We introduce a database (HAB11) of electronic coupling matrix elements (H(ab)) for electron transfer in 11 π-conjugated organic homo-dimer cations. High-level ab inito calculations at the multireference configuration interaction MRCI+Q level theory, n-electron valence state perturbation theory NEVPT2, and (spin-component scaled) approximate coupled cluster model (SCS)-CC2 are reported this to assess performance three DFT methods decreasing computational cost, including constrained density...

A new database (HAB7-) of electronic coupling matrix elements (Hab) for electron transfer in seven medium-sized negatively charged π-conjugated organic dimers is introduced. Reference data are obtained with spin-component scaled approximate coupled cluster method (SCS-CC2) and large basis sets. Assessed DFT-based approaches include constrained density functional theory (CDFT), fragment-orbital DFT (FODFT), self-consistent charge tight-binding (FODFTB) the recently described analytic overlap...

Coupled-cluster theory with single, double, and perturbative triple excitations (CCSD(T)) is widely considered to be the "gold standard" of ab initio quantum chemistry. Using domain-based pair natural orbital local correlation concept (DLPNO-CCSD(T)), these calculations can performed on systems hundreds atoms at an accuracy ∼99.9% canonical CCSD(T) method. This allows for providing reference adsorption energetics solid surfaces approaching 1 kcal/mol. invaluable asset, not least assessment...

Solar energy-driven processes for biomass valorization are priority the growing industrialized society. To address this challenge, efficient visible light-active photocatalyst selective oxidation of biomass-derived platform chemical is highly desirable. Herein, 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) was achieved by light-driven photocatalysis over titania. Pristine titania photocatalytically inactive under light, so an unconventional approach employed light (λ=515 nm)...

Although bowl-shaped N-pyrrolic polycyclic aromatic hydrocarbons (PAHs) can achieve excellent electron-donating ability, their application for optoelectronics is hampered by typically low photoluminescence quantum yields (PLQYs). To address this issue, we report the synthesis and characterization of a series curved fully conjugated nitrogen-doped PAHs. Through structural modifications to electron-accepting moiety, are able switch mechanism luminescence between thermally activated delayed...

Simulation of charge transport in organic semiconducting materials requires the development strategies for very fast yet accurate estimation electronic coupling matrix elements electron transfer between molecules (transfer integrals, Hab). A well-known relation that is often exploited this purpose approximately linear dependence with respect to overlap corresponding diabatic state wave functions a given donor-acceptor pair. Here we show single such can be established large number different...

The capability of organic emitters to harvest triplet excitons via a thermally activated delayed fluorescence (TADF) process has opened new era in optoelectronics. Nevertheless, low brightness, and consequently an insufficient roll-off ratio, constitutes bottleneck for their practical applications the domain light-emitting diodes (OLEDs). To address this formidable challenge, we developed design desymmetrized naphthalimide (NMI) featuring annulated indole with set auxiliary donors on its...

The heterolytic splitting of hydrogen by two types [2.2]paracyclophane derived bisphosphines (1, 2a and 2b) in combination with tris(pentafluorophenyl)borane (3) at room temperature is described. corresponding frustrated Lewis pairs (FLPs) exhibit different behavior the activation hydrogen. This results from diverse steric electronic properties bisphosphines. reactivity was exploited first diastereoselective domino hydrosilylation/hydrogenation reaction catalyzed FLPs.

Abstract Graphene-based nanohybrids are good candidates for various applications. However, graphene exhibits some unwanted features such as low solubility in an aqueous solution or tendency to aggregate, limiting its potential On the contrary, derivatives, oxide (GO) and reduced (RGO), have excellent properties can be easily produced large quantities. GO/RGO with porphyrins were shown possess great field of photocatalytic hydrogen production, pollutant photodegradation, optical sensing, drug...

Transition, post-transition and rare earth metal complexes supported by (O,N)- (N,N)-type ligands dominate organometallic photochemistry. However, despite a vast number of aminobenzoate having been reported, aluminium being globally abundant, alkylaluminium anthranilates have not yet considered as effective luminophores. Herein, using family commercially available anthranilic acid (anth-H2) its N-substituted derivatives, we report the isolation characterisation series unique tetrameric...

Transition, post-transition and rare earth metal complexes supported by (O,N)- (N,N)-type ligands dominate organometallic photochemistry. However, despite a vast number of aminobenzoate having been reported, aluminium being globally abundant, alkylaluminium anthranilates have not yet considered as effective luminophores. Herein, using family commercially available anthranilic acid (anth-H2) its N-substituted derivatives, we report the isolation characterisation series unique tetrameric...

8-Aminoquinoline (8AQ) is the building block for many medicinal molecules. However, redox properties of 8AQ, which are important understanding stability drugs based on 8AQ in human body, have not been studied detail before. We used cyclic voltammetry and pulse voltammetric techniques to investigate anodic as well cathodic electrochemical behaviour a wide pH range. also applied UV-Vis spectroscopy get better deprotonation due changes. In addition, quantum chemical studies exploring energy...

Transition, post‐transition and rare earth metal complexes supported by (O,N)‐ (N,N)‐type ligands dominate organometallic photochemistry. However, despite a vast number of aminobenzoate having been reported, aluminium being globally abundant, alkylaluminium anthranilates have not yet considered as effective luminophores. Herein, using family commercially available composed anthranilic acid (anth‐H2) its N‐substituted derivatives, we report the isolation characterisation series unique...

Transition, post‐transition and rare earth metal complexes supported by (O,N)‐ (N,N)‐type ligands dominate organometallic photochemistry. However, despite a vast number of aminobenzoate having been reported, aluminium being globally abundant, alkylaluminium anthranilates have not yet considered as effective luminophores. Herein, using family commercially available composed anthranilic acid (anth‐H2) its N‐substituted derivatives, we report the isolation characterisation series unique...

Two novel cationic−anionic Cu( ii ) and Co( complexes with the N -scorpionate ligand have been synthesised characterised. The obtained are first reported examples of compounds tested for catecholase activity.

The reaction of GeBr with LiSi(SiMe3)3 leads to the metalloid cluster compound [(THF)2Li]3Ge14[Si(SiMe3)3]5 (1). After introduction a first this type, in which 14 germanium atoms form an empty polyhedron, [(THF)2Li]3Ge14[Ge(SiMe3)3]5 (2), we present here further investigations on 1 obtain preliminary insight into its chemical and bonding properties. molecular structure is determined via X-ray crystal solution using synchrotron radiation. electronic Ge14 polyhedron examined by quantum...

Noncovalent nanohybrids between meso-(p-hydroxyphenyl)porphyrin (TPPH) and graphene oxide (GO) sheets were studied as a function of pH. The overall charge the TPPH molecule changes negative (−4), neutral, positive (+2) depending on pH solution. Results Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis confirm successful noncovalent functionalization GO with TPPH. We applied number methods to probe ground-state well excited-state interaction components...

The present study explores the influence of graphene oxide (GO) on deactivation pathways excited states zinc 5,10,15,20-tetrakis(4-(hydroxyphenyl))porphyrin (ZnTPPH). interaction light with free ZnTPPH molecules and adsorbed sheets was probed via UV-vis spectroscopy, fluorescence femtosecond pump-probe technique nanosecond flash photolysis. Formation ground-state ZnTPPH-GO complex in solution monitored by red-shift porphyrin Soret absorption band. It found that Stern-Volmer quenching can be...

Two graphene oxide nanoassemblies using 5-(4-(aminophenyl)-10,15,20-triphenylporphyrin (TPPNH2) were fabricated by two synthetic methods: covalent (GO-CONHTPP) and noncovalent bonding. GO-CONHTPP was achieved through amide formation at the periphery of GO sheets hybrid material fully characterized FTIR, XPS, Raman spectroscopy, SEM. Spectroscopic measurements together with theoretical calculations demonstrated that assembling TPPNH2 on surface in DMF-H2O (1:2, v/v) via non-covalent...

Hyperfluorescence (HF), a relatively new phenomenon utilizing the transfer of excitons between two luminophores, requires careful pairwise tuning molecular energy levels and is proposed to be crucial step towards development new, highly effective OLED systems. To date, barely few HF yellow emitters with desired narrowband emission but moderate external quantum efficiency (EQE < 20%) have been reported. This because systematic strategy embracing both Förster resonance (FRET) triplet singlet...

Despite promising optoelectronic features of N-doped polycyclic aromatic hydrocarbons (PAHs), their use as functional materials remains underdeveloped due to limited post-functionalization. Facing this challenge, a novel design PAHs with D–A–D electronic structure for thermally activated delayed fluorescence (TADF) emitters was performed. Implementing set auxiliary donors at the meta position protruding phenyl ring quinoxaline triggers an increase in charge-transfer property simultaneously...