Primary Photophysics of Nicotinamide Chromophores in Their Oxidized and Reduced Forms.

Nicotinamide adenine dinucleotide (NADH) is an important enzyme cofactor with emissive properties that allow it to be used in fluorescence microscopies to study cell metabolism. Its oxidized form NAD+, on the other hand, is considered to produce negligible fluorescence. In this contribution, we describe the photophysics of the isolated nicotinamidic system in both its reduced and oxidized states. This was achieved through the study of model molecules that do not carry the adenine nucleotide since its absorbance would overlap with the absorption spectrum of the nicotinamidic chromophores. We studied three model molecules: nicotinamide (niacinamide, an oxidized form without nitrogen substitution), the oxidized chromophore 1-benzyl-3-carbamoyl-pyridinium bromide (NBzOx), and its reduced form 1-benzyl-1,4-dihydronicotinamide (NBz). For a full understanding of the dynamics, we performed both femtosecond-resolved emission and transient absorption experiments. The oxidized systems, nicotinamide and NBzOx, have similar photophysics, where the originally excited bright state decays on an ultrafast timescale of less than 400 fs. The depopulation of this state is followed by excited-state positive absorption signals, which evolve in two timescales: the first one is from 1 to a few picoseconds and is followed by a second decaying component of 480 ps for nicotinamide in water and of 80-90 ps for nicotinamide in methanol and NBzOx in aqueous solution. The long decay times are assigned as the S1 lifetimes populated from the original higher-lying bright singlet, where this state is nonemissive but can be detected by transient absorption. While for NBzOx in aqueous solution and for nicotinamide in methanol, the S1 signal decays to the solvent-only level, for the aqueous solutions of nicotinamide, a small transient absorption signal remains after the 480 ps decay. This residual signal was assigned to a small population of triplet states formed during the slower S1 decay for nicotinamide in water. The experimental results were complemented by XMS-CASPT2 calculations, which reveal that in the oxidized forms, the rapid evolution of the initial π-π* state is due to a direct crossing with lower-energy dark n-π* singlet states. This coincides with the experimental observation of long-lived nonemissive states (80 to 480 ps depending on the system). On the other hand, the reduced model compound NBz has a long-lived emissive π-π* S1 state, which decays with a 510 ps time constant, similarly to the parent compound NADH. This is consistent with the XMS-CASPT2 calculations, which show that for the reduced chromophore, the dark states lie at higher energies than the bright π-π* S1 state.

Two-photon isomerization properties of donor-acceptor Stenhouse adducts.

Donor-acceptor Stenhouse adducts (DASAs) are important photo-responsive molecules that undergo electrocyclic reactions after light absorption. From these properties, DASAs have received extensive attention as photo-switches with negative photochromism. Meanwhile, several photochemical applications require isomerization events to take place in highly localized volumes at variable depths. Such focused photoreactions can be achieved if the electronic excitation is induced through a non-linear optical process. In this contribution we describe DASAs substituted with extended donor groups which provide them with significant two-photon absorption properties. We characterized the photo-induced transformation of these DASAs from the open polymethinic form to their cyclopentenic isomer with the use of 800 nm femtosecond pulses. These studies verified that the biphotonic excitation produces equivalent photoreactions as linear absorbance. We also determined these DASAs' two-photon absorption cross sections from measurements of their photoconverted yield after biphotonic excitation. As we show, specific donor sections provide these systems with important biphotonic cross-sections as high as 615 GM units. Such properties make these DASAs among the most non-linearly active photo-switchable molecules. Calculations at the TDDFT level with the optimally tuned range-separated functional OT-CAM-B3LYP, together with quadratic response methods indicate that the non-linear photochemical properties in these molecules involve higher lying electronic states above the first excited singlet. This result is consistent with the observed relation between their two-photon chemistry and the onset of their short wavelength absorption features around 400 nm. This is the first report of the non-linear photochemistry of DASAs. The two-photon isomerization properties of DASAs extend their applications to 3D-photocontrol, non-linear lithography, variable depth birefringence, and localized drug delivery schemes.

Solvent Effects on the Singlet-Triplet Couplings in Nitroaromatic Compounds.

Nitrated polycyclic molecules can present the largest singlet-triplet crossing rates among organic molecules. This implies that most of these compounds have no detectable steady-state fluorescence. In addition, some nitroaromatics undergo a complex series of photoinduced atom rearrangements that result in nitric oxide dissociation. The overall photochemistry of these systems depends critically on the competition between the rapid intersystem crossing channel and other excited-state pathways. In this contribution, we sought to characterize the degree of stabilization of the S1 state due to solute-solvent interactions, and to quantify the effect of such stabilization on their photophysical pathways. We studied 2- and 4-nitropyrene (2-NP and 4-NP), which are atypically emissive nitroaromatics in a series of solvents. From steady-state and time-resolved measurements, the S1 state of these molecules shows significant stabilization as the solvent polarity is increased. On the other hand, specific triplet states that are iso-energetic with the emissive singlet (T3 for 2-NP and T2 for 4-NP) in nonpolar solvents become slightly de-stabilized upon increasing the solvent polarity. These combined effects result in rapid singlet-triplet population transfer in nonpolar solvents for both molecules. In contrast, for solvents with even slightly higher polarities, the first excited singlet is stabilized in relation to the specific triplet states, leading to much longer S1 lifetimes. These effects can be summarized as a highly solvent-dependent coupling/decoupling of the manifolds. Similar effects are also likely to be present in other nitroaromatics where there is a dynamic competition between nitric oxide dissociation and intersystem crossing. The drastic effects of the solvent polarity in the manifold crossing pathway should be taken into consideration in both theoretical and experimental studies of nitroaromatics.

A fast approximate extension of the interacting quantum atoms energy decomposition to excited states.

An approach is developed for the fast calculation of the interacting quantum atoms energy decomposition (IQA) from the information contained in the first order reduced density matrix only. The proposed methodology utilizes an approximate exchange-correlation density from Density Matrix Functional Theory without the need to evaluate the correlation-exchange contribution directly. Instead, weight factors are estimated to decompose the exact Vxc into atomic and pairwise contributions. In this way, the sum of the IQA contributions recovers the energy obtained from the electronic structure calculation. This method can, hence, be applied to obtain atomic contributions in excited states on the same footing as in their ground states using any method that delivers the reduced first-order density matrix. In this way, one can locate chromophores from first principles quantum chemical calculations. Test calculations on the ground and excited states of a set of small molecules indicate that the scaled atomic contributions reproduce vertical electronic transition energies calculated exactly. This approach may be useful to extend the applicability of the IQA approach in the study of large photochemical systems especially when the calculations of the second order reduced density matrices is prohibitive or not possible.

Experimental and theoretical study of novel aminobenzamide-aminonaphthalimide fluorescent dyads with a FRET mechanism.

In this work, both experimental and theoretical methods were used to study the photophysical and metal ion binding properties of a series of new aminobenzamide-aminonaphthalimide (2ABZ-ANAPIM) fluorescent dyads. The 2-aminobenzamide (2ABZ) and 6-aminonaphthalimide (ANAPIM) fluorophores were linked through alkyl chains (C2 to C6) to obtain four fluorescent dyads. These dyads present a highly efficient (0.61 to 0.98) Förster Resonant Energy Transfer (FRET) from the 2ABZ to the ANAPIM due to the 2ABZ emission and ANAPIM excitation band overlap and the configurational stacking of both aromatic systems which allows the energy transfer. These dyads interact with Cu2+ and Hg2+ metal ions in solution inhibiting the FRET mechanism by the cooperative coordination of both 2ABZ and ANAPIM moieties. Both experimental and theoretical results are consistent and describe clearly the photophysical and coordination properties of these new dyads.

Implementation of the interacting quantum atom energy decomposition using the CASPT2 method.

We present an implementation of the interacting quantum atom (IQA) energy decomposition scheme using the complete active space second-order perturbation theory (CASPT2). This combination yields a real-space interpretation tool with a proper account of the static and dynamic correlation that is particularly relevant for the description of processes in electronic excited states. The IQA/CASPT2 approach allows determination of the energy redistribution that takes place along a photophysical/photochemical deactivation path in terms of self- and interatomic contributions. The applicability of the method is illustrated by the description of representative processes spanning different bonding regimes: noble gas excimer and exciplex formation, the reaction of ozone with a chlorine atom, and the photodissociations of formaldehyde and cyclobutane. These examples show the versatility of using CASPT2 with the significant information provided by the IQA partition to describe chemical processes with a large multiconfigurational character.

Feynman Force Analysis of Chemical Processes in Terms of Topological Atomic Contributions.

The nature of the chemical bond is analyzed in terms of the atomic contributions to the Feynman forces using the Quantum Theory of Atoms in Molecules and the Interacting Quantum Atoms method. This approach provides a means for quantifying the relationship between the atomic electronic reorganization and the evolution of functional group interactions with the forces exerted on the nuclear framework during a chemical transformation. Using this decomposition scheme, the forces driving a chemical process are locally assigned to atoms or functional group contributions. The interatomic component of the forces can be ascribed as bonding forces; their exchange-correlation and electrostatic contributions reveal the nature of the interactions affecting the forces on the nuclei. This method is used to analyze the chemical interactions involved in the formation of ground and excited state diatomic molecules, the prototropism of formamide, the Diels-Alder cycloaddition of 1,3-butadiene with ethylene, and the Jahn-Teller effect of hydrated transition metal complexes.

Exotic Bonding Regimes Uncovered in Excited States.

Real-space tools were employed to show that the chemical bonding scenario used routinely to understand ground states lacks the necessary flexibility in excited states. It is shown that, even for two-center, two-electron bonds, the real-space bond orders have exotic values that have never been reported. The nature of these situations was uncovered by using electron-counting techniques that provide an appealing statistical interpretation of bonding descriptors, together with simple physical models. Bond orders greater than one as well as negative bond orders for a single bonding electron pair emerge in situations in which the electrons in the pair show a gregarious (bosonic) instead of the usual lonely (fermionic) behavior. In the first case the gregarious pair is intra-atomic, whereas the coupling is interatomic in the second. A number of examples are used to substantiate these claims.

Unveiling the role of intra and interatomic interactions in the energetics of reaction schemes: a quantum chemical topology analysis.

In this work we present a detailed analysis of selected reaction schemes in terms of the atomic components of the electronic energy defined by the quantum theory of atoms in molecules and the interacting quantum atoms method. The aim is to provide an interpretation tool for the energy change involved in a chemical reaction by means of the atomic and interaction contributions to the energies of the molecules involved. Ring strain in cyclic alkanes, the resonance energy of aromatic and antiaromatic molecules, local aromaticity in polycyclic aromatic hydrocarbons, intermolecular bonding in hydrogen fluoride clusters, and hydration of d-block metal dications were selected for the study. It was found that in addition to the changes in the strong C-C interactions in the carbon skeleton of the organic molecular rings, other contributions not usually considered to be important such as those between C and H atoms (either bonded or not) need to be considered in order to account for the net energy changes. The analysis unveils the role of the ionic and covalent contributions to the hydrogen bonding in HF clusters and the energetic origin and extent of cooperative effects involved. Moreover, the "double-hump" behavior observed for the hydration energy trend of [M(H2O)6]2+ complexes is explained in terms of the deformation energy of the metal cation and the increasingly covalent metal-water interactions. In addition, proper comparisons with the description provided by other methodologies are briefly discussed. The topological approach proposed in this contribution proves to be useful for the description of energy changes of apposite reaction schemes in chemically meaningful terms.

Energetic Analysis of Conjugated Hydrocarbons Using the Interacting Quantum Atoms Method.

A number of aromatic, antiaromatic, and nonaromatic organic molecules was analyzed in terms of the contributions to the electronic energy defined in the quantum theory of atoms in molecules and the interacting quantum atoms method. Regularities were found in the exchange and electrostatic interatomic energies showing trends that are closely related to those of the delocalization indices defined in the theory. In particular, the CC interaction energies between bonded atoms allow to rationalize the energetic stabilization associated with the bond length alternation in conjugated polyenes. This approach also provides support to Clar's sextet rules devised for aromatic systems. In addition, the H⋯H bonding found in some of the aromatic molecules studied was of an attractive nature, according to the stabilizing exchange interaction between the bonded H atoms. © 2017 Wiley Periodicals, Inc.

Chemical bonding in excited states: Energy transfer and charge redistribution from a real space perspective.

This work provides a novel interpretation of elementary processes of photophysical relevance from the standpoint of the electron density using simple model reactions. These include excited states of H2 taken as a prototype for a covalent bond, excimer formation of He2 to analyze non-covalent interactions, charge transfer by an avoided crossing of electronic states in LiF and conical interesections involved in the intramolecular scrambling in C2 H4 . The changes of the atomic and interaction energy components along the potential energy profiles are described by the interacting quantum atoms approach and the quantum theory of atoms in molecules. Additionally, the topological analysis of one- and two-electron density functions is used to explore basic reaction mechanisms involving excited and degenerate states in connection with the virial theorem. This real space approach allows to describe these processes in a unified way, showing its versatility and utility in the study of chemical systems in excited states. © 2017 Wiley Periodicals, Inc.