Second-order nonlinear optical properties of X-shaped pyrazine derivatives.

This work reports an investigation of the second-order NLO properties of two isomer series of X-shaped pyrazine derivatives, by means of HRS measurements and DFT calculations. The systems differ in the relative position of the donor and acceptor substituents with respect to the axis formed by the nitrogen atoms of the central pyrazine ring. Although the magnitude of the second harmonic signal is similar, HRS measurements revealed that the anisotropy of the NLO response strongly differs in the two chromophore series, the one of the 2,3-isomers being strikingly dipolar, while the one of the 2,6-isomers is mostly octupolar. The experimental observations are well supported by DFT calculations. In particular, the sum-over-states approach allows us to rationalize the different NLO anisotropies observed in the two isomer series through a detailed analysis of the symmetry of the low-lying excited states.

Generation of multiple triplet states in an orthogonal bodipy dimer: a breakthrough spectroscopic and theoretical approach.

Generation of triplet states in assemblies of organic chromophores is extremely appealing for their potential use in optoelectronic applications. In this work, we investigate the intricacies of triplet state generation in an orthogonal BODIPY dimer by combining delayed photoemission techniques with electronic structure calculations. Our analysis provides a deep understanding of the electronic states involved, and describes different competing deactivation channels beyond prompt radiative decay. In particular, we identify charge-transfer (CT) mediated intersystem crossing (ISC) as the most likely mechanism for the triplet state generation in this system. The different emission bands at long times can be associated with delayed fluorescence, CT emission and phosphorescence from multiple low-energy triplets. Interestingly, the dependence of the yield of triplet state population and emission profiles with the solvent polarity evidences the decisive role of the CT configuration in the fate of the photoactivated dimer, controlling the relative ISC, reverse ISC, and internal conversion efficiencies. Overall, the present results provide a rather complete description of the delayed photophysics in the BODIPY dimer, but are not able to fully rationalize the unexpected photoluminescence recorded at long wavelengths (≥ 900 nm). We hypothesize that the origin of this emission, not present in BODIPY monomers, emerges from intermonomer interactions triggered by intramolecular distortions opening up a new vision in the controverted mechanism driving the photophysical behavior from orthogonally linked organic monomers.

Can aluminum, a non-redox metal, alter the thermodynamics of key biological redox processes? The DPPH-QH2 radical scavenging reaction as a test case.

The increased bioavailability of aluminum has led to a concern about its toxicity on living systems. Among the most important toxic effects, it has been proven that aluminum increases oxidative stress in biological systems, a controversial fact, however, due to its non-redox nature. In the present work, we characterize in detail how aluminum can alter redox equilibriums by analyzing its effects on the thermodynamics of the redox scavenging reaction between DPPH., a radical compound often used as a reactive oxygen species model, and hydroquinones, a potent natural antioxidant. For the first time, theoretical and experimental redox potentials within aluminum biochemistry are directly compared. Our results fully agree with experimental reduction and oxidation potentials, unequivocally revealing how aluminum alters the spontaneity of the reaction by stabilizing the reduction of DPPH⋅ to DPPH- and promoting a proton transfer to the diazine moiety, leading to the production of a DPPH-H species. The capability of aluminum to modify redox potentials shown here confirms previous experimental findings on the role of aluminum to interfere with free radical scavenging reactions, affecting the natural redox processes of living organisms.

Mild Open-Shell Character of BODIPY and Its Impact on Singlet and Triplet Excitation Energies.

This study describes and rationalizes the electronic structure of BODIPY combining a large variety of quantum chemistry methods and computational tools. Examination of the obtained results using state-of-the-art electronic structure analyses provides a new and complete interpretation of the nature of low-lying electronic states in BODIPY and elucidates the limitations of excited-state methods in the computation of T1 and S1 energies, that is, systematic under- and overestimation of time-dependent density functional theory energies, respectively, and a large overestimation of the T1/S1 energy gap. Our analysis identifies the important role and physical origin of the mild open-shell character in the BODIPY ground state, that is, strong highest occupied and lowest unoccupied molecular orbital exchange interactions. The study provides guidelines for the accurate quantification of the T1/S1 gap, which is extremely relevant for the computational investigation of the photophysical properties of BODIPY and its derivatives. These conclusions should be taken into consideration in order to predict and interpret conspicuous photoactivated phenomena such as intersystem crossing, singlet fission, and triplet-triplet annihilation. Moreover, we believe that our study might provide new ideas and strategies for the analysis of other molecular chromophores.

Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates.

A cationic nickel complex of the bis(8-quinolyl)(3,5-di-tert-butylphenoxy)phosphine (NPN) ligand, [(NPN)NiCl]+, is a precursor to efficient catalysts for the hydrosilation of alkenes with a variety of hydrosilanes under mild conditions and low catalyst loadings. DFT studies reveal the presence of two coupled catalytic cycles based on [(NPN)NiH]+ and [(NPN)NiSiR3]+ active species, with the latter being more efficient for producing the product. The preferred silyl-based catalysis is not due to a more facile insertion of alkene into the Ni-Si (vs. Ni-H) bond, but by consistent and efficient conversions of the hydride to the silyl complex.

Fluoreno[2,1-a]fluorene: an ortho-naphthoquinodimethane-based system with partial diradical character.

Fluoreno[2,1-a]fluorene, a molecule comprising fused ortho-quinodimethane units in a 1,5-napthoquinodimethane core, has been prepared and investigated with spectroscopy (UV-Vis-NIR, 1H-NMR and Raman), SQUID magnetometry, spectroelectrochemistry and quantum chemistry. While para-quinodimethanes with a 2,6-substitution pattern exist as closed-shell species and meta-quinodimethanes with 2,7-substitution favour a ground electronic state with very large diradical character, our 1,5-substituted ortho-naphthoquinodimethane-based system exhibits an intermediate degree of diradical character.

Quantum Mechanics/Molecular Mechanics Studies on the Relative Reactivities of Compound I and II in Cytochrome P450 Enzymes.

The cytochromes P450 are drug metabolizing enzymes in the body that typically react with substrates through a monoxygenation reaction. During the catalytic cycle two reduction and protonation steps generate a high-valent iron (IV)-oxo heme cation radical species called Compound I. However, with sufficient reduction equivalents present, the catalytic cycle should be able to continue to the reduced species of Compound I, called Compound II, rather than a reaction of Compound I with substrate. In particular, since electron transfer is usually on faster timescales than atom transfer, we considered this process feasible and decided to investigate the reaction computationally. In this work we present a computational study using density functional theory methods on active site model complexes alongside quantum mechanics/molecular mechanics calculations on full enzyme structures of cytochrome P450 enzymes. Specifically, we focus on the relative reactivity of Compound I and II with a model substrate for O⁻H bond activation. We show that generally the barrier heights for hydrogen atom abstraction are higher in energy for Compound II than Compound I for O⁻H bond activation. Nevertheless, for the activation of such bonds, Compound II should still be an active oxidant under enzymatic conditions. As such, our computational modelling predicts that under high-reduction environments the cytochromes P450 can react with substrates via Compound II but the rates will be much slower.

An Objective Alternative to IUPAC's Approach To Assign Oxidation States.

The IUPAC has recently clarified the term oxidation state (OS), and provided algorithms for its determination based on the ionic approximation (IA) of the bonds supported by atomic electronegativities (EN). Unfortunately, there are a number of exceptions and ambiguities in IUPAC's algorithms when it comes to practical applications. Our comprehensive study reveals the critical role of the chemical environment on establishing the OS, which cannot always be properly predicted using fix atomic EN values. By identifying what we define here as subsystems of enhanced stability within the molecular system, the OS can be safely assigned in many cases without invoking exceptions. New insights about the effect of local aromaticity upon OS are revealed. Moreover, we prove that there are intrinsic limitations of the IA that cannot be overcome. In this context, the effective oxidation state (EOS) analysis arises as a robust and general scheme to derive an OS without any external guidance.

Metal Cluster Electrides: A New Type of Molecular Electride with Delocalised Polyattractor Character.

Electrides are ionic substances containing isolated electrons. These confined electrons are topologically characterised by a quasi-atom, that is, a non-nuclear attractor (NNA) of the electron density. The electronic structure of the octahedral 4 A1g Li6+ and 5 A1g Be6 species shows that these species have a large number of NNAs. These NNAs have highly delocalised electron densities and, as a result, the chemical bonding pattern of these systems is reminiscent of that in solid metals, in which metal cations are surrounded by a "sea" of delocalised valence electrons. We propose the term metal cluster electrides to refer to this new class of compounds. In this study, we establish a computational protocol to identify, characterize, and design metal cluster electrides and we elucidate the intricate bonding patterns of this particular type of species.

Reactivity Patterns of (Protonated) Compound†II and Compound†I of Cytochrome P450: Which is the Better Oxidant?

The cytochromes P450 are versatile enzymes in human physiology that perform substrate hydroxylation reactions extremely efficiently. In this work, we present results of a computational study on the reactivity patterns of Compound I, Compound II, and protonated Compound II with model substrates, and we address the question of which of these compounds is the most effective oxidant? All calculations, regardless of the substrate, implicated that Compound I is the superior oxidant of the three. However, Compound II and protonated Compound II were found to react with free energies of activation that are only a few kcal mol-1 higher in energy than those obtained with Compound I. Therefore, Compound II and protonated Compound II should be able to react with aliphatic groups with moderate C-H bond strengths. We have analysed all results in detail and have given electronic, thermochemical, valence bond, and molecular orbital rationalizations on the reactivity differences and explained experimental product distributions. Overall, the findings implied that alternative oxidants could operate alongside Compound I in complex reaction mechanisms of enzymatic and synthetic iron porphyrinoid complexes.

Iron and Manganese Catalysts for the Selective Functionalization of Arene C(sp(2) )-H Bonds by Carbene Insertion.

The first examples of the direct functionalization of non-activated aryl sp(2) C-H bonds with ethyl diazoacetate (N2 CHCO2 Et) catalyzed by Mn- or Fe-based complexes in a completely selective manner are reported, with no formation of the frequently observed cycloheptatriene derivatives through competing Buchner reaction. The best catalysts are Fe(II) or Mn(II) complexes bearing the tetradentate pytacn ligand (pytacn= 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane). When using alkylbenzenes, the alkylic C(sp(3) )-H bonds of the substituents remained unmodified, thus the reaction being also selective toward functionalization of sp(2) C-H bonds.

Oxidation States from Wave Function Analysis.

We introduce a simple and general scheme to derive from wavefuntion analysis the most appropriate atomic/fragment electron configurations in a molecular system, from which oxidation states can be inferred. The method can be applied for any level of theory for which the first-order density matrix is available, and unlike others, it is not restricted to transition metal complexes. The method relies on the so-called spin-resolved effective atomic orbitals which for the present purpose is extended here to deal with molecular fragments/ligands. We describe in detail the most important points of the new scheme, in particular the hierarchical fragment approach devised for practical applications. A number of transition metal complexes with different formal oxidation states and spin states and a set of organic and inorganic compounds are provided as illustrative examples of the new scheme. Challenging systems such as transition state structures are also tackled on equal footing.

Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent.

The reaction mechanisms for alkane hydroxylation catalyzed by non-heme Fe(V)O complexes presented in the literature vary from rebound stepwise to concerted highly asynchronous processes. The origin of these important differences is still not completely understood. Herein, in order to clarify this apparent inconsistency, the hydroxylation of a series of alkanes (methane and substrates bearing primary, secondary, and tertiary C-H bonds) through a Fe(V)O species, [Fe(V)(O)(OH)(PyTACN)](2+) (PyTACN = 1-(2'-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane), has been computationally examined at the gas phase and in acetonitrile solution. The initial breaking of the C-H bond can occur via hydrogen atom transfer (HAT), leading to an intermediate where there is an interaction between the radical substrate and [Fe(IV)(OH)2(PyTACN)](2+), or through hydride transfer to form a cationic substrate interacting with the [Fe(III)(OH)2(PyTACN)](+) species. Our calculations show the following: (i) except for methane in the rest of the alkanes studied, the intermediate formed by R(+) and [Fe(III)(OH)2(PyTACN)](+) is more stable than that involving the alkyl radical and the [Fe(IV)(OH)2(PyTACN)](2+) complex; (ii) in spite of (i), the first step of the reaction mechanism for all substrates is a HAT instead of hydride abstraction; (iii) the HAT is the rate-determining step for all analyzed cases; and (iv) the barrier for the HAT decreases along methane → primary → secondary → tertiary carbon. The second part of the reaction mechanism corresponds to the rebound process. Therefore, the stereospecific hydroxylation of alkane C-H bonds by non-heme Fe(V)(O) species occurs through a rebound stepwise mechanism that resembles that taking place at heme analogues. Finally, our study also shows that, to properly describe alkane hydroxylation processes mediated by Fe(V)O species, it is essential to consider the solvent effects during geometry optimizations. The use of gas-phase geometries explains the variety of mechanisms for the hydroxylation of alkanes reported in the literature.

On the existence and characterization of molecular electrides.

Electrides are ionic compounds thus far appearing in the solid state, where the anionic part is constituted by isolated electrons. We herein provide an unambiguous computational means to distinguish electrides from similar species, proving the existence of some electrides in the gas phase. We also put forward a recipe to design new electrides.

The mechanism of stereospecific C-H oxidation by Fe(Pytacn) complexes: bioinspired non-heme iron catalysts containing cis-labile exchangeable sites.

A detailed mechanistic study of the hydroxylation of alkane C-H bonds using H2O2 by a family of mononuclear non heme iron catalysts with the formula [Fe(II)(CF3SO3)2(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the α and γ positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis-labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The C-H hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that C-H hydroxylation is performed by highly electrophilic [Fe(V)(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the C-H bond, followed by rebound of the hydroxyl ligand. The [Fe(V)(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic-labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the α substituent of the pyridine, and this reactivity behavior is rationalized by computational methods.