Conjugated polymers have attracted much attention in recent years, as they can combine the best features of metals or inorganic semiconducting materials (excellent electrical and optical properties) with those synthetic (mechanical flexibility, simple processing, low-cost production), thereby creating altogether new scientific synergies technological opportunities. In search for more efficient methods preparation conjugated polymers, this Perspective reports advances field direct...

A substituent-based design strategy induces and enhances inversions in the excited state singlet–triplet gaps a wide range of potential organic light-emitting molecules.

Molecules with inversion of the singlet and triplet excited-state energies are highly promising for development organic light-emitting diodes (OLEDs). To date, azaphenalenes only class molecules where these inversions have been identified. Here, we screen a curated database crystal structures to identify existing compounds violations Hund's rule in lowest excited states. We two further classes this behavior. The first, zwitterions, has limited relevance molecular emitters as singlet-triplet...

New phosphine-based ligands and DFT calculations for defect-free conjugated polymers by direct (hetero)arylation polymerization (DHAP).

Molecules where the first excited singlet state is lower in energy than triplet have potential to revolutionize OLEDs. This inverted singlet-triplet gap violates Hund's rule and currently there are only a few molecules which known this property. Here, we screen complete set of non-alternant hydrocarbons consisting 5-, 6-, 7-membered rings fused into two-, three- four-ring polycyclic systems. We identify several symmetry ground-state structure broken due bond-length alternation. Through...

Frustrated Lewis pairs (FLPs), featuring reactive combinations of acids and bases, have been utilized for myriad metal-free homogeneous catalytic processes. Immobilizing the active sites to a solid support, especially porous scaffolds, has shown great potential ameliorate FLP catalysis by circumventing some its inherent drawbacks, such as poor product separation catalyst recyclability. Nevertheless, designing immobilized pair (LPASs) is challenging due requirement placing donor acceptor...

We recently leveraged the FORMED repository made of 116,687 synthesizeable molecules to deploy fragment-based high-throughput virtual screening (HTVS) and genetic algorithm (GA) searches singlet fission (SF) molecular candidates. With these approaches, both prototypical (e.g., acenes, boron-dipyrromethane (BODIPY)) unknown heteroatom-rich mesoionic) classes chromophore candidates fulfilling stringent SF energetic requirements were identified. Yet, reliance on pre-defined fragments limits...

Singlet fission (SF) has demonstrated significant promise for boosting the power conversion efficiency (PCE) of solar cells. Traditionally, SF is targeted as an intermolecular process; however, its dependence on crystal packing makes molecular design difficult. In contrast, intramolecular (iSF) enables exploration tunable bichromophoric systems following well-defined structure–property relationships. this work, we propose a set parameters to screen conjugated donor–acceptor copolymer...

Organic molecules are emerging candidates for the next generation of cost-effective active materials Li-ion batteries. Small diimide building blocks such as pyromellitic (PMDI) have attracted much attention because their high theoretical capacity. Many strategies been undertaken to limit well-known phenomenon dissolution material in electrolyte. Such include preparation salts and synthesis polyimides or macrocycles. Since dibromopyromellitic dimiide exhibits almost no sp2 cross-coupling...

We systematically varied the degree of fluorination along backbone a series highly regioregular 3-hexylthiophene-based polymers, P3HT-50F, P3HT-33F, and P3HT-25F, in which 50%, 33%, 25% thiophene units within polymer chain contain fluorine atoms available 4-position, respectively. These materials were homopolymerized using Kumada catalyst transfer polycondensation method from set mono-fluorinated bi-, ter-, quarterthiophenes to ensure high regioregularity evenly spaced conjugated backbone....

The immobilization of molecular catalysts imposes spatial constraints on their active site. We reveal that in bifunctional catalysis such can also be utilized as an appealing handle to boost intrinsic activity through judicious control the site geometry. To demonstrate this, we develop a pragmatic approach, based nonlinear scaling relationships, map arrangements acid-base components frustrated Lewis pairs (FLPs) performance catalytic hydrogenation CO

A computational study of the direct arylation reaction was undertaken to understand origin nonselective β-couplings observed in thiophene-based polymers prepared by (hetero)arylation polymerization (DHAP). The reactivities and selectivities C–H bond activations were studied for concerted metalation–deprotonation mechanism on model thiophene substrates using density functional theory (DFT) domain-based local pair natural orbital coupled cluster with singles, doubles, perturbative triples...

The high-throughput exploration and screening of molecules for organic electronics involves either a 'top-down' curation mining existing repositories, or 'bottom-up' assembly user-defined fragments based on known synthetic templates. Both are time-consuming approaches requiring significant resources to compute electronic properties accurately. Here, is combined with through automatic statistical models, thus providing platform the fragment-based discovery materials. This study generates...

Molecules where the lowest excited singlet state is lower in energy than triplet are highly promising for a number of organic materials applications as efficiency limitations stemming from spin statistics overcome. All molecules known to possess such singlet-triplet inversions exhibit pattern spatially alternating but nonoverlapping HOMO and LUMO orbitals, meaning states local character. Here, we demonstrate that derivatives bicyclic hydrocarbon calicene Hund's rule violations...

Intramolecular singlet fission (iSF) has shown potential to improve the power conversion efficiency in photovoltaic devices by promoting splitting of a photon-absorbing exciton into two triplet excitons within single molecule. Among different possibilities, donor–acceptor modular strategy copolymers great promise its ability undergo iSF under certain conditions. However, number reported literature remains remarkably narrow, and clear trends for molecular design better candidates have not yet...

Abstract Molecules with inversion of the singlet and triplet excited‐state energies are highly promising for development organic light‐emitting diodes (OLEDs). To date, azaphenalenes only class molecules where these inversions have been identified. Here, we screen a curated database crystal structures to identify existing compounds violations Hund's rule in lowest excited states. We two further classes this behavior. The first, zwitterions, has limited relevance molecular emitters as...

Singlet fission has shown potential for boosting the power conversion efficiency of solar cells, but scarcity suitable molecular materials hinders its implementation. We introduce an uncertainty‐controlled genetic algorithm (ucGA) based on ensemble machine learning predictions from different representations that concurrently optimizes excited state energies, synthesizability, and singlet exciton size discovery materials. The ucGA allows us to efficiently explore chemical space spanned by...

Abstract Mesoionic imidazolylidenes are recognized as excellent electron‐donating ligands in organometallic and main group chemistry. However, these carbene typically show poor π‐accepting properties. A computational analysis of 71 mesoionic that bear different aryl or heteroaryl substituents C2 position was performed. The study has revealed a diphenyltriazinyl (Dpt) substituent renders the corresponding particularly π‐acidic. results could be corroborated experimentally. imidazolylidene...

The reorganization energy (λ), which quantifies the structural rearrangement of a molecule when accommodating charge, is key parameter in evaluation charge mobility molecular solids. However, it unclear how λ influenced by conformational isomerism, diverse amorphous Here, we examine space family model organic hole transport materials (HTMs), derived from triphenylamine core–arm template, and probe effect complexity on λ. We observe an extreme dependence conformer geometry sterically...

Abstract The immobilization of molecular catalysts imposes spatial constraints on their active site. We reveal that in bifunctional catalysis such can also be utilized as an appealing handle to boost intrinsic activity through judicious control the site geometry. To demonstrate this, we develop a pragmatic approach, based nonlinear scaling relationships, map arrangements acid–base components frustrated Lewis pairs (FLPs) performance catalytic hydrogenation CO 2 . resulting shows fixing...

Singlet fission (SF) is a promising multiexciton-generating process. Its demanding energy splitting criterion - that the S1 must be at least twice of T1 has limited range materials capable SF. We propose heteroatom oxidation as robust strategy to achieve sufficient S1/T1 splitting, and demonstrate potential this approach for intramolecular

The high-throughput molecular exploration and screening of organic electronic materials often starts with either a 'top-down' mining existing repositories, or the 'bottom-up' assembly fragments based on predetermined rules known synthetic templates. In both instances, datasets used are produced case-by-case basis, require high-quality computation properties extensive user input: curation in top-down approach, construction fragment library introduction for linking them bottom-up approach....