A BF3-catalyzed atom-economical fluorocarbamoylation reaction of alkyne-tethered carbamoyl fluorides is reported. The catalyst acts as both a fluoride source and Lewis acid activator, thereby enabling the formal insertion alkynes into strong C-F bonds through halide recycling mechanism. developed method provides access to 3-(fluoromethylene) oxindoles γ-lactams with excellent stereoselectivity, including fluorinated derivatives known protein kinase inhibitors. Experimental computational...

The generation of interlayer charge transfer excitons upon photoexcitation is strongly desirable for two-dimensional (2D) materials stacked through van der Waals interactions. In this work, we investigate photoinduced in silicanes (SiH) with three typical stackings. A concept the regional natural hole orbital and its conjugated particle developed to characterize excited states solids. This method delivers bonding information about explains formation certain types nanomaterials. Utilizing...

Ligand functionalization leads to enormous ranges of band edge energies silicanes. The can be predicted by empirical functions.

The minimum energy structures, i.e., trans-HONO, cis-HONO, HNO2, and OH + NO, as well the corresponding transition states, TStrans↔cis, TS1,2H-shift, TS1,3H-shift, on ground state potential surface (PES) of HONO have been characterized at CCSD(T)-F12/cc-pVTZ-F12 level theory. Using same theory, a six-dimensional (6D) PES, encompassing trans- cis-isomers associated state, is fit in sum-of-products form using neural network exponential fitting functions. A second PES developed based ab initio...

We used quantum chemistry methods at the levels of mixed-reference spin-flip time-dependent density functional theory and multireference perturbation to study diboron- diaza-doped anthracenes phenanthrenes. This class structures recently surged as potential singlet fission chromophores. studied electronic their excited states clarified reasons why they satisfy or fail energy criteria for Many have S1 not dominated by HOMO → LUMO excitation, so cannot be described using conventional two site...

Accurate modelling of nonadiabatic transitions and electron-phonon interactions in extended systems is essential for understanding the charge energy transfer photovoltaic photocatalytic materials. The extensive computational costs advanced excited state methods have stimulated development many approximations to study molecular dynamics (NA-MD) solid-state In this work, we present a novel ▵SCF-NA-MD methodology that aims account electron-hole back-reaction critical photoinduced nuclear...

Singlet fission is a highly desired process in photovoltaic devices as it can significantly enhance photoelectric conversion efficiency. Exploitation of this photovoltaics hindered by the lack appropriate chromophores. We used mixed-reference spin-flip time-dependent density functional theory (TDDFT) to investigate five dicarbonyl anthracenes and phenanthrenes, with purpose design singlet Two molecules were found be promising candidates. For all molecules, oxygen lone pair orbitals involved...

The field of π-conjugated organic materials has seen significant advances in recent years. However, enhancing the functionality well-established, mass-produced compounds remains a considerable challenge, despite being an intriguing strategy for designing high-value with low production costs. In this context, vat dyes, known their wide range colors and extensive use textile industry are particularly attractive. Here, we present innovative approach that conjoins phosphorus heterocycles dye Vat...

The Libra-X software for non-adiabatic molecular dynamics is reported. It used to comprehensively study the charge transfer at boron subphtalocyanine chloride (SubPc)/fullerene (C₆₀) interface.

A six-dimensional potential energy surface (PES) for formyl fluoride (HFCO) is fit in a sum-of-products form using neural network exponential fitting functions. The ab initio data upon which the based were computed at explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12]/cc-pVTZ-F12 level of theory. PES accurate (RMSE = 10 cm(-1)) up to 000 cm(-1) above zero point covers most experimentally measured IR data. validated by computing...

The ground state potential energy and dipole moment surfaces for CS2 have been determined at the CASPT2/C:cc-pVTZ,S:aug-cc-pV(T+d)Z level of theory. surface has fit to a sum-of-products form using neural network method with exponential neurons. A generic interface between fitting Heidelberg MCTDH software package is demonstrated. also potfit procedure in MCTDH. For fits low-energy regions potential, requires fewer parameters than achieve high accuracy; global are comparable two methods....

Abstract In 2016, a diazadiborinine molecule was synthesized ( Nature Commun . 2016 , 7 11871). The core structure of this is 6‐membered π system with trans stitching up two NCB fragments. This identical to model singlet fission chromophore that one us (T.Z.) proposed in 2014 J. Am. Chem. Soc 136 12638–12647.) Inspired by resemblance, we performed quantum chemistry calculations design series chromophores based on the framework. essence impair aromaticity framework substitutions and/or...

Singlet fission is of key importance in harvesting solar energy cells, as it generates a pair triplet excitons on the incidence photon. This phenomenon not yet widely employed organic photovoltaics industry mostly because rarity singlet chromophores. Pyrazino[2,3-g]quinoxaline-1,4,6,9-tetraoxide was recently designed smallest intramolecular chromophore, and undergoes fastest with 16 fs time scale. The subsequent separation generated triplet-pair likewise their efficient generation. Through...

In this paper, the use of neural network (NN) method with exponential neurons for directly fitting ab initio data to generate potential energy surfaces (PESs) in sum-of-product form will be discussed. The utility approach highlighted using fits CS 2 , HFCO, and HONO ground state PESs based upon high-level data. Using a generic interface between PES fitting, which is performed MATLAB, Heidelberg multi-configuration time-dependent Hartree (MCTDH) software package, have been tested via...

Understanding the dynamics of electron-ion energy transfer in warm dense (WD) matter is important to measurement equation state (EOS) properties and for understanding balance dynamic simulations. In this work, we present a comprehensive investigation nonadiabatic electron relaxation thermal excitation aluminum under high pressure temperature. Using quantum-classical trajectory surface hopping approaches, examine role couplings electronic decoherence electron-nuclear WD aluminum. The computed...

Reaction of dithienophospholes with quinones provides hypervalent phosphorus species square-pyramidal geometry and promising reactivity.

We designed an intramolecular singlet fission (iSF) chromophore, pyrazino[2,3-g]quinoxaline-1,4,6,9-tetraoxide. Appropriate substitutions into anthracene enhance the tetraradical character, so that molecule accommodates a pair of triplet excitons in its lowest excited state. Our simulation showed 16 fs fast iSF design, which is new record. The design also sets record small size chromophore and high exciton density. can be synthesized by oxidizing tertiary N centers existent...

Alkylidene dihydropyridines (ADHPs) are electron-rich nucleophilic intermediates that can be readily prepared by dearomatization of 4-alkylpyridines using chloroformate reagents and mild base. Their stability reactivity tuned with the reagent used as evidenced NMR chemical shifts oxidation potentials. ADHPs ethyl, allyl trichloroethyl undergo decomposition under an oxygen atmosphere at different rates (ethyl > trichloroethyl), predominantly to corresponding 4-acylpyridine. The derived from...

Open AccessCCS ChemistryCOMMUNICATION11 May 2021Postsynthetic Crystalline Transformation in Two-Dimensional Perovskites via Organothiol-Based Chemistry Zilong Yuan†, Liang Zhao†, Ekadashi Pradhan, Ming Lai, Tao Zeng and Zhenyu Yang Yuan† MOE Laboratory of Bioinorganic Synthetic Chemistry, Lehn Institute Functional Materials, School Sun Yat-sen University, Guangzhou, Guangdong 510275 , Zhao† Pradhan Department York Toronto, ON M3J1P3 Lai *Corresponding author: E-mail Address: [email...

Singlet fission is a highly desired process in organic photovoltaic devices. It splits one singlet exciton into two triplet excitons and enhances the power-conversion efficiency. However, exploitation of this devices plagued by small number chromophores. In work, we designed series chromophores introducing N-oxyl fragments anthracene. The diradical character brought structural reorganizations response to excitation lowest state allow some investigated molecules satisfy thermodynamic energy...

Spatial degeneracy of electronic states closely connects spin–orbit coupling and vibronic coupling, which together determine properties materials, especially heavy element compounds. Accurate description those materials entails accurate mathematical formulas for Hamiltonians. For the first time ever, we in this work derive Hamiltonian formalism to describe all Jahn–Teller pseudo-Jahn–Teller problems axial symmetries. The conventional one-electron approximation was foundation previous studies...

We synthesized a novel Lewis acidic aminoborane containing phenothiazyl substituent and demonstrated its potential to catalytically promote the dehydrocoupling of tin hydrides. The observed reactivity would imply homolytic frustrated pair type mechanism, however computational analysis suggests heterolytic mechanism for this reaction. This result represents one first systems dehydrocouple stannanes in fashion.

We used quantum chemistry methods at the levels of mixed-reference spin-flipping time-dependent density functional theory and multireference perturbation to study diboron- diaza-doped anthracenes phenanthrenes. This class structures recently surged as potential singlet fission chromophores. studied electronic their excited states clarify reasons why they satisfy or fail energy criteria for Many have S 1 not dominated by HOMO->LUMO excitation, so that cannot be described using conventional...

A series of luminescent, neutral pentacoordinate dithieno[3,2-b:2',3'-d]phosphole compounds was synthesized by [4+1] cycloaddition o-quinones with the corresponding trivalent phospholes. The electronic and geometrical modification π-conjugated scaffold implemented here impacts aggregation behavior species in solution. It proved successful generating improved Lewis acidity phosphorus center that then leveraged for small-molecule activation. Hydride abstraction from an external substrate...