A 2-pyridyl-2,1-borazaronaphthalene derivative as forefather of a new class​ of bidentate ligands: synthesis and application in luminescent Ir(III) complexes

Borazaro compounds (or azaborines) are aromatic compounds in which a C=C unit is replaced by an isoelectronic B-N unit. The possibility to generate chemical diversity has led to an increasing interest in azaborines, especially in the fields of biomedical research and optoelectonics. In particular, Dewar’s synthesis of borazaronaphthalene is a common starting step to obtain different 1,2-azaborines via nucleophilic substitution on the boron atom. Here we present the synthesis of a novel 1,2-azaborine (i.e. 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene, named FAAH) via functionalization of 2-chloro-4-methyl-2,1-borazaronaphthalene with a 2-pyridyl unit. FAAH can be used as an anionic bidentate ligand for transition metal complexes, since it can chelate the metal center with both the pyridine and the azaborine nitrogen atoms. FAAH was used for the synthesis of a series of neutral luminescent Ir(III) complexes (named FAV, FAB and FAR) of general formula [Ir(C^N )2(FAA)], where C^N indicates three different cyclometalating ligands: i.e. 2-phenylpyridine in the case of FAV; 2-(2,4-difluorophenyl)pyridine in the case of FAB; 2-methyl-3-phenylquinoxaline in the case of FAR. The reaction yields are quite low, however it was always possible to characterize all the compounds by means of NMR spectroscopy. A complete photophysical and theoretical characterization is also presented. FAAH displays a good chemical stability and a high photoluminescence quantum yield (up to 28 % in solution). On the contrary, the Iridium complexes undergo degradation over time in solution. Despite this stability problem, it was possible to get a good understanding of the photophysics of the three complexes: the emission of both FAV and FAB is observed around 500 nm and arises from a 3LC state centered on the azaborine ligand. In the case of FAR, the emitting state is basically 3MLCT/3LLCT in nature and the resulting broad and unstructured emission band is centered around 700 nm

The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations

Simulation of photoinduced processes in organic chromophores: mapping photochemically relevant states for accurate dynamics

The simulation of ultrafast photoinduced processes is a fundamental step towards the understanding of the underlying molecular mechanism and interpretation/prediction of experimental data. Performing a computer simulation of a complex photoinduced process is only possible introducing some approximations but, in order to obtain reliable results, the need to reduce the complexity must balance with the accuracy of the model, which should include all the relevant degrees of freedom and a quantitatively correct description of the electronic states involved in the process. This work presents new computational protocols and strategies for the parameterisation of accurate models for photochemical/photophysical processes based on state-of-the-art multiconfigurational wavefunction-based methods. The required ingredients for a dynamics simulation include potential energy surfaces (PESs) as well as electronic state couplings, which must be mapped across the wide range of geometries visited during the wavepacket/trajectory propagation. The developed procedures allow to obtain solid and extended databases reducing as much as possible the computational cost, thanks to, e.g., specific tuning of the level of theory for different PES regions and/or direct calculation of only the needed components of vectorial quantities (like gradients or nonadiabatic couplings). The presented approaches were applied to three case studies (azobenzene, pyrene, visual rhodopsin), all requiring an accurate parameterisation but for different reasons. The resulting models and simulations allowed to elucidate the mechanism and time scale of the internal conversion, reproducing or even predicting new transient experiments. The general applicability of the developed protocols to systems with different peculiarities and the possibility to parameterise different types of dynamics on an equal footing (classical vs purely quantum) prove that the developed procedures are flexible enough to be tailored for each specific system, and pave the way for exact quantum dynamics with multiple degrees of freedom

Diffractive Imaging of Conical Intersections Amplified by Resonant Infrared Fields

International audienc

Photoisomerization transition state manipulation by entangled two-photon absorption

We demonstrate how two-photon excitation with quantum light can influence elementary photochemical events. The azobenzene trans → cis isomerization following entangled two-photon excitation is simulated using quantum nuclear wave packet dynamics. Photon entanglement modulates the nuclear wave packets by coherently controlling the transition pathways. The photochemical transition state during passage of the reactive conical intersection in azobenzene photoisomerization is strongly affected with a noticeable alteration of the product yield. Quantum entanglement thus provides a novel control knob for photochemical reactions. The distribution of the vibronic coherences during the conical intersection passage strongly depends on the shape of the initial wave packet created upon quantum light excitation. X-ray signals that can experimentally monitor this coherence are simulated

Coupled Electronic and Nuclear Motions during Azobenzene Photoisomerization Monitored by Ultrafast Electron Diffraction

International audienc

Unveiling the spatial distribution of molecular coherences at conical intersections by covariance X-ray diffraction signals

International audienceThe outcomes and timescales of molecular nonadiabatic dynamics are decisively impacted by the quantum coherences generated at localized molecular regions. In time-resolved X-ray diffraction imaging, these coherences create distinct signatures via inelastic photon scattering, but they are buried under much stronger background elastic features. Here, we exploit the rich dynamical information encoded in the inelastic patterns, which we reveal by frequency-dispersed covariance ultrafast powder X-ray diffraction of stochastic X-ray free-electron laser pulses. This is demonstrated for the photoisomerization of azobenzene involving the passage through a conical intersection, where the nuclear wave packet branches and explores different quantum pathways. Snapshots of the coherence dynamics are obtained at high frequency shifts, not accessible with conventional diffraction measurements. These provide access to the timing and to the confined spatial distribution of the valence electrons directly involved in the conical intersection passage. This study can be extended to full three-dimensional imaging of conical intersections with ultrafast X-ray and electron diffraction

Time-Resolved X-ray Absorption Spectroscopy: An MCTDH Quantum Dynamics Protocol.

Expressions for linear and nonlinear spectroscopy simulation in the X-ray window in which the time evolution of a photoexcited molecular system is treated via quantum dynamics are derived. By leveraging on the peculiar properties of core-excited/ionized states, first- and third-order response functions are recast in the limit of time-scale separation between the extremely short core-state lifetime and the (comparably longer) electronic-state transfer and nuclear vibrational motion. This work is a natural extension of Segatta et al. (J. Chem. Theory Comput. 2023, 19, 2075-2091), in which some of the present authors coupled MCTDH quantum dynamics to spectroscopy simulation at different levels of sophistication. Full quantum dynamics and approximate expressions are compared by simulating X-ray transient absorption spectroscopy at the carbon K-edge in the pyrene molecule

Enabling Image-Based Streamflow Monitoring at the Edge

Monitoring streamflow velocity is of paramount importance for water resources management and in engineering practice. To this aim, image-based approaches have proved to be reliable systems to non-intrusively monitor water bodies in remote places at variable flow regimes. Nonetheless, to tackle their computational and energy requirements, offload processing and high-speed internet connections in the monitored environments, which are often difficult to access, is mandatory hence limiting the effective deployment of such techniques in several relevant circumstances. In this paper, we advance and simplify streamflow velocity monitoring by directly processing the image stream in situ with a low-power embedded system. By leveraging its standard parallel processing capability and exploiting functional simplifications, we achieve an accuracy comparable to state-of-the-art algorithms that typically require expensive computing devices and infrastructures. The advantage of monitoring streamflow velocity in situ with a lightweight and cost-effective embedded processing device is threefold. First, it circumvents the need for wideband internet connections, which are expensive and impractical in remote environments. Second, it massively reduces the overall energy consumption, bandwidth and deployment cost. Third, when monitoring more than one river section, processing \u201cat the very edge\u201d of the system efficiency improves scalability by a large margin, compared to offload solutions based on remote or cloud processing. Therefore, enabling streamflow velocity monitoring in situ with low-cost embedded devices would foster the widespread diffusion of gauge cameras even in developing countries where appropriate infrastructure might be not available or too expensive

Nonlinear Molecular Electronic Spectroscopy via MCTDH Quantum Dynamics: From Exact to Approximate Expressions

We present an accurate and efficient approach to computing the linear and nonlinear optical spectroscopy of a closed quantum system subject to impulsive interactions with an incident electromagnetic field. It incorporates the effect of ultrafast nonadiabatic dynamics by means of explicit numerical propagation of the nuclear wave packet. The fundamental expressions for the evaluation of first- and higher-order response functions are recast in a general form that can be used with any quantum dynamics code capable of computing the overlap of nuclear wave packets evolving in different states. Here we present the evaluation of these expressions with the multiconfiguration time-dependent Hartree (MCTDH) method. Application is made to pyrene, excited to its lowest bright excited state S2 which exhibits a sub-100-fs nonadiabatic decay to a dark state S1. The system is described by a linear vibronic coupling Hamiltonian, parametrized with multiconfiguration electronic structure methods. We show that the ultrafast nonadiabatic dynamics can have a remarkable effect on the spectral line shapes that goes beyond simple lifetime broadening. Furthermore, a widely employed approximate expression based on the time scale separation of dephasing and population relaxation is recast in the same theoretical framework. Application to pyrene shows the range of validity of such approximations