Computational design of boron-free triangular molecules with inverted singlet-triplet energy gap.

A novel, computationally designed, class of triangular-shape organic molecules with an inverted singlet-triplet (IST) energy gap is investigated with ab initio electronic structure methods. The considered molecular systems are cyclic oligomers and their common feature is electronic conjugation along the molecular rim. Vertical excitation energies from the electronic ground state to the lowest singlet and triplet excited states were computed, as well as vertical emission energies from these states to the ground state. The results underscore the significance of optimizing excited-state geometries to accurately describe the optoelectronic properties of IST molecules, in particular with respect to their application in OLEDs.

Photo-oxidation of methanol in complexes with pyrido[2,3-b]pyrazine: a nonadiabatic molecular dynamics study.

Excited-state Proton-Coupled Electron Transfer (PCET) constitutes a key step in the photo-oxidation of small, electron-rich systems possessing acidic hydrogen atoms, such as water or alcohols, which can play a vital role in green hydrogen production. In this contribution, we employ ab initio quantum-chemical methods and on-the-fly nonadiabatic molecular dynamics simulations to study the mechanism and the photodynamics of PCET in 1 : 1 pyrido[2,3-b]pyrazine complexes with methanol. We find the process to be ultrafast and efficient when the intramolecular hydrogen bond is formed with one of the ß-positioned nitrogen atoms. The complex exhibiting a hydrogen bond with an isolated nitrogen site, on the contrary, shows much lower reactivity. We explain this effect with the stabilization of the reactive ππ* charge-transfer electronic state in the former case.

Harnessing Proton-Coupled Electron Transfer for Hydrogenation of Aza-Arenes: Photochemistry of Quinoxaline Derivatives in Methanol.

Three quinoxaline derivatives are investigated both experimentally and theoretically to assess their ability for the methanol oxidation and harvesting of hydrogen. In inert solvents, the nonplanar compounds exhibit very weak fluorescence from the lowest excited singlet state, whereas the planar and rigid chromophore emits non-Kasha fluorescence from the S2(ππ*) state despite the proximity of the S1(nπ*) state. In methanol, hydrogen-bonded complexes with solvent molecules are formed, and in all chromophores, the lowest singlet state is populated after excitation of the S2(ππ*) state. The switch from non-Kasha emission of the planar compound in inert solvents to regular emission in methanol is related to reduced symmetry of the hydrogen-bonded complex with methanol which results in effective mixing of ππ* and nπ* states and fast internal conversion to the lowest excited singlet state. The S1(nπ*) state of the hydrogen-bonded complex has charge-transfer character, and for all compounds in methanol, hydrogen transfer to the chromophore is observed. The chromophores retain the transferred hydrogen atoms, serving both as photocatalysts and as hydrogen storage materials. Undesired dark side reactions that occur are also discussed.

Excited-state singlet-triplet inversion in hexagonal aromatic and heteroaromatic compounds.

The inversion of the energies of the lowest singlet (S1) and lowest triplet (T1) excited states in violation of Hund's multiplicity rule is a rare phenomenon in stable organic molecules. S1-T1 inversion has significant consequences for the photophysics and photochemistry of organic chromophores. In this work, wave-function based ab initio computational methods were employed to explore the possibility of S1-T1 inversion in hexagonal polycyclic aromatic and heteroaromatic compounds. In these molecules, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are two-fold degenerate. The HOMO-LUMO transition gives rise to three singlet and three triplet excited states. While the singlet-triplet energy gap ΔST, defined as the energy difference between the S1 state and the T1 state, is clearly positive for benzene, it is predicted to be close to zero for borazine, the boron nitride analogue of benzene. Although ΔST decreases with increasing size of hexagonal polycyclic aromatics, it remains positive up to circumcoronene (19 rings). However, symmetry-preserving substitution of C-C pairs by B-N groups in the interior, keeping the conjugation of the outer rim intact, results in compounds with robustly negative ΔST. These findings establish the existence of a new family of boron carbon nitrides with inverted singlet-triplet gaps.

Local Hydrogen Bonding Determines Branching Pathways in Intermolecular Heptazine Photochemistry.

Heptazine is the molecular core of the widely studied photocatalyst carbon nitride. By analyzing the excited-state intermolecular proton-coupled electron-transfer (PCET) reaction between a heptazine derivative and a hydrogen-atom donor substrate, we are able to spectroscopically identify the resultant heptazinyl reactive radical species on a picosecond time scale. We provide detailed spectroscopic characterization of the tri-anisole heptazine:4-methoxyphenol hydrogen-bonded intermolecular complex (TAHz:MeOPhOH), using femtosecond transient absorption spectroscopy and global analysis, to reveal distinct product absorption signatures at ∼520, 1250, and 1600 nm. We assign these product peaks to the hydrogenated TAHz radical (TAHzH•) based on control experiments utilizing 1,4-dimethoxybenzene (DMB), which initiates electron transfer without concomitant proton transfer, i.e., no excited-state PCET. Additional control experiments with radical quenchers, protonation agents, and UV-vis-NIR spectroelectrochemistry also corroborate our product peak assignments. These spectral assignments allowed us to monitor the influence of the local hydrogen-bonding environment on the resulting evolution of photochemical products from excited-state PCET of heptazines. We observe that the preassociation of heptazine with the substrate in solution is extremely sensitive to the hydrogen-bond-accepting character of the solvent. This sensitivity directly influences which product signatures we detect with time-resolved spectroscopy. The spectral signature of the TAHzH• radical assigned in this work will facilitate future in-depth analysis of heptazine and carbon nitride photochemistry. Our results may also be utilized for designing improved PCET-based photochemical systems that will require precise control over local molecular environments. Examples include applications such as preparative synthesis involving organic photoredox catalysis, on-site solar water purification, as well as photocatalytic water splitting and artificial photosynthesis.

Conformation of the Ester Group Governs the Photophysics of Highly Polarized Benzo[g]coumarins.

Photosensitizers that display "unusual" emission from upper electronically excited states offer possibilities for initiating higher-energy processes than what the governing Kasha's rule postulates. Achieving conditions for dual fluorescence from multiple states of the same species requires molecular design and conditions that favorably tune the excited-state dynamics. Herein, we switch the position of the electron-donating NMe2 group around the core of benzo[g]coumarins (BgCoum) and tune the electronic coupling and the charge-transfer character of the fluorescent excited states. For solvents with intermediate polarity, three of the four regioisomers exhibit fluorescence from two different excited states with bands that are well separated in the visible and the near-infrared spectral regions. Computational analysis, employing ab initio methods, reveals that the orientation of an ester on the pyrone ring produces two conformers responsible for the observed dual fluorescence. Studies with solid solvating media, which restricts the conformational degrees of freedom, concur with the computational findings. These results demonstrate how "seemingly inconsequential" auxiliary substituents, such as the esters on the pyrone coumarin rings, can have profound effects leading to "anti-Kasha" photophysical behavior important for molecular photonics, materials engineering, and solar-energy science.

Saddle-shaped aza-nanographene with multiple odd-membered rings.

A saddle-shaped aza-nanographene containing a central 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) has been prepared via a rationally designed four-step synthetic pathway encompassing intramolecular direct arylation, the Scholl reaction, and finally photo-induced radical cyclization. The target non-alternant, nitrogen-embedded polycyclic aromatic hydrocarbon (PAH) incorporates two abutting pentagons between four adjacent heptagons forming unique 7-7-5-5-7-7 topology. Such a combination of odd-membered-ring defects entails a negative Gaussian curvature within its surface with a significant distortion from planarity (saddle height ≈ 4.3 Å). Its absorption and fluorescence maxima are located in the orange-red region, with weak emission originating from the intramolecular charge-transfer character of a low-energy absorption band. Cyclic voltammetry measurements revealed that this stable under ambient conditions aza-nanographene underwent three fully reversible oxidation steps (two one-electron followed by one two-electron) with an exceptionally low first oxidation potential of E ox1 = -0.38 V (vs. Fc/Fc+).

Migration of Subtalar Implants in Paediatric Flatfoot Correction: A Pilot Study in Synthetic Bone Models.

BACKGROUND: Subtalar implant migration as a complication following subtalar arthroeresis has been described in the scientific literature. However, clinical studies do not allow for unequivocally determining the underlying causes. The aim of the study is to determine the risk of migration of two geometric types of subtalar implants. Biomechanical tests were carried out on a synthetic bone model with a soft tissue substitute, which allowed for reduction of variability of results caused by biological differences. MATERIAL AND METHODS: A foot model mirroring natural anatomy was made from synthetic bone and a silicone soft tissue substitute with the same hardness as that of the soft tissues of the foot. Two types of 11 mm Ti6Al4V titanium alloy implants were studied, namely, a rectangular subtalar screw and a cylindrical subtalar screw, a type commonly used in flatfoot reconstruction surgery in children. The screws were placed in the sinus tarsi and subjected to cyclic loading (up to 1,000,000 cycles at a frequency of 5 Hz, with a maximum load of 500 N). Comparative pull-out force tests were performed immediately following implantation and after the dynamic loading test. Wyniki. Following the dynamic loading test, all 12 samples were qualified for the pull-out force test. Cylindrical screws demonstrated higher pull-out force values both for the samples tested immediately following implantation and for those that underwent dynamic loading. Implants of the same shape did not show statistically significant differences in the Mann-Whitney U test (p >0.05). Wniosek. The synthetic research model produces reproducible results in the assessment of risk of implant migration. Long-term loading does not significantly affect the risk of implant migration.

Photochemical Hydrogen Storage with Hexaazatrinaphthylene.

When irradiated with violet light, hexaazatrinaphthylene (HATN) extracts a hydrogen atom from an alcohol forming a long-living hydrogenated species. The apparent kinetic isotope effect for fluorescence decay time in deuterated methanol (1.56) indicates that the lowest singlet excited state of the molecule is a precursor for intermolecular hydrogen transfer. The photochemical hydrogenation occurs in several alcohols (methanol, ethanol, isopropanol) but not in water. Hydrogenated HATN can be detected optically by an absorption band at 1.78 eV as well as with EPR (electron paramagnetic resonance) and NMR techniques. Mass spectrometry of photoproducts reveal di-hydrogenated HATN structures along with methoxylated and methylated HATN molecules which are generated through the reaction with methoxy radicals (remnants from alcohol splitting). Experimental findings are consistent with the theoretical results which predicted that for the excited state of the HATN-solvent molecular complex, there exists a barrierless hydrogen transfer from methanol but a small barrier for the similar oxidation of water.

Water Oxidation and Hydrogen Evolution with Organic Photooxidants: A Theoretical Perspective.

In this Perspective, we discuss a novel water-splitting scenario, namely the direct oxidation of water molecules by organic photooxidants in hydrogen-bonded chromophore-water complexes. In comparison with the established scenario of semiconductor-based water splitting, the distance of electron transfer processes is thereby reduced from mesoscopic scales to the Ångström scale, and the time scale is reduced from milliseconds to femtoseconds, which suppresses competing loss processes. The concept is illustrated by computational studies for the heptazine-H2O complex. The excited-state landscape of this complex has been characterized with ab initio electronic-structure methods and the proton-coupled electron-transfer dynamics has been explored with nonadiabatic dynamics simulations. A unique feature of the heptazine chromophore is the existence of a low-lying and exceptionally long-lived 1ππ* state in which a substantial part of the photon energy can be stored for hundreds of nanoseconds and is available for the oxidation of water molecules. The calculations reveal that the absorption spectra and the photochemical functionalities of heptazine chromophores can be systematically tailored by chemical substitution. The options of harvesting hydrogen and the problems posed by the high reactivity of OH radicals are discussed.

Tuning the aromatic backbone twist in dipyrrolonaphthyridinediones.

This communication describes the photophysical behavior of three analogs of cyclophane bearing the dipyrrolonaphthyridinedione (DPND) core. In these molecules, intersystem crossing (ISC) can be successfully induced by distinct changes in the deviation from planarity within the DPND core, allowing at the same time the emission maximum to shift from the green to red region of the visible spectrum without any synthetic modifications of the chromophore structure. This finding may build the foundation for a new paradigm for inducing ISC-type transitions within other centrosymmetric and planar cross-conjugated chromophores.

Potent strategy towards strongly emissive nitroaromatics through a weakly electron-deficient core.

Nitroaromatics seldom fluoresce. The importance of electron-deficient (n-type) conjugates, however, has inspired a number of strategies for suppressing the emission-quenching effects of the strongly electron-withdrawing nitro group. Here, we demonstrate how such strategies yield fluorescent nitroaryl derivatives of dipyrrolonaphthyridinedione (DPND). Nitro groups near the DPND core quench its fluorescence. Conversely, nitro groups placed farther from the core allow some of the highest fluorescence quantum yields ever recorded for nitroaromatics. This strategy of preventing the known processes that compete with photoemission, however, leads to the emergence of unprecedented alternative mechanisms for fluorescence quenching, involving transitions to dark nπ* singlet states and aborted photochemistry. Forming nπ* triplet states from ππ* singlets is a classical pathway for fluorescence quenching. In nitro-DPNDs, however, these ππ* and nπ* excited states are both singlets, and they are common for nitroaryl conjugates. Understanding the excited-state dynamics of such nitroaromatics is crucial for designing strongly fluorescent electron-deficient conjugates.

Modern Theoretical Approaches to Modeling the Excited-State Intramolecular Proton Transfer: An Overview.

The excited-state intramolecular proton transfer (ESIPT) phenomenon is nowadays widely acknowledged to play a crucial role in many photobiological and photochemical processes. It is an extremely fast transformation, often taking place at sub-100 fs timescales. While its experimental characterization can be highly challenging, a rich manifold of theoretical approaches at different levels is nowadays available to support and guide experimental investigations. In this perspective, we summarize the state-of-the-art quantum-chemical methods, as well as molecular- and quantum-dynamics tools successfully applied in ESIPT process studies, focusing on a critical comparison of their specific properties.

Are Heptazine-Based Organic Light-Emitting Diode Chromophores Thermally Activated Delayed Fluorescence or Inverted Singlet-Triplet Systems?

Two chromophores derived from heptazine, HAP-3MF and HAP-3TPA, were synthesized and tested as emitters in light-emitting diodes (OLEDs) by Adachi and co-workers. Both emitters were shown to exhibit quantum efficiencies which exceed the theoretical maximum of conventional fluorescent OLEDs. The enhanced emission efficiency was explained by the mechanism of thermally activated delayed fluorescence (TADF). In the present work, the electronic excitation energies and essential features of the topography of the excited-state potential-energy surfaces of HAP-3MF and HAP-3TPA have been investigated with a wave function-based ab initio method (ADC(2)). It is found that HAP-3MF is an inverted singlet-triplet (IST) system; that is, the energies of the S1 and T1 states are robustly inverted in violation of Hund's multiplicity rule. Notably, HAP-3MF presumably is the first IST emitter which was implemented in an OLED device. In HAP-3TPA, on the other hand, the vertical excitation energies of the S1 and T1 states are essentially degenerate. The excited states exhibit vibrational stabilization energies of similar magnitude along different relaxation coordinates, resulting in adiabatic excitation energies which also are nearly degenerate. HAP-3TPA is found to be a chromophore at the borderline of TADF and IST systems. The spectroscopic data reported by Adachi and co-workers for HAP-3MF and HAP-3TPA are analyzed in light of these computational results.

Triangular boron carbon nitrides: an unexplored family of chromophores with unique properties for photocatalysis and optoelectronics.

It has recently been shown that cycl[3.3.3]azine and heptazine (1,3,4,6,7,9,9b-heptaazaphenalene) as well as related azaphenalenes exhibit inverted singlet and triplet states, that is, the energy of the lowest singlet excited state (S1) is below the energy of the lowest triplet excited state (T1). This feature is unique among all known aromatic chromophores and is of outstanding relevance for applications in photocatalysis and organic optoelectronics. Heptazine is the building block of the polymeric material graphitic carbon nitride which is an extensively explored photocatalyst in hydrogen evolution photocatalysis. Derivatives of heptazine have also been identified as efficient emitters in organic light emitting diodes (OLEDs). In both areas, the inverted singlet-triplet gap of heptazine is a highly beneficial feature. In photocatalysis, the absence of a long-lived triplet state eliminates the activation of atmospheric oxygen, which is favourable for long-term operational stability. In optoelectronics, singlet-triplet inversion implies the possibility of 100% fluorescence efficiency of electron-hole recombination. However, the absorption and luminescence wavelengths of heptazine and the S1-S0 transition dipole moment are difficult to tune for optimal functionality. In this work, we employed high-level ab initio electronic structure theory to devise and characterize a large family of novel heteroaromatic chromophores, the triangular boron carbon nitrides. These novel heterocycles inherit essential spectroscopic features from heptazine, in particular the inverted singlet-triplet gap, while their absorption and luminescence spectra and transition dipole moments are widely tuneable. For applications in photocatalysis, the wavelength of the absorption maximum can be tuned to improve the overlap with the solar spectrum at the surface of earth. For applications in OLEDs, the colour of emission can be adjusted and the fluorescence yield can be enhanced.

Bowl-Shaped Pentagon- and Heptagon-Embedded Nanographene Containing a Central Pyrrolo[3,2-b]pyrrole Core.

A bowl-shaped nitrogen-doped nanographene composed of a pyrrolo[3,2-b]pyrrole core substituted with six arene rings circularly bonded with one another has been prepared via a concise synthetic strategy encompassing the multicomponent tetraarylpyrrolopyrrole (TAPP) synthesis, the Scholl reaction, and intramolecular direct arylation. This synthesis represents the first case of programmed sequential intramolecular direct arylation reactions utilizing the different reactivity of C-Br and C-Cl bonds. The target compound contains two central pentagons confined between two adjacent heptagons-the inverse Stone-Thrower-Wales topology. The presence of both five- and seven-membered rings in the final structure is responsible for interesting properties such as a perpendicularly aligned dipole moment, absorption and fluorescence in the orange-red region, weak emission originating from the charge-transfer character of a low-energy absorption band, and a high lying HOMO. In the solid state slipped convex-to-convex π-π stacking dominates.

Substituent effects on the photophysical properties of tris(salicylideneanilines).

The role of electron acceptor/donor group substitution on the photophysical properties of tris(salicylideneanilines) (TSANs) was investigated. These compounds were synthesised and characterised through spectroscopic techniques including steady state absorption and emission spectroscopies. Their photochemical reaction mechanisms and properties were explored with the aid of ab initio methods of quantum chemistry. The obtained results allow us to verify the dependence of multiple emission bands on the substitution of electron donating and accepting groups to the tris(salicylideneaniline) core. The results also stress the differences in phosphorescence behaviour of TSANs for which this type of emission has not been reported so far.

Effect of previous lowering of skin temperature on the time of safe exposure to a hot environment: a case study.

Objective. The purpose of the study was to determine the influence of initial conditions of a microclimate on volunteers' permissible exposure limits to a hot and humid environment. Materials and methods. Eighteen experimental studies with the participation of three volunteers were performed under controlled microclimate conditions (two climate chambers). The skin temperature and body core temperature were measured after they had stabilized in the following microclimate conditions: temperature of 17, 21 and 23 °C, relative humidity of 50% and hot microclimate conditions, i.e., temperature of 35 and 42 °C, humidity of 80% and physical work load at 30 W. The time needed to reach a body core temperature of 38 °C was determined under hot conditions. Heat accumulation was calculated. Results. Lowering volunteers' skin temperature under conditions of stabilized physiological parameters prolongs the time necessary for the body core temperature to reach 38 °C during physical work in a hot and humid environment. Conclusions. Appropriate acclimatization before exposure may prolong the time of safe work in a hot environment, e.g., during activities of rescue services.

The influence of air humidity on human heat stress in a hot environment.

This article aims to present the physical adaptation capabilities of a human, seen as a response to extreme hot and dry or hot and humid conditions. Adaptation capabilities are expressed as safe exposure time in two variants: at rest and during physical activity. The study shows the results of calculations of the variability over time of the core temperature and skin temperature as well as heat balance. Calculations were made according to Standard No. EN ISO 7933:2005 on the basis of assumed and actual meteorological data. The results of the calculations show that in these conditions a hot but dry environment enables a human (although to a limited extent) to stay and perform low physical activity, provided access to drinking water is ensured. In contrast, a hot but humid environment causes more serious problems, due to the inability to reduce skin temperature by evaporation of sweat from the skin surface.

Photooxidation of water with heptazine-based molecular photocatalysts: Insights from spectroscopy and computational chemistry.

We present a conspectus of recent joint spectroscopic and computational studies that provided novel insight into the photochemistry of hydrogen-bonded complexes of the heptazine (Hz) chromophore with hydroxylic substrate molecules (water and phenol). It was found that a functionalized derivative of Hz, tri-anisole-heptazine (TAHz), can photooxidize water and phenol in a homogeneous photochemical reaction. This allows the exploration of the basic mechanisms of the proton-coupled electron-transfer (PCET) process involved in the water photooxidation reaction in well-defined complexes of chemically tunable molecular chromophores with chemically tunable substrate molecules. The unique properties of the excited electronic states of the Hz molecule and derivatives thereof are highlighted. The potential energy landscape relevant for the PCET reaction has been characterized by judicious computational studies. These data provided the basis for the demonstration of rational laser control of PCET reactions in TAHz-phenol complexes by pump-push-probe spectroscopy, which sheds light on the branching mechanisms occurring by the interaction of nonreactive locally excited states of the chromophore with reactive intermolecular charge-transfer states. Extrapolating from these results, we propose a general scenario that unravels the complex photoinduced water-splitting reaction into simple sequential light-driven one-electron redox reactions followed by simple dark radical-radical recombination reactions.