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Photocatalysis appears as one of the most promising avenues to shift towards sustainable sources of energy, owing to its ability to transform solar light into chemical energy, e.g. production of chemical fuels via oxygen evolution (OER) and CO 2 reduction (CO 2 RR) reactions. Ti metal-organic frameworks (MOFs) and graphitic carbon nitride derivatives, i.e. poly-heptazine imides (PHI) are appealing CO 2 RR and OER photo-catalysts respectively. Engineering of an innovative Z-scheme heterojunction by assembling a Ti-MOF and PHI offers an unparalleled opportunity to mimick an artificial photosynthesis device for dual CO 2 RR/OER catalysis. Along this path, understanding of the photophysical processes controlling the MOF/PHI interfacial charge recombination is vital to fine tune the electronic and chemical features of the two components and devise the optimum heterojunction. To address this challenge, we developed a modelling approach integrating force field Molecular Dynamics (MD), Time-Dependent Density Functional Theory (TD-DFT) and Non-Equilibrium Green Function DFT (NEGF-DFT) tools with the aim of systematically exploring the structuring, the opto-electronic and transport properties of MOF/PHI heterojunctions. We revealed that the nature of the MOF/PHI interactions, the interfacial charge transfer directionality and the absorption energy windows of the resulting heterojunctions can be fine tuned by incorporating Cu species in the MOF and/or doping PHI with mono- or divalent cations. Interestingly, we demonstrated that the interfacial charge transfer can be further boosted by engineering MOF/PHI device junctions and application of negative bias. Overall, our generalizable computational methodology unravelled that the performance of CO 2 RR/OER photoreactors can be optimized by chemical and electronic tuning of the components but also by device design based on reliable structure-property rules, paving the way towards practical exploitation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Organic semiconductors combine flexible tailoring of their optoelectronic properties by synthetic means with strong light-matter coupling, which is advantageous for organic electronic device applications. Although spatially selective deposition has been demonstrated, lateral patterning of organic films with simultaneous control of molecular and crystalline orientation is lacking as traditional lithography is not applicable. Here, a new patterning approach based on surface-localized F-centers (halide vacancies) generated by electron irradiation of alkali halides is presented, which allows structural control of molecular adlayers. Combining optical and atomic force microscopy, X-ray diffraction, and density functional theory (DFT) calculations, it is shown that dinaphthothienothiophene (DNTT) molecules adopt an upright orientation on pristine KCl surfaces, while the F-centers stabilize a recumbent orientation, and that these orientations are maintained in thicker films. This specific nucleation results also in different crystallographic morphologies, namely, densely packed islands and jagged fibers, each epitaxially aligned on the KCl surface. Spatially selective surface irradiation can also be used to create patterns of F-centers and thus laterally patterned DNTT films, which can be further transferred to any (including elastomer) substrate due to the water solubility of the alkali halide growth templates.

Lead-free perovskites are attracting increasing interest as nontoxic materials for advanced optoelectronic applications. Here, we report on a family of silver/bismuth bromide double perovskites with lower dimensionality obtained by incorporating phenethylammonium (PEA) as an organic spacer, leading to the realization of two-dimensional double perovskites in the form of (PEA) 4 AgBiBr 8 ( n = 1) and the first reported (PEA) 2 CsAgBiBr 7 ( n = 2). In contrast to the situation prevailing in lead halide perovskites, we find a rather weak influence of electronic and dielectric confinement on the photophysics of the lead-free double perovskites, with both the 3D Cs 2 AgBiBr 6 and the 2D n = 1 and n = 2 materials being dominated by strong excitonic effects. The large measured Stokes shift is explained by the inherent soft character of the double-perovskite lattices, rather than by the often-invoked band to band indirect recombination. We discuss the implications of these results for the use of double perovskites in light-emitting applications., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Nowadays, semiconducting heterojunction-based devices exhibit the best photocatalytic performance, with transition metal oxides such as tungsten (WO 3 ) and titanium (TiO 2 ) being the workhorse materials employed in these composites. Contrary to their bulk counterparts, WO 3 and TiO 2 nanostructures offer a huge versatility because their optoelectronic properties (i.e., energy levels) can be tuned by modifying their size, morphology, and composition, thus being, in principle, able to optimize the electron/hole injection barriers inside the device. However, this approach requires a deep fundamental knowledge of their structure-property relationships, which are extremely difficult to access from experiments. In this context, we employed state-of-the-art theoretical methods to determine the size and morphology dependency of the energetic alignment in WO 3 /WO 3 and TiO 2 /WO 3 nanostructure heterojunctions. Our results demonstrated that any type of alignment can be achieved by the proper choice of the nanostructures involved in the junction, while setting important rules for the design of efficient multicomponent devices.

A number of factors contribute to orbital energy alignment with respect to the Fermi level in molecular tunnel junctions. Here, we report a combined experimental and theoretical effort to quantify the effect of metal image potentials on the highest occupied molecular orbital to Fermi level offset, ε h , for molecular junctions based on self-assembled monolayers (SAMs) of oligophenylene ethynylene dithiols (OPX) on Au. Our experimental approach involves the use of both transport and photoelectron spectroscopy to extract the offsets, ε h trans and ε h UPS , respectively. We take the difference in these quantities to be the image potential energy eV image . In the theoretical approach, we use density functional theory (DFT) to calculate directly eV image between positive charge on an OPX molecule and the negative image charge in the Au. Both approaches yield eV image ∼ -0.1 eV per metal contact, meaning that the total image potential energy is ∼-0.2 eV for an assembled junction with two Au contacts. Thus, we find that the total image potential energy is 25-30% of the total offset ε h , which means that image charge effects are significant in OPX junctions. Our methods should be generally applicable to understanding image charge effects as a function of molecular size, for example, in a variety of SAM-based junctions.

Bilirubin (BR) is the main end-product of the hemoglobin catabolism. For decades, its photophysics has been mainly discussed in terms of ultrafast deactivation of the excited state in solution, where, indeed, BR shows a very low green emission quantum yield (EQY), 0.03%, resulting from an efficient nonradiative isomerization process. Herein, we present, for the first time, unique and exceptional photophysical properties of solid-state BR, which amend by changing the type of crystal, from a closely packed α crystal to an amorphous loosely packed β crystal. BR α crystals show a very bright red emission with an EQY of ca. 24%, whereas β crystals present, in addition, a low green EQY of ca. 0.5%. By combining density functional theory (DFT) calculations and time-resolved emission spectroscopy, we trace back this dual emission to the presence of two types of BR molecules in the crystal: a "stiff" monomer, M1, distorted by particularly strong internal H-bonds and a "floppy" monomer, M2, having a structure close to that of BR in solution. We assign the red strong emission of BR crystals to M1 present in both the α and β crystals, while the low green emission, only present in the amorphous (β) crystal, is interpreted as M2 emission. Efficient energy-transfer processes from M2 to M1 in the closely packed α crystal are invoked to explain the absence of the green component in its emission spectrum. Interestingly, these unique photophysical properties of BR remain in polar solvents such as water. Based on these unprecedented findings, we propose a new model for the phototherapy scheme of BR inside the human body and highlight the usefulness of BR as a strong biological fluorescent probe.

Planar donor-acceptor-donor (D-A-D) organic molecules have been highlighted as promising photothermal agents due to their good light-to-heat conversion ratio, easy degradation, and chemical tunability. Very recently, it has been demonstrated that their photothermal conversion can be boosted by appending rather long alkyl chains. Despite this behavior being tentatively associated with the population of a nonradiative twisted intramolecular charge transfer (TICT) state driven by an intramolecular motion, the precise mechanisms and the role played by the environment, and most notably aggregation, still remain elusive. In this context, we carried out a series of time-dependent density functional theory (TD-DFT) calculations combined with molecular dynamics (MD) simulations to achieve a realistic description of the isolated and aggregated systems. Our theoretical models unambiguously evidence that the population of CT states is very unlikely in both cases, whereas the light-triggered heat dissipation can be ascribed to the activation of specific vibrational degrees of freedom related to the relative motion of the peripheral chains. Overall, our results clearly corroborate the active role played by the alkyl substituents in the photothermal conversion through vibrational motion, while breaking from the conventional picture, which invokes the formation of dark TICT states in loosely packed aggregates.

Transistors operate by controlling the current flowing from a source to a drain electrode via a third electrode (gate), thus giving access to a binary treatment (ON/OFF or 0/1) of the signal currently exploited in microelectronics. Introducing a second independent lever to modulate the current would allow for more complex logic functions amenable to a single electronic component and hence to new opportunities for advanced electrical signal processing. One avenue is to add this second dimension with light by incorporating photochromic molecules in current organic-based electronic devices. In this Spotlight, we describe different concepts that have been implemented in organic thin films and in molecular junctions as well as some pitfalls that have been highlighted thanks to theoretical modeling.

Tungsten trioxide (WO 3 )-derived nanostructures have emerged recently as feasible semiconductors for photocatalytic purposes due to their visible-light harvesting that overcomes the drawbacks presented by TiO 2 -derived nanoparticles (NPs). However, applications are still limited by the lack of fundamental knowledge at the nanoscale due to poor understanding of the physical processes that affect their photoactivity. To fill this gap, we report here a detailed computational study using a combined density functional theory (DFT)- GW scheme to investigate the electronic structure of realistic WO 3 NPs containing up to 1680 atoms. Different phases and morphologies are considered to provide reliable structure-property relationships. Upon proper benchmark of our DFT- GW methodology, we use this highly accurate approach to establish relevant rules for the design of photoactive WO 3 nanostructures by pointing out the most stable morphologies at the nanoscale and the appropriate size regime at which the photoactive efficiency is enhanced.

It is important, but challenging, to measure the (photo)induced switching of molecules in different chemical environments, from solution through thin layers to solid bulk crystals. We compare the cis-trans conformational switching of commercial azobenzene molecules in different liquid and solid environments: polar solutions, liquid polymers, 2D nanostructures and 3D crystals. We achieve this goal by using complementary techniques: optical absorption spectroscopy, femtosecond transient absorption spectroscopy, Kelvin probe force microscopy and reflectance spectroscopy, supported by density functional theory calculations. We could observe the same molecule showing fast switching in a few picoseconds, when studied as an isolated molecule in water, or slow switching in tens of minutes, when assembled in 3D crystals. It is worth noting that we could also observe switching for small ensembles of molecules (a few attomoles), representing an intermediate case between single molecules and bulk structures. This was achieved using Kelvin probe force microscopy to monitor the change of surface potential of nanometric thin 2D islands containing ca. 106 molecules each, self-assembled on a substrate. This approach is not limited to azobenzenes, but can be used to observe molecular switching in isolated ensembles of molecules or other nano-objects and to study synergistic molecular processes at the nanoscale.

Control over the energy level alignment in molecular junctions is notoriously difficult, making it challenging to control basic electronic functions such as the direction of rectification. Therefore, alternative approaches to control electronic functions in molecular junctions are needed. This paper describes switching of the direction of rectification by changing the bottom electrode material M = Ag, Au, or Pt in M-S(CH 2 ) 11 S-BTTF//EGaIn junctions based on self-assembled monolayers incorporating benzotetrathiafulvalene (BTTF) with EGaIn (eutectic alloy of Ga and In) as the top electrode. The stability of the junctions is determined by the choice of the bottom electrode, which, in turn, determines the maximum applied bias window, and the mechanism of rectification is dominated by the energy levels centered on the BTTF units. The energy level alignments of the three junctions are similar because of Fermi level pinning induced by charge transfer at the metal-thiolate interface and by a varying degree of additional charge transfer between BTTF and the metal. Density functional theory calculations show that the amount of electron transfer from M to the lowest unoccupied molecular orbital (LUMO) of BTTF follows the order Ag > Au > Pt. Junctions with Ag electrodes are the least stable and can only withstand an applied bias of ±1.0 V. As a result, no molecular orbitals can fall in the applied bias window, and the junctions do not rectify. The junction stability increases for M = Au, and the highest occupied molecular orbital (HOMO) dominates charge transport at a positive bias resulting in a positive rectification ratio of 83 at ±1.5 V. The junctions are very stable for M = Pt, but now the LUMO dominates charge transport at a negative bias resulting in a negative rectification ratio of 912 at ±2.5 V. Thus, the limitations of Fermi level pinning can be bypassed by a judicious choice of the bottom electrode material, making it possible to access selectively HOMO- or LUMO-based charge transport and, as shown here, associated reversal of rectification.

Fitting the I/V curves of molecular junctions by simple analytical models is often done to extract relevant molecular parameters such as energy level alignment or interfacial electronic coupling to build up useful property-relationships. However, such models can suffer from severe limitations and hence provide unreliable molecular parameters. This is illustrated here by extracting key molecular parameters by fitting computed voltage-dependent transmission spectra and by comparing them to the values obtained by fitting the calculated I/V curves with a typical Lorentzian model used in the literature. Doing so, we observe a large discrepancy between the two sets of values which warns us about the risks of using simple fitting expressions. Interestingly, we demonstrate that the quality of the fit can be improved by imposing the low bias conductance and Seebeck coefficient of the junction to be recovered in the fitting procedure.

Recently synthetized iron complexes have achieved long-lived excited states and stabilities which are comparable, or even superior, to their ruthenium analogues, thus representing an eco-friendly and cheaper alternative to those materials based on rare metals. Most of computational tools which could help unravel the origin of this large efficiency rely on ab-initio methods which are not able, however, to capture the nanosecond time scale underlying these photophysical processes and the influence of their realistic environment. Therefore, it exists an urgent need of developing new low-cost, but still accurate enough, computational methodologies capable to deal with the steady-state and transient spectroscopy of transition metal complexes in solution. Following this idea, here we focus on the comparison between general-purpose transferable force-fields (FFs), directly available from existing databases, and specific quantum mechanical derived FFs (QMD-FFs), obtained in this work through the Joyce procedure. We have chosen a recently reported Fe III complex with nanosecond excited-state lifetime as a representative case. Our molecular dynamics (MD) simulations demonstrated that the QMD-FF nicely reproduces the structure and the dynamics of the complex and its chemical environment within the same precision as higher cost QM methods, whereas general-purpose FFs failed in this purpose. Although in this particular case the chemical environment plays a minor role on the photo physics of this system, these results highlight the potential of QMD-FFs to rationalize photophysical phenomena provided an accurate QM method to derive its parameters is chosen.

We report a novel class of star-shaped multiazobenzene photoswitches comprising individual photochromes connected to a central trisubstituted 1,3,5-benzene core. The unique design of such C 3 -symmetric molecules, consisting of conformationally rigid and pseudoplanar scaffolds, made it possible to explore the role of electronic decoupling in the isomerization of the individual azobenzene units. The design of our tris-, bis-, and mono(azobenzene) compounds limits the π-conjugation between the switches belonging to the same molecule, thus enabling the efficient and independent isomerization of each photochrome. An in-depth experimental insight by making use of different complementary techniques such as UV-vis absorption spectroscopy, high performance liquid chromatography, and advanced mass spectrometry methods as ion mobility revealed an almost complete absence of electronic delocalization. Such evidence was further supported by both experimental (electrochemistry, kinetical analysis) and theoretical (DFT calculations) analyses. The electronic decoupling provided by this molecular design guarantees a remarkably efficient photoswitching of all azobenzenes, as evidenced by their photoisomerization quantum yields, as well as by the Z-rich UV photostationary states. Ion mobility mass spectrometry was exploited for the first time to study multiphotochromic compounds revealing the occurrence of a large molecular shape change in such rigid star-shaped azobenzene derivatives. In view of their high structural rigidity and efficient isomerization, our multiazobenzene photoswitches can be used as key components for the fabrication of complex stimuli-responsive porous materials.

The effect of doping on the electronic properties in bulk single-walled carbon nanotube (SWCNT) samples is studied for the first time using a new in situ Raman spectroelectrochemical method, and further verified by DFT calculations and photoresponse. We use p-/n-doped SWCNTs prepared by diazonium reactions as a versatile chemical strategy to control the SWCNT behavior. The measured and calculated data testify an acceptor effect of 4-aminobenzenesulfonic acid (p-doping), and a donor effect (n-doping) in the case of benzyl alcohol. In addition, pristine and covalently functionalized SWCNTs were used for the preparation of photoactive film electrodes. The photocathodic current in the photoelectrochemical cell is consistently modulated by the doping group. These results validate the in situ Raman spectroelectrochemistry as a unique tool box for predicting the electronic properties of functionalized SWCNTs in the form of thin films and their operational functionality in thin film devices for future optoelectronic applications.

We report the synthesis of a novel C 3 -symmetrical multiphotochromic molecule bearing three azobenzene units at positions 1, 3, 5 of the central phenyl ring. The unique geometrical design of such a rigid scaffold enables the electronic decoupling of the azobenzene moieties to guarantee their simultaneous isomerization. Photoswitching of all azobenzenes in solution was demonstrated by means of UV-vis absorption spectroscopy and high performance liquid chromatography (HPLC) analysis. Scanning tunneling microscopy investigations at the solid-liquid interface, corroborated by molecular modeling, made it possible to unravel the dynamic self-assembly of such systems into ordered supramolecular architectures, by visualizing and identifying the patterns resulting from three different isomers, thereby demonstrating that the multiphotochromism is retained when the molecules are confined in two dimensions.

Perchlorotriphenylmethyl (PTM) radical-based compounds are widely exploited as molecular switching units. However, their application in optoelectronics is limited by the fact that they exhibit intense absorption bands only in a narrow range of the UV region around 385 nm. Recent experimental works have reported new PTM based compounds which present a broad absorption in the visible region although the origin of this behavior is not fully explained. In this context, Time-Dependent Density Functional Theory (TD-DFT) calculations have been performed to rationalize the optical properties of these compounds. Moreover, a new compound based on PTM disubstituted with bistriazene units has been synthetized and characterized to complete the set of available experimental data on related compounds. The results point to the delocalization of the Highest Occupied Molecular Orbital (HOMO) of the substituents along the PTM core as the origin of the new high absorption bands in the visible region. As a consequence, the absorption of the PTM-based compounds can be tuned via the choice of the nature of the donor substituent, type of connection, and number of substituents., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Edge functionalization of bottom-up synthesized graphene nanoribbons (GNRs) with anthraquinone and naphthalene/perylene monoimide units has been achieved through a Suzuki coupling of polyphenylene precursors bearing bromo groups, prior to the intramolecular oxidative cyclo-dehydrogenation. High efficiency of the substitution has been validated by MALDI-TOF MS analysis of the functionalized precursors and FT-IR, Raman, and XPS analyses of the resulting GNRs. Moreover, AFM measurements demonstrated the modulation of the self-assembling behavior of the edge-functionalized GNRs, revealing that GNR-PMI formed an intriguing rectangular network. This result suggests the possibility of programming the supramolecular architecture of GNRs by tuning the functional units.