absolute values of these rate constants are discussed.