Suppression of Dexter transfer by covalent encapsulation for efficient matrix-free narrowband deep blue hyperfluorescent OLEDs.

Hyperfluorescence shows great promise for the next generation of commercially feasible blue organic light-emitting diodes, for which eliminating the Dexter transfer to terminal emitter triplet states is key to efficiency and stability. Current devices rely on high-gap matrices to prevent Dexter transfer, which unfortunately leads to overly complex devices from a fabrication standpoint. Here we introduce a molecular design where ultranarrowband blue emitters are covalently encapsulated by insulating alkylene straps. Organic light-emitting diodes with simple emissive layers consisting of pristine thermally activated delayed fluorescence hosts doped with encapsulated terminal emitters exhibit negligible external quantum efficiency drops compared with non-doped devices, enabling a maximum external quantum efficiency of 21.5%. To explain the high efficiency in the absence of high-gap matrices, we turn to transient absorption spectroscopy. It is directly observed that Dexter transfer from a pristine thermally activated delayed fluorescence sensitizer host can be substantially reduced by an encapsulated terminal emitter, opening the door to highly efficient 'matrix-free' blue hyperfluorescence.

Singlet Fission in Pechmann Dyes: Planar Chromophore Design and Understanding.

Singlet fission in organic chromophores holds the potential for enhancing photovoltaic efficiencies beyond the single-junction limit. The most basic requirement of a singlet fission material is that it has a large energy gap between its first singlet and triplet excited states. Identifying such compounds is not simple and has been accomplished either through computational screening or by subtle modifications of previously known fission materials. Here, we propose an approach that leverages ground and excited-state aromaticity combined with double-bond conformation to establish simple qualitative design rules for predicting fundamental optical properties without the need for computational modeling. By investigating two Pechmann dye isomers, we demonstrate that although their planarity and degree of charge transfer are similar, singlet fission is active in the isomer with a trans-conformation, while the cis-isomer exhibits greater favorability for polaronic processes, experimentally validated using ultrafast and electron spin resonance spectroscopy. Our results offer a new design perspective that provides a rational framework for tailoring optoelectronic systems to specific applications such as singlet fission or triplet-triplet annihilation.

Reducing undesired solubility of squarephaneic tetraimide for use as an organic battery electrode material.

Locally aromatic alkyl-N-substituted squarephaneic tetraimide (SqTI) conjugated macrocycles are four-electron reducible, owing to global aromaticity and presumed global Baird aromaticity of the dianion and tetraanion states, respectively. However, their good solubility inhibits their application as a battery electrode material. By applying sidechain removal as a strategy to reduce SqTI solubility, we report the development of its unsubstituted derivative SqTI-H, which was obtained directly from squarephaneic tetraanhydride by facile treatment with hexamethyldisilazane and MeOH. Compared to alkyl-N-substituted SqTI-Rs, SqTI-H exhibited further improved thermal stability and low neutral state solubility in most common organic solvents, owing to computationally demonstrated hydrogen-bonding capabilities emanating from each imide position on SqTI-H. Reversible solid state electrochemical reduction of SqTI-H to the globally aromatic dianion state was also observed at -1.25 V vs. Fc/Fc+, which could be further reduced in two stages. Preliminary testing of SqTI-H in composite electrodes for lithium-organic half cells uncovered imperfect cycling performance, which may be explained by persistent solubility of reduced states, necessitating further optimisation of electrode fabrication procedures to attain maximum performance.

Quantification of the Ionic Character of Multiconfigurational Wave Functions: The Qat Diagnostic.

The complete active space self-consistent field (CASSCF) method is a cornerstone in modern excited-state quantum chemistry providing the starting point for most common multireference computations. However, CASSCF, when used with a minimal active space, can produce significant errors (>2 eV) even for the excitation energies of simple hydrocarbons if the states of interest possess ionic character. After illustrating this problem in some detail, we present a diagnostic for ionic character, denoted as Q at, that is readily computed from the transition density. A set of 11 molecules is considered to study errors in vertical excitation energies. State-averaged CASSCF obtains a mean absolute error (MAE) of 0.87 eV for the 34 singlet states considered. We highlight a strong correlation between the obtained errors and the Q at diagnostic, illustrating its power to predict problematic cases. Conversely, using multireference configuration interaction with single and double excitations and Pople's size extensivity correction (MR-CISD+P), excellent results are obtained with an MAE of 0.11 eV. Furthermore, correlations with the Q at diagnostic disappear. In summary, we hope that the presented diagnostic will facilitate reliable and user-friendly multireference computations on conjugated organic molecules.

Surface Hopping Dynamics on Vibronic Coupling Models.

The simulation of photoinduced non-adiabatic dynamics is of great relevance in many scientific disciplines, ranging from physics and materials science to chemistry and biology. Upon light irradiation, different relaxation processes take place in which electronic and nuclear motion are intimately coupled. These are best described by the time-dependent molecular Schrödinger equation, but its solution poses fundamental practical challenges to contemporary theoretical chemistry. Two widely used and complementary approaches to this problem are multiconfigurational time-dependent Hartree (MCTDH) and trajectory surface hopping (SH). MCTDH is an accurate fully quantum-mechanical technique but often is feasible only in reduced dimensionality, in combination with approximate vibronic coupling (VC) Hamiltonians, or both (i.e., reduced-dimensional VC potentials). In contrast, SH is a quantum-classical technique that neglects most nuclear quantum effects but allows nuclear dynamics in full dimensionality by calculating potential energy surfaces on the fly. If nuclear quantum effects do not play a central role and a linear VC (LVC) Hamiltonian is appropriate-e.g., for stiff molecules that generally keep their conformation in the excited state-then it seems advantageous to combine the efficient LVC and SH techniques. In this Account, we describe how surface hopping based on an LVC Hamiltonian (SH/LVC)-as recently implemented in the SHARC surface hopping package-can provide an economical and automated approach to simulate non-adiabatic dynamics. First, we illustrate the potential of SH/LVC in a number of showcases, including intersystem crossing in SO2, intra-Rydberg dynamics in acetone, and several photophysical studies on large transition-metal complexes, which would be much more demanding or impossible to perform with other methods. While all of the applications provide very useful insights into light-induced phenomena, they also hint at difficulties faced by the SH/LVC methodology that need to be addressed in the future. Second, we contend that the SH/LVC approach can be useful to benchmark SH itself. By the use of the same (LVC) potentials as MCTDH calculations have employed for decades and by relying on the efficiency of SH/LVC, it is possible to directly compare multiple SH test calculations with a MCTDH reference and ponder the accuracy of various correction algorithms behind the SH methodology, such as decoherence corrections or momentum rescaling schemes. Third, we demonstrate how the efficiency of SH/LVC can also be exploited to identify essential nuclear and electronic degrees of freedom to be employed in more accurate MCTDH calculations. Lastly, we show that SH/LVC is able to advance the development of SH protocols that can describe nuclear dynamics including explicit laser fields-a very challenging endeavor for trajectory-based schemes. To end, this Account compiles the typical costs of contemporary SH simulations, evidencing the great advantages of using parametrized potentials. The LVC model is a sleeping beauty that, kissed by SH, is fueling the field of excited-state molecular dynamics. We hope that this Account will stimulate future research in this direction, leveraging the advantages of the SH/VC schemes to larger extents and extending their applicability to uncharted territories.

Using diketopyrrolopyrroles to stabilize double excitation and control internal conversion.

Diketopyrrolopyrrole (DPP) is a pivotal functional group to tune the physicochemical properties of novel organic photoelectronic materials. Among multiple uses, DPP-thiophene derivatives forming a dimer through a vinyl linker were recently shown to quench the fluorescence observed in their isolated monomers. Here, we explain this fluorescence quenching using computational chemistry. The DPP-thiophene dimer has a low-lying doubly excited state that is not energetically accessible for the monomer. This state delays the fluorescence allowing internal conversion to occur first. We characterize the doubly excited state wavefunction by systematically changing the derivatives to tune the π-scaffold size and the acceptor and donor characters. The origin of this state's stabilization is related to the increase in the π-system and not to the charge-transfer features. This analysis delivers core conceptual information on the electronic properties of organic chromophores arranged symmetrically around a vinyl linker, opening new ways to control the balance between luminescence and internal conversion.

Non-Kasha fluorescence of pyrene emerges from a dynamic equilibrium between excited states.

Pyrene fluorescence after a high-energy electronic excitation exhibits a prominent band shoulder not present after excitation at low energies. The standard assignment of this shoulder as a non-Kasha emission from the second-excited state (S2) has been recently questioned. To elucidate this issue, we simulated the fluorescence of pyrene using two different theoretical approaches based on vertical convolution and nonadiabatic dynamics with nuclear ensembles. To conduct the necessary nonadiabatic dynamics simulations with high-lying electronic states and deal with fluorescence timescales of about 100 ns of this large molecule, we developed new computational protocols. The results from both approaches confirm that the band shoulder is, in fact, due to S2 emission. We show that the non-Kasha behavior is a dynamic-equilibrium effect not caused by a metastable S2 minimum. However, it requires considerable vibrational energy, which can only be achieved in collisionless regimes after transitions into highly excited states. This strict condition explains why the S2 emission was not observed in some experiments.

Squarephaneic Tetraanhydride: A Conjugated Square-Shaped Cyclophane for the Synthesis of Porous Organic Materials.

Aromatic carboxylic anhydrides are ubiquitous building blocks in organic materials chemistry and have received considerable attention in the synthesis of organic semiconductors, pigments, and battery electrode materials. Here we extend the family of aromatic carboxylic anhydrides with a unique new member, a conjugated cyclophane with four anhydride groups. The cyclophane is obtained in a three-step synthesis and can be functionalised efficiently, as shown by the conversion into tetraimides and an octacarboxylate. Crystal structures reveal the high degree of porosity achievable with the new building block. Excellent electrochemical properties and reversible reduction to the tetraanions are shown for the imides; NMR and EPR measurements confirm the global aromaticity of the dianions and evidence the global Baird aromaticity of the tetraanions. Considering the short synthesis and unique properties, we expect widespread use of the new building block in the development of organic materials.

Hierarchical Assembly of a Micro- and Macroporous Hydrogen-Bonded Organic Framework with Tailored Single-Crystal Size.

Porous organic molecular materials represent an emergent field of research in Chemistry and Materials Science due to their unique combination of properties. To enhance their performance and expand the number of applications, the incorporation of hierarchical porosity is required, as exclusive microporosity entails several limitations. However, the integration of macropores in porous organic molecular materials is still an outstanding challenge. Herein, we report the first example of a hydrogen-bonded organic framework (MM-TPY) with hierarchical skeletal morphology, containing stable micro- and macroporosity. The crystal size, from micro to centimetre scale, can be controlled in a single step without using additives or templates. The mechanism of assembly during the crystal formation is compatible with a skeletal crystal growth. As proof of concept, we employed the hierarchical porosity as a platform for the dual, sequential and selective co-recognition of molecular species and microparticles.

Excited-state symmetry breaking in 9,10-dicyanoanthracene-based quadrupolar molecules: the effect of donor-acceptor branch length.

Excited-state symmetry breaking is investigated in a series of symmetric 9,10-dicyanoanthracenes linked to electron-donating groups on the 2 and 6 positions via different spacers, allowing for a tuning of the length of the donor-acceptor branches. The excited-state properties of these compounds are compared with their dipolar single-branch analogues. The changes in electronic structure upon their optical excitation are monitored by transient electronic spectroscopy in the visible and near-infrared regions as well as by transient vibrational spectroscopy in the mid-infrared. Our results reveal that, with the shortest branches, electronic excitation remains distributed almost symmetrically over the molecule even in polar environments. Upon increasing the donor-acceptor distance, excitation becomes unevenly distributed and, with the longest one, it fully localises on one branch in polar solvents. The influence of the branch length on the propensity of quadrupolar dyes to undergo excited-state symmetry breaking is rationalised in terms of the balance between interbranch coupling and solvation energy.

The role of excited-state character, structural relaxation, and symmetry breaking in enabling delayed fluorescence activity in push-pull chromophores.

Thermally activated delayed fluorescence (TADF) is a current promising route for generating highly efficient light-emitting devices. However, the design process of new chromophores is hampered by the complicated underlying photophysics. In this work, four closely related donor-π-acceptor-π-donor systems are investigated, two of which were synthesised previously, with the aim of elucidating their varying effectiveness for TADF. We outline that the frontier orbitals are insufficient for discriminating between the molecules. Subsequently, a detailed analysis of the excited states at a correlated ab initio level highlights the presence of a number of closely spaced singlet and triplet states of varying character. Results from five density functionals are compared against this reference revealing dramatic changes in, both, excited state energies and wavefunctions following variations in the amount of Hartree-Fock exchange included. Excited-state minima are optimised in solution showing the crucial role of structural variations and symmetry breaking for producing a strongly emissive S1 state. The adiabatic singlet-triplet gaps thus obtained depend strongly on the range separation parameter used in the hybrid density functional calculations. More generally, this work highlights intricate differences present between singlet and triplet excited state wavefunctions and the challenges in describing them accurately.

Software for the frontiers of quantum chemistry: An overview of developments in the Q-Chem 5 package.

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear-electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an "open teamware" model and an increasingly modular design.

Visualisation of Chemical Shielding Tensors (VIST) to Elucidate Aromaticity and Antiaromaticity.

Aromaticity is a central concept in chemistry, pervading areas from biochemistry to materials science. Recently, chemists also started to exploit intricate phenomena such as the interplay of local and global (anti)aromaticity or aromaticity in non-planar systems and three dimensions. These phenomena pose new challenges in terms of our fundamental understanding and the practical visualisation of aromaticity. To overcome these challenges, a method for the visualisation of chemical shielding tensors (VIST) is developed here that allows for a 3D visualisation with quantitative information about the local variations and anisotropy of the chemical shielding. After exemplifying the method in different planar hydrocarbons, we study two non-planar macrocycles to show the unique benefits of the VIST method for molecules with competing π-conjugated systems and conclude with a norcorrole dimer showing clear evidence of through-space aromaticity. We believe that the VIST method will be a highly valuable addition to the computational toolbox.

Multireference Approaches for Excited States of Molecules.

Understanding the properties of electronically excited states is a challenging task that becomes increasingly important for numerous applications in chemistry, molecular physics, molecular biology, and materials science. A substantial impact is exerted by the fascinating progress in time-resolved spectroscopy, which leads to a strongly growing demand for theoretical methods to describe the characteristic features of excited states accurately. Whereas for electronic ground state problems of stable molecules the quantum chemical methodology is now so well developed that informed nonexperts can use it efficiently, the situation is entirely different concerning the investigation of excited states. This review is devoted to a specific class of approaches, usually denoted as multireference (MR) methods, the generality of which is needed for solving many spectroscopic or photodynamical problems. However, the understanding and proper application of these MR methods is often found to be difficult due to their complexity and their computational cost. The purpose of this review is to provide an overview of the most important facts about the different theoretical approaches available and to present by means of a collection of characteristic examples useful information, which can guide the reader in performing their own applications.

Toward an understanding of electronic excitation energies beyond the molecular orbital picture.

Tuning the energies of molecular excited states is a central research theme in modern chemistry with high relevance for optoelectronic applications and chemical synthesis. Whereas frontier orbitals have proven to be an intuitive and simple model in many cases, they can only provide a very rough approximation of the underlying wavefunctions. The purpose of this Perspective is to explore how our qualitative understanding of electronic excitation processes can be promoted beyond the molecular orbital picture by exploiting methods and insights from modern quantum chemistry. For this purpose, the physics of a correlated electron-hole pair is analysed in detail to show the origin of exchange repulsion and a dynamic Coulomb attraction, which determine its energy aside from the orbital energies. Furthermore, we identify and discuss the two additional effects of secondary orbital relaxation and de-excitations. Rules for reconstructing these four contributions from general excited-state computations are presented and their use is exemplified in three case studies concerned with the relative ordering of the singlet and triplet ππ* and nπ* states of uracil, the large energetic differences between the first singlet and triplet states of the polyacenes, and the assignment of plasmonic states in octatetraene. Finally, we lay out some general ideas for how the knowledge gained could ultimately lead to new design principles for tuning molecular excitation energies as well as for diagnosing possible shortcomings of commonly used electronic structure methods.

The generality of the GUGA MRCI approach in COLUMBUS for treating complex quantum chemistry.

The core part of the program system COLUMBUS allows highly efficient calculations using variational multireference (MR) methods in the framework of configuration interaction with single and double excitations (MR-CISD) and averaged quadratic coupled-cluster calculations (MR-AQCC), based on uncontracted sets of configurations and the graphical unitary group approach (GUGA). The availability of analytic MR-CISD and MR-AQCC energy gradients and analytic nonadiabatic couplings for MR-CISD enables exciting applications including, e.g., investigations of π-conjugated biradicaloid compounds, calculations of multitudes of excited states, development of diabatization procedures, and furnishing the electronic structure information for on-the-fly surface nonadiabatic dynamics. With fully variational uncontracted spin-orbit MRCI, COLUMBUS provides a unique possibility of performing high-level calculations on compounds containing heavy atoms up to lanthanides and actinides. Crucial for carrying out all of these calculations effectively is the availability of an efficient parallel code for the CI step. Configuration spaces of several billion in size now can be treated quite routinely on standard parallel computer clusters. Emerging developments in COLUMBUS, including the all configuration mean energy multiconfiguration self-consistent field method and the graphically contracted function method, promise to allow practically unlimited configuration space dimensions. Spin density based on the GUGA approach, analytic spin-orbit energy gradients, possibilities for local electron correlation MR calculations, development of general interfaces for nonadiabatic dynamics, and MRCI linear vibronic coupling models conclude this overview.

A complementary approach to conjugated N-acyliminium formation through photoredox-catalyzed intermolecular radical addition to allenamides and allencarbamates.

An intermolecular radical addition, using photoredox catalysis, to allenamides and allencarbamates is reported. This transformation synthesizes N-acyl-N'-aryl-N,N'-allylaminals, and proceeds by a conjugated N-acyliminium intermediate that previously has principally been generated by electrophilic activation methods. The radical adds to the central carbon of the allene giving a conjugated N-acyliminium that undergoes nucleophilic addition by arylamines and alcohols.

Red-shifted delayed fluorescence at the expense of photoluminescence quantum efficiency - an intramolecular charge-transfer molecule based on a benzodithiophene-4,8-dione acceptor.

Employing the thiophene based quinone, benzo[1,2-b:4,5-b']dithiophene-4,8-dione, as the electron-accepting moiety alongside N-phenylcarbazole donors to produce a donor-π-acceptor-π-donor (D-π-A-π-D) molecule has yielded a new red emitter displaying delayed fluorescence. This new molecule shows strongly (over 100 nm) red-shifted emission when compared to an anthraquinone based analogue. Cyclic voltammetry complemented by computational insights prove that this red-shift is due to the significantly stronger electron-accepting ability of the thiophene quinone compared to anthraquinone. Photophysical and computational studies of this molecule have revealed that while the presence of the thiophene containing acceptor facilitates rapid intersystem crossing which is comparable to anthraquinone analogues, the reverse intersystem crossing rate is slow and non-radiative decay is rapid which we can attribute to low-lying locally excited states. This limits the total photoluminescence quantum efficiency to less than 10% in both solution and the solid state. These results provide a useful example of how very minor structural variations can have a defining impact on the photophysical properties of new molecular materials.

Dynamics of benzene excimer formation from the parallel-displaced dimer.

Excimers play a key role in a variety of excited-state processes, such as exciton trapping, fluorescence quenching, and singlet-fission. The dynamics of benzene excimer formation in the first 2 ps after S1 excitation from the parallel-displaced geometry of the benzene dimer is reported here. It was simulated via nonadiabatic surface-hopping dynamics using the second-order algebraic diagrammatic construction (ADC(2)). After excitation, the benzene rings take ∼0.5-1.0 ps to approach each other in a parallel-stacked structure of the S1 minimum and stay in the excimer region for ∼0.1-0.4 ps before leaving due to excess vibrational energy. The S1-S2 gap widens considerably while the rings visit the excimer region in the potential energy surface. Our work provides detailed insight into correlations between nuclear and electronic structure in the excimer and shows that decreased ring distance goes along with enhanced charge transfer and that fast exciton transfer happens between the rings, leading to the equal probability of finding the exciton in each ring after around 1.0 ps.

Highly efficient surface hopping dynamics using a linear vibronic coupling model.

We report an implementation of the linear vibronic coupling (LVC) model within the surface hopping dynamics approach and present utilities for parameterizing this model in a blackbox fashion. This results in an extremely efficient method to obtain qualitative and even semi-quantitative information about the photodynamical behavior of a molecule, and provides a new route toward benchmarking the results of surface hopping computations. The merits and applicability of the method are demonstrated in a number of applications. First, the method is applied to the SO2 molecule showing that it is possible to compute its absorption spectrum beyond the Condon approximation, and that all the main features and timescales of previous on-the-fly dynamics simulations of intersystem crossing are reproduced while reducing the computational effort by three orders of magnitude. The dynamics results are benchmarked against exact wavepacket propagations on the same LVC potentials and against a variation of the electronic structure level. Four additional test cases are presented to exemplify the broader applicability of the model. The photodynamics of the isomeric adenine and 2-aminopurine molecules are studied and it is shown that the LVC model correctly predicts ultrafast decay in the former and an extended excited-state lifetime in the latter. Futhermore, the method correctly predicts ultrafast intersystem crossing in the modified nucleobase 2-thiocytosine and its absence in 5-azacytosine while it fails to describe the ultrafast internal conversion to the ground state in the latter.