A mountaineering strategy to excited states: Accurate vertical transition energies and benchmarks for substituted benzenes.

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, benzonitrile, chlorobenzene, fluorobenzene, nitrobenzene, among others. To establish theoretical best estimates for these vertical excitation energies, we have employed advanced coupled-cluster methods including iterative triples (CC3 and CCSDT) and, when technically possible, iterative quadruples (CC4). These high-level computational approaches provide a robust foundation for benchmarking a series of popular wave function methods. The evaluated methods all include contributions from double excitations (ADC(2), CC2, CCSD, CIS(D), EOM-MP2, STEOM-CCSD), along with schemes that also incorporate perturbative or iterative triples (ADC(3), CCSDR(3), CCSD(T)(a) ⋆ $$ {}^{\star } $$ , and CCSDT-3). This systematic exploration not only broadens the scope of the QUEST database but also facilitates a rigorous assessment of different theoretical approaches in the framework of a homologous chemical series, offering valuable insights into the accuracy and reliability of these methods in such cases. We found that both ADC(2.5) and CCSDT-3 can provide very consistent estimates, whereas among less expensive methods SCS-CC2 is likely the most effective approach. Importantly, we show that some lower order methods may offer reasonable trends in the homologous series while providing quite large average errors, and vice versa. Consequently, benchmarking the accuracy of a model based solely on absolute transition energies may not be meaningful for applications involving a series of similar compounds.

Difluoro Dipyridomethene Boron Complexes: Synthesis, Characterization, and Ab Initio Calculations.

Molecular engineering studies on the meso-cyano difluoro dipyridomethene boron complexes are presented and two series (a and b) of novel fluorophores are extensively studied. Halogenated derivatives were reacted under Suzuki-Miyaura or Sonogashira cross coupling reactions to introduce electron-donating or electron-withdrawing functional groups on positions 1 and 2 of the aromatic ligand. All derivatives were obtained in 14-90% yields and studied in detail by structural, photophysical, and computational analyses. Both series display excellent emissive properties in solution with blue to orange fluorescence emission upon blue light absorption and promising features as solid emitters. All the spectroscopic measurements are supported and confirmed by first-principles theoretical calculations combining TD-DFT and CC2. Series b, featuring an aryl substituent onto position 1 of the aromatic core, showed significantly large Stokes shifts values.

One- and two-photon absorption spectra of organoboron complexes: vibronic and environmental effects.

We synthesized a series of four parent aza-ß-ketoiminate organoboron complexes and performed spectroscopic studies using both experimental and computational techniques. We studied how benzannulation influences the vibronic structure of the UV/Vis absorption bands with a focus on the bright lowest-energy π → π* electronic excitation. Theoretical simulations, accounting for inhomogeneous broadening effects using different embedding schemes, allowed gaining in-depth insights into the observed differences in band shapes induced by structural modifications. We observed huge variations in the distributions of vibronic transitions depending on the position of benzannulation. By and large, the harmonic approximation combined with the adiabatic hessian model delivers qualitatively correct band shapes for the one-photon absorption spectra, except in one case. We also assessed the importance of non-Condon effects (accounted for by the linear term in Herzberg-Teller expansion of the dipole moment) for S0 → S1 band shapes. It turned out that non-Condon contributions have no effect on the band shape in one-photon absorption spectra. In contrast, these effects significantly change the Franck-Condon band shapes of the two-photon absorption spectra. For one of the studied organoboron complexes we also performed a preliminary exploration of mechanical anharmonicity, resulting in an increase of the intensity of the 0-0 transition, which improves the agreement with the experimental data compared to the harmonic model.

Assessing the accuracy of TD-DFT excited-state geometries through optimal tuning with GW energy levels.

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 parameters obtained for three different types of systems: molecules composed of a few atoms, 4-(dimethylamino)benzonitrile (DMABN), and conjugated dyes. To this end, we used wave-function results as benchmarks. Next, we evaluate the accuracy of the theoretically simulated spectra as compared to the experimental ones for five large dyes. Our results show that, besides small compact molecules for which tuning LC-PBE does not allow obtaining geometries more accurate than those computed with standard functionals, tuned range-separated functionals are clearly to be favored, not only for ES geometries but also for 0-0 energies, band shapes, and intensities for absorption and emission spectra. In particular, the results indicate that GW-tuned LC-PBE functionals provide improved matching with experimental spectra as compared to conventionally tuned functionals. It is an open question whether TD-DFT with GW-tuned functionals can qualitatively mimic the actual many-body Bethe-Salpeter (BSE/GW) formalism for which analytic ionic gradients remain to be developed.

Non-uniform sampling to enhance the performance of compact NMR for characterizing new psychoactive substances.

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 costs. For more than a decade, compact NMR spectrometers have changed this paradigm. It was recently shown that a dedicated analytical workflow combining compact NMR and databases could identify the molecular structure of NPS, in spite of the lower spectral dispersion and sensitivity of compact spectrometers. This approach relies on 1H-13C HSQC to both recognize NPS and elucidate the structure of unknown substances. Still, its performance is limited by the need to compromise between resolution and experiment time. Here, we show that this strategy can be significantly improved by implementing non-uniform sampling (NUS) to improve spectral resolution in the 13C dimension of HSQC at no cost in terms of experiment time. Gains in the range of 3 to 4 in resolution are achieved for pure NPS and for a mixture. Finally, 2D HSQC with NUS was applied to improve the identification of NPS with the assistance of databases. The resulting method appears as a useful tool for the characterization of NPS in mixtures, which is essential for forensic laboratories.

Lysosomes Targeting pH Activable Imaging-Guided Photodynamic Agents.

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 cells is of paramount importance to reduce the side effects that are typical of the current worldwide approved PS. Here we report a new series of aniline- and iodine-substituted BODIPY derivatives (1-3) as promising lysosome-targeting and pH-responsive theranostic PS, which displayed a significant in vitro light-induced cytotoxicity, efficient imaging properties and low dark toxicity (for 2 and 3). These compounds were obtained in few reproducible synthetic steps and good yields. Spectroscopic and electrochemical measurements along with computational calculations confirmed the quenching of the emissive properties of the PS, while both fluorescence and 1 O2 emission were obtained only under acidic conditions inducing amine protonation. The pKa values and pH-dependent emissive properties of 1-3 being established, their cellular uptake and activation in the lysosomal vesicles (pH≈4-5) were confirmed by their co-localization with the commercial LysoTracker deep red and light-induced cytotoxicity (IC50 between 0.16 and 0.06 µM) against HeLa cancer cells.

Heteroaryl-Substituted Bis-Anils: Aggregation-Induced Emission (AIE) Derivatives with Tunable ESIPT Emission Color and pH Sensitivity.

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 nature of the peripheral substitution, leading to a wide range of emission wavelengths (from green to the near infra-red). Moreover, upon introduction of strong electron-withdrawing groups such as cyano (CN), a competition between ESIPT and deprotonation is observed leading to the emission of the anionic species at low water percentage. This observation led to the synthesis of an additional mixed AIE fluorophore, functionalized by methoxy groups on one side and cyano groups on the other side. Upon addition of water, this dye displays first anionic emission, followed by typical AIE/ESIPT red fluorescence upon formation of the aggregates. TD-DFT calculations on selected AIE dyes were performed to rationalize the nature of the emissive transitions in these derivatives.

Tuning the Photophysical Properties of Aza-BODIPYs in the Near-Infrared Region by Introducing Electron-Donating Thiophene Substituents.

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 positive impact of the thiophene group that behave as a secondary donor group leading to an enhancement of the intramolecular charge transfer process in comparison to previously reported aza-BODIPY dyes. This heterocycle has also been found to tune the oxidative potential and to stabilize the electro-generated species.

Intrinsically Switchable Electroactive Fluorophores Based on λ5 -Biphosphinines.

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, the λ5 -biphosphinines directly connected through a C-C bond in 4,4-position display two easily accessible and reversible oxidations highlighting their multi-stage redox character. The in situ formed radical cations are studied by spectro-electrochemistry and electron paramagnetic resonance. Finally, electrochemical modulation of fluorescence (electrofluorochromism) was performed and revealed the potential of these intrinsically switchable electroactive fluorophores for further applications as switchable materials.

Interplay between Dual-State and Aggregation-Induced Emission with ESIPT Scaffolds Containing Triphenylamine Substituents: Experimental and Theoretical Studies.

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 display excited-state intramolecular proton transfer. We show that depending on the nature of the π-conjugated scaffold, different photophysical processes are observed: aggregation-induced emission or dual-state emission, with a modulation of the fluorescence color and redox properties. The photophysical properties are further rationalized with the help of ab initio calculations.

Excited state potential energy surfaces of N-phenylpyrrole upon twisting: reference values and comparison between BSE/GW and TD-DFT.

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 Cluster method accounting for the impact of the contributions from the triples, many-body Green's function GW and Bethe-Salpeter equation (BSE) formalisms, as well as Time-Dependent Density Functional Theory (TD-DFT) using various exchange-correlation functionals. Our findings confirm that the BSE formalism is more reliable than TD-DFT for close-lying ES with mixed CT/LE nature. More specifically, BSE/GW yields a more accurate evolution of the excited state PES than TD-DFT when compared to the reference coupled cluster values. BSE/GW PES curves also show negligible exchange-correlation functional starting point dependency in sharp contrast with their TD-DFT counterparts.

Solid-state emitters presenting a modular excited-state proton transfer (ESIPT) process: recent advances in dual-state emission and lasing applications.

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 highly sensitive to the immediate environment leading to the engineering of a wide range of stimuli-responsive fluorescent dyes. With the structural diversity of ESIPT-capable fluorophores being large, many applications have been targeted over the years in the fields of optoelectronics, biology and luminescent displays. This review wishes to point out two emerging applications concerning ESIPT fluorophores, which are the answer for the quest for emitters fluorescing both in solution and in the solid state, and those capable of light amplification.

Excess and excited-state dipole moments of real-life dyes: a comparison between wave-function, BSE/GW, and TD-DFT values.

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 states (ES), in organic dyes. We compare the results obtained with wave-function methods [ADC(2), CC2, and CCSD], time-dependent density functional theory (TD-DFT), and BSE/evGW levels of theory. First, we compute the evolution of the dipole moments of the two lowest singlet excited states of 4-(dimethylamino)benzonitrile (DMABN) upon twisting of the amino group. Next, we use a set of 25 dyes having ES characters ranging from locally excited to charge transfer to determine both µES and Δµ. For DMABN our results show that BSE/evGW provides Δµ values closer to the CCSD reference and more consistent trends than TD-DFT. Moreover, a statistical analysis of both Δµ and µES for the set of 25 dyes shows that the BSE/evGW accuracy is comparable or sometimes slightly better than that of TD-M06-2X and TD-CAM-B3LYP, BSE/evGW outperforming TD-DFT in challenging cases (zwitterionic and cyanine transitions). Finally, the starting point dependency of BSE/evGW seems to be larger for Δµ, ES dipoles, and oscillator strengths than for transition energies.

First-Principles Calculations of Excited-State Decay Rate Constants in Organic Fluorophores.

In this Perspective, we discuss recent advances made to evaluate from first-principles the excited-state decay rate constants of organic fluorophores, focusing on the so-called static strategy. In this strategy, one essentially takes advantage of Fermi's golden rule (FGR) to evaluate rate constants at key points of the potential energy surfaces, a procedure that can be refined in a variety of ways. In this way, the radiative rate constant can be straightforwardly obtained by integrating the fluorescence line shape, itself determined from vibronic calculations. Likewise, FGR allows for a consistent calculation of the internal conversion (related to the non-adiabatic couplings) in the weak-coupling regime and intersystem crossing rates, therefore giving access to estimates of the emission yields when no complex photophysical phenomenon is at play. Beyond outlining the underlying theories, we summarize here the results of benchmarks performed for various types of rates, highlighting that both the quality of the vibronic calculations and the accuracy of the relative energies are crucial to reaching semiquantitative estimates. Finally, we illustrate the successes and challenges in determining the fluorescence quantum yields using a series of organic fluorophores.

Phospha-cyanines in Their Ideal Polymethine State: Synthesis and Structure-Property Relationships.

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 experimental/theoretical approach. Based on the study of the single-crystal X-ray diffraction structures, all phospha-cyanines present a bond length alternation close to zero, independently of the substituents and counterions, which indicates an ideal polymethine state. All these compounds display the typical cyanine-like UV-vis absorption with an intense and sharp transition with a vibronic shoulder despite possessing a reverse electronic configuration compared to "classical" cyanines. Time-dependent density-functional theory calculations allowed us to fully rationalize the optical properties (absorption/emission wavelengths, luminescence quantum yields). Interestingly, due to the tetrahedral shape of the P atom, the optical properties are independent of the counterion, which is in marked contrast with N-analogues, which enables predictive engineering of the phospha-cyanines regardless of the medium in which they are used.

Lagrangian Z-vector approach to Bethe-Salpeter analytic gradients: Assessing approximations.

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 electric field. In this framework, we assess the accuracy of neglecting the screened Coulomb potential derivatives, a common approximation in the Bethe-Salpeter community, as well as the impact of replacing the GW quasiparticle energy gradients by their Kohn-Sham analogs. The pros and cons of these approaches are benchmarked using both a set of small molecules for which very accurate reference data are available and the challenging case of increasingly extended push-pull oligomer chains. The resulting approximate Bethe-Salpeter analytic gradients are shown to compare well with the most accurate time-dependent density-functional theory (TD-DFT) data, curing in particular most of the pathological cases encountered with TD-DFT when a nonoptimal exchange-correlation functional is used.

Tris-benzo[cd]indole Cyanine Enables the NIR-photosensitized Radical and Thiol-ene Polymerizations at 940†nm.

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 highlight an efficient free-radical NIR-polymerization up to a 100 % acrylates C=C bonds conversion even under air conditions. Such an important initiating performance was obtained by incorporating our NIR-sensitizer into a three-component system leading to its self-regeneration. This original photoredox cycle was thoroughly investigated through the identification of each intermediary species using EPR spectroscopy.

Gold-Catalyzed 1,2-Aryl Shift and Double Alkyne Benzannulation.

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 proceeds only in the presence of cationic gold catalyst, and it leads to heretofore unknown π-expanded, centrosymmetric pyrrolo[3,2-b]pyrroles. The utility is verified in the preparation of 13 products that bear six conjugated rings. The observed compatibility with various functional groups allows for increased tunability with regard to the photophysical properties as well as providing sites for further functionalization. Computational studies of the reaction mechanism revealed that the formation of the six-membered rings accompanied with a 1,2-aryl shift is both kinetically and thermodynamically favourable over plausible formation of products containing 7-membered rings. Steady-state UV/Visible spectroscopy reveals that upon photoexcitation, the prepared S-shaped N-doped nanographenes undergo mostly radiative relaxation leading to large fluorescence quantum yields. Their optical properties are rationalized through time-dependent density functional theory calculations. We anticipate that this chemistry will empower the creation of new materials with various functionalities.

Color-Tunable Multifunctional Excited-State Intramolecular Proton Transfer Emitter: Stimulated Emission of a Single Dye.

The excited-state intramolecular proton transfer chromophores were regarded as good materials for laser action generation due to their inherent four-level photocycle. The excitation-dependent properties of these compounds enable light amplification from two distinct forms: both enol and keto, making it possible to obtain dual fluorescence emission. Herein, we report that a third option is possible for the first time stimulated emission was realized with a deprotonated ESIPT molecule based on a novel rigidified 2-(2'-hydroxyphenyl)benzothiazole derivative, triggering the possibility to fabricate real-time tunable active material. Through the rational engineering of the ratio of each emissive species, a red-green-blue device was fabricated with the possibility of white light generation. The degenerated two-wave mixing setup was applied to construct a continuously tunable distributed feedback laser.

Hetero-Substituted αß-Fused BODIPY.

Here, we report the synthesis and properties of heterosubtituted αß-fused BODIPY fluorophores. The compounds were obtained in good yields by sequential and selective Stille cross-coupling reactions from 2,3,5,6-tetrahalo-BODIPY, allowing the introduction of different substituents at the 3,5 and 2,6 positions of the BODIPY ring. The final fused compounds were synthesized using oxidative cyclisation with ferrous chloride. The fully fused compounds show a strong bathochromically shifted emission along with a hyperchromic shift of the absorption maxima. The fluorescence quantum yields remain relatively large for compounds emitting in this wavelength range. Computational studies have been carried out to fully understand the photophysical behaviour of these dyes.