Denis Jacquemin

• PhD
• Professor at Nantes Université

In this perspective, we present an overview of the determination of excited-state properties of "real-life" dyes, and notably of their optical absorption and emission spectra, performed during the last decade with time-dependent density functional theory (TD-DFT). We discuss the results obtained with both vertical and adiabatic (vibronic) approxima...

In this tutorial review, we show how Time-Dependent Density Functional Theory (TD-DFT) has become a popular tool for computing the signatures of electronically excited states, and more specifically, the properties directly related to the optical (absorption and emission) spectra of molecules. We discuss the properties that can be obtained with wide...

In this perspective, we present an overview of recent progress on Time-Dependent Density Functional Theory (TD-DFT) with a specific focus on its accuracy and on models able to take into account environmental effects, including complex media. To this end, we first summarise recent benchmarks and define an average TD-DFT accuracy in reproducing excit...

From an endophytic strain of Cophinforma mamane isolated from the leaves of Bixa orellana, a previously undescribed γ-butyrolactone compound (2) and three new cyclopentapeptides (3-5) have been isolated from the same strain, along with the known (4R)-striatisporolide A (1). Their structures were elucidated through extensive spectral analysis and DP...

In this article, it describes the synthesis of a series of fluorophores consisting of N‐alkyl or N‐aryl pyridinium groups connected at different positions of a 2‐(2′‐hydroxyphenyl)benzoxazole scaffold and the exploration of the photophysical properties in solution (dichloromethane) and in the solid state, as amorphous powders. All dyes display a ba...

To elucidate the molecular structure of the difluoro dipyridomethene system and to establish structure–property relationships, an extensive synthetic work is reported. Four classes of novel fluorescent BF2‐DIPYR complexes are prepared via Suzuki–Miyaura cross‐coupling reaction from the corresponding mono‐ and bis‐brominated dyes in moderate to good...

Computer simulations play a pivotal role in interpreting experimental two-photon absorption (2PA) spectra. One of the key aspects of the simulation of these spectra is to take into account the vibrational fine structure of the bands in electronic spectra. This is typically done by employing Franck–Condon (FC) term and low-order terms in the Herzber...

Two compact far-red cationic benzoquinone diimine dyes were synthesized, having molecular weights lower than 400 or 300 Da and featuring light absorption properties centered around 700 nm. Their redox and...

The present work is focused on designing novel heteroaromatic systems, formally a hybrid of dibenzo[b,f]oxazepines and 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs). Straightforward synthesis affords a family of rigid, centrosymmetric, π-expanded aromatic heterocycles amenable to facile post-functionalization. The rigidified molecular architecture is r...

Excited-state absorption (ESA) corresponds to the transition between two electronic excited states and is a fundamental process for probing and understanding light-matter interactions. Accurate modeling of ESA is indeed often required to interpret time-resolved experiments. In this contribution, we present a dataset of 53 ESA oscillator strengths i...

Tuning the synthesis of quinoxaline derivatives toward a new family of azamacrocycles.

Drastic changes to the character of the acidic catalyst enable the reversal of the double alkyne benzannulation reaction output. In the presence of a strong Brønsted acid, 1,4-dihydropyrrolopyrroles undergo transformation which results in the formation of two 7-membered rings. Computational studies imply that the thermodynamically unfavored 7-membe...

Here we present a highly versatile synthetic strategy based on twofold 6π‐electrocyclization accompanied with HBr elimination as a novel approach towards centrosymmetric multi‐heteroatom‐doped nanographenes build around an electron‐rich 1,4‐dihydropyrrolo[3,2‐b]pyrrole core. A straightforward synthesis from readily available substrates offers a uni...

Combining bioresources and photo-induced polymerization is a promising way to design sustainable and high-performing antibacterial materials. In this study, we propose a green synthesis of bio-based materials with dual antibacterial properties by photopolymerization. Two new methacrylate-based hydroxyanthraquinones derived from purpurin and alizari...

This review provides a comprehensive examination of the applications of the seminal coupling principle introduced by Siegfried Dähne and Dieter Leupold in 1966. Their heuristic and groundbreaking work proposed that combining multiple polymethine subunits within a single chromophore enables orbital coupling, consequently narrowing the HOMO–LUMO gap,...

The synthesis and the studies of optical and electronic properties of new bis‐indenone‐fused tetraazaanthracene isomers as electron accepting materials are reported. TD‐DFT calculations have been also undertaken and corroborate experiments. Organic field effect transistors demonstrated unipolar n‐type characteristics and average electron mobility v...

Here we present a highly versatile synthetic strategy based on twofold 6π-electrocyclization accompanied with HBr elimination as a novel approach towards centrosymmetric multi-heteroatom-doped nanographenes build around an electron-rich 1,4-dihydropyrrolo[3,2-b]pyrrole core. A straightforward synthesis from readily available substrates offers a uni...

The outcome of the reaction of tetracyanoethylene with 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) strongly depends on the character of the substituents present at positions 2 and 5. With electron-withdrawing substituents, the reaction does not occur at all, while, in contrast, the presence of electron-donating substituents yields addition–eliminatio...

Chiral molecular materials able to emit circularly polarized luminescence (CPL) have attracted considerable interest in the last decades, due to the potential of CP-light in a wide range of applications....

This article reports the synthesis, along with structural and photophysical characterization of 2‐(2’‐hydroxyphenyl)benzazole derivatives functionalized with various azaheterocycles (pyridine, pyrimidine, terpyridine). These compounds show dual‐state emission properties, that is intense fluorescence both in solution and in the solid‐state with a ra...

To expand the QUEST database of highly-accurate vertical transition energies, we consider a series of large organic chromogens ubiquitous in dye chemistry, such as anthraquinone, azobenzene, BODIPY, and naphthalimide. We compute, at the CC3 level of theory, the singlet and triplet vertical transition energies associated with the low-lying excited s...

We describe the synthesis, full photophysical study, and ab initio calculations of 2‐(2’‐hydroxyphenyl)benzazole (HBX) fluorophores substituted, at the meta position of the phenol group, by pyridine derivatives. HBX are commonly used as model dyes to study the stimuli‐induced modulation of the Excited State Intramolecular Proton Transfer (ESIPT) pr...

Two new benzobisimidazole platforms incorporating 7-hydroxyquinoline moieties were synthesized and characterized to explore potential multiple proton transfer processes. Combining experimental analysis with theoretical insights, we investigated the photophysical properties and...

This study presents the synthesis and characterization of phenazinium dyes with absorption ranging from red to far-red, as well as emission extending into the far-red to near-infrared (NIR) region. The procedure involves the post-functionalization of a triamino-phenazinium that was recently reported as a theranostic agent. The introduction of elect...

In the realm of photochemistry, the significance of double excitations (also known as doubly excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement in key electronic transitions essential in light-induced chemical reactions as well as their challenging nature from the computational theoreti...

Non-adiabatic dynamics simulations have become a standard approach to explore photochemical reactions. Such simulations require underlying potential energy surfaces and couplings between them, calculated at a chosen level of theory, yet this aspect is rarely assessed. Here, in combination with the popular trajectory surface hopping dynamics method,...

We reexamine ΔCCSD, a state-specific coupled-cluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient when dealing with doubly excited states, a domain in which the standard equation-of-motion CCSD (EOM-CCSD) formalism f...

In an effort to expand the existing QUEST database of accurate vertical transition energies [Véril et al. WIREs Comput. Mol. Sci. 2021 , 11 , e1517], we have modeled more than 100 electronic excited states of different natures (local, charge‐transfer, Rydberg, singlet, and triplet) in a dozen of mono‐ and di‐substituted benzenes, including aniline,...

We synthesized a series of four parent aza-β-ketoiminate organoboron complexes and performed spectroscopic studies using both experimental and computational techniques. We studied how benzannulation influences the vibronic structure of the...

Excited-State Intramolecular Proton Transfer (ESIPT) emission is associated with intense single or multiple fluorescence in the solid-state, along with enhanced photostability and sensitivity to the close environment. As a result, ESIPT probes are attractive candidates for ratiometric sensing of a variety of substrates. A new family of ESIPT fluoro...

We study the accuracy of excited state (ES) geometries using optimally tuned LC-PBE functionals with tuning based on GW quasiparticle energies. We compare the results obtained with the PBE, PBE0, non-tuned, and tuned LC-PBE functionals with available high-level CC reference values as well as experimental data. First, we compare ES geometrical param...

A series of six azaborahelicenes with varying electron-donor substitution at the 4-position of the aryl residue (i.e., naphthyl) or with variable π-extension of the aryl residue (thianthrenyl, anthryl, pyrenyl) was prepared with an efficient and flexible synthetic protocol. These different types of functionalization afforded notably pronounced intr...

This study highlights the outstanding photo-initiating properties of two new visible-light absorbing benzophenone porphyrin-based photosensitizers (PBP and PBPZn) for the free-radical (FRP), cationic (CP) photopolymerization and thiol-ene reactions under visible...

Quadrupolar A-D-A-type 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) bearing pyridinium and quinolinium substituents emit in the 500–600 nm region. The enhancement of electronic communication between the electron-rich heterocyclic core and electron-deficient peripheral substituents turned out to be crucial for achieving emission enhancement in viscous...

A series of heptamethine-oxonol dyes featuring different heterocyclic end groups were designed with the aim to explore structure-properties relationships in π-extend coupled polymethines. These dyes can be stabilised under three different protonation states, affording dicationic derivatives with an aromatic core, cationic heptamethines, and zwitte...

Efficient and robust analytical methods are needed to improve the identification and subsequent regulation of new psychoactive substances (NPS). NMR spectroscopy is a unique method able to determine the structure of small molecules such as NPS even in mixtures. However, high‐field NMR analysis is associated with expensive purchase and maintenance c...

To enrich and enhance the diversity of the quest database of highly accurate excitation energies [Véril, M.; et al. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2021, 11, e1517], we report vertical transition energies in transition metal compounds. Eleven diatomic molecules with a singlet or doublet ground state containing a fourth-row transition met...

Charge transfer (CT) is key for molecular photonics, governing the optical properties of chromophores comprising electron-rich and electron-deficient components. In photoexcited dyes with an acceptor–donor–acceptor or donor–acceptor–donor architecture, CT breaks their quadrupolar symmetry and yields dipolar structures manifesting pronounced solvato...

The tandem intramolecular hydroarylation of alkynes accompanied by a 1,2‐aryl shift is described. Harnessing the unique electron‐rich character of 1,4‐dihydropyrrolo[3,2‐b]pyrrole scaffold, we demonstrate that the hydroarylation of alkynes proceeds at the already occupied positions 2 and 5 leading to a 1,2‐aryl shift. Remarkably, the reaction proce...

In this work, we assess the accuracy of the Bethe-Salpeter equation (BSE) many-body Green's function formalism, adopting the eigenvalue-self-consistent evGW exchange-correlation kernel, for the calculation of the excited-state (μES) and excess dipole moments (Δμ), the latter ones being the changes of dipole amplitude between the ground and excited...

The first ever case of a tandem intramolecular hydroarylation of alkynes accompanied by a 1,2‐aryl shift is described. Harnessing the unique electron‐rich character of 1,4‐dihydropyrrolo[3,2‐b]pyrrole scaffolds, we have demonstrated that the hydroarylation of alkynes proceeds at the already occupied positions 2 and 5 leading to a 1,2‐aryl shift. Re...

A near‐infrared‐absorbing heptamethine (HM⁺) incorporating three bulky benzo[cd]indole heterocycles was designed to efficiently prevent self‐aggregation of the dye, which results in a strong enhancement of its photoinitiating reactivity as compared to a parent bis‐benzo[cd]indole heptamethine (HMCl⁺) used as a reference system. In this context, we...

We report the synthesis and full characterization of a family of phosphorus containing polymethine cyanines (phospha-cyanines). The compounds are easily prepared in two steps starting from readily available phosphanes. The impact of the P-substituents and the counterions on the structural and optical properties is investigated through a joint exper...

A near‐infrared‐absorbing heptamethine (HM+) incorporating three bulky benzo[cd]indole heterocycles was designed to efficiently prevent self‐aggregation of the dye, which results in a strong enhancement of its photoinitiating reactivity as compared to a parent bis‐benzo[cd]indole heptamethine (HMCl+) used as a reference system. In this context, we...

Defining a theoretical model systematically delivering accurate ab initio predictions of the fluorescence quantum yields of organic dyes is highly desirable for designing improved fluorophores in a systematic rather than trial-and-error way. To this end, the first required step is to obtain reliable radiative rates (kr), as low kr typically preclud...

This study presents the synthesis, the spectroscopic and electrochemical properties of new bis‐ and tetra‐substituted azaboron‐dipyrromethene (aza‐BODIPY) dyes substituted by different electron donating groups connected to the aza‐BODIPY core through a thiophene unit. In line with theoretical calculations, experimental measurements point out the po...

We present an implementation of excited-state analytic gradients within the Bethe–Salpeter equation formalism using an adapted Lagrangian Z-vector approach with a cost independent of the number of perturbations. We focus on excited-state electronic dipole moments associated with the derivatives of the excited-state energy with respect to an electri...

We detail the synthesis of a series of fluorophores containing triphenylamine derivatives along with their photophysical, electrochemical, and electronic structure properties. These compounds include molecular structures derived from imino-phenol (anil) and hydroxybenzoxazole scaffolds originating from similar salicylaldehyde derivatives and displa...

The from-first-principles calculation of fluorescence quantum yields (FQYs) and lifetimes of organic dyes remains very challenging. In this manuscript we extensively test the static machinery to calculate FQYs. Specifically, we perform an extensive analysis on the parameters influencing the intersystem crossing (ISC), internal conversion (IC), and...

The synthesis and full characterization of a family of stable λ⁵‐biphosphinines connected in 4,4‐position through a variety of π‐conjugated bridges is reported. The impact of the π‐bridge on the optical (absorption/emission) and redox properties was investigated using a joint experimental/theoretical approach. In contrast to the π‐extended ones, th...

This review aims at providing a broad readership of material and physical chemists, as well as those interested in ab initio calculations, about recent advances in the fields of dual solution-solid emitters and lasing applications based on organic dyes displaying an excited-state intramolecular proton transfer (ESIPT) process. ESIPT is known to be...

The straightforward access to N- or C-substituted dinitro-tetraamino-phenazines (P1-P5) is enabled in oxidative conditions via formation of two intermolecular C-N bonds from accessible 5-nitrobenzene-1,2,4-triamine precursors. The photophysical studies revealed green absorbing and orange-red emitting dyes, with enhanced fluorescence in the solid st...

Photodynamic therapy (PDT) is a photochemistry‐based medical treatment combining light at a specific wavelength and a photosensitizer (PS) in the presence of oxygen. Application of PDT as a conventional treatment is limited and clearly the approval in clinics of new PS is challenging. The selective accumulation of the PS in the targeted malignant c...

The change of molecular dipole moment induced by photon absorption is key to interpret the measured optical spectra. Except for compact molecules, time-dependent density functional theory (TD-DFT) remains the only theory allowing to quickly predict excited-state dipoles (μES), albeit with a strong dependency on the selected exchange-correlation fun...

The results of electronic and vibrational structure simulations are an invaluable support for interpreting experimental absorption/emission spectra, which stimulates the development of reliable and cost-effective computational protocols. In this work, we contribute to these efforts and propose an efficient first-principle protocol for simulating vi...

Curcuma derivatives are widely used as natural pigments in the food industry. Recent biological studies demonstrated that one of its major components, curcuminoids, might also positively impact human health. Herein, we use theoretical tools to combine cisplatin, the golden standard of chemotherapy, to curcuminoid analogues that have previously show...

Within the heteroacene family, azapentacenes have received much attention in organic electronic devices due to their unique physico-chemical properties. This is particularly true for the 5,14-dihydro-5,7,12,14-tetraazapentacene despite its poor solubility in organic solvents which logically hindered the study of its electrochemical behavior. Conseq...

Photochemical reactions are widely modeled using the popular trajectory surface hopping (TSH) method, an affordable mixed quantum-classical approximation to the full quantum dynamics of the system. TSH is able to account for nonadiabatic effects using an ensemble of trajectories, which are propagated on a single potential energy surface at a time a...

The puzzling case of the mixing between the charge transfer (CT) and local excited (LE) characters upon twisting of the geometry of N-phenylpyrrole (N-PP) is investigated considering the six low-lying singlet excited states (ES). The theoretical calculations of the potential energy surfaces (PES) have been performed for these states using a Coupled...

A new class of push-pull 1,1,4,4-tetracyanobutadienes (TCBDs) chromophores bearing a γ-pyranylidene as a pro-aromatic donor group have been developed, characterized and studied for their electrochemical, photophysical and second-order nonlinear optical (NLO) properties. [2 + 2] Cycloaddition-retroelectrocyclizations (CA-RE) with tetracyanoethylene...

The two‐step synthesis, structural, and photophysical properties of a series of heteroaryl‐substituted bis‐anil derivatives presenting aggregation‐induced emission (AIE) coupled with an excited‐state intramolecular proton transfer (ESIPT) process is described. The fluorescence color of the aggregates can be fine tuned by changing the electronic nat...

We report the synthesis and characterization of benzophospholes oxides featuring ethoxy substituent on the P atom and electro-donating amino groups on the lateral phenyl groups. The optical and redox properties of these compounds are studied experimentally and computationally (TD-DFT). In particular, we show how the nature of the donor allows to fi...

We report the synthesis and characterization of benzophospholes oxides featuring ethoxy substituent on the P atom and electro-donating amino groups on the lateral phenyl groups. The optical and redox properties...

Fully transparent and colorless Dye Sensitized Solar Cells have recently gained much attention due to their unconventional properties. Following the known strategy to redshift the absorption band of diketopyrrolopyrrole chromophores...

Thanks to the rise of efficient push-pull non-fullerene acceptors (NFAs), bulk-heterojunction organic solar cells have reached a high level of competitiveness with maximum power conversion efficiency over 18% for binary...

Chemical reactions are central for the creation of new materials, drug design and many more fields. The access to high reaction yields is of great importance to reduce cost, increase...

We report ground- and excited-state dipole moments and oscillator strengths (computed in different "gauges" or representations) of full configuration interaction (FCI) quality using the selected configuration interaction method known as Configuration Interaction using a Perturbative Selection made Iteratively (CIPSI). Thanks to a set encompassing 3...

We report ground- and excited-state dipole moments and oscillator strengths (computed in different ``gauges'' or representations) of full configuration interaction (FCI) quality using the selected configuration interaction method known as \textit{Configuration Interaction using a Perturbative Selection made Iteratively} (CIPSI). Thanks to a set enc...

Understanding the impact of the excited state wavefunction confinement is crucial for the engineering of the photophysical properties and applications of organic chromophores. In the present contribution, the localization of the triplet state wavefunctions of some symmetric ethyne/butadiyne bridged bodipy dimers and asymmetric bodipy derivatives pr...

Precise tuning of the fluorescence quantum yield, vital for countless applications of fluorophores, remains exceptionally challenging due to numerous factors affecting energy dissipation phenomena often leading to its counterintuitive behavior. In contrast to the absorption and emission wavelength which can be precisely shifted to the desired range...

In order to investigate the joint influence of the conformation flexibility and the matching of the energies of the charge-transfer (CT) and the localized triplet excited ( ³ LE) states on the thermally activated delayed fluorescence (TADF) in electron donor–acceptor molecules, a series of compact electron donor–acceptor dyads and a triad were prep...

Understanding the impact of the excited state wavefunction confinement is crucial for the engineering of the photophysical properties and applications of organic chromophores. In the present contribution, the localization of the triplet state wavefunctions of some symmetric ethyne / butadiyne bridged BODIPY dimers and asymmetric BODIPY derivatives...