TADF Invariant of Host Polarity and Ultralong Fluorescence Lifetimes in a Donor-Acceptor Emitter Featuring a Hybrid Sulfone-Triarylboron Acceptor.

10H-Dibenzo[b,e][1,4]thiaborinine 5,5-dioxide (SO2B)-a high triplet (T1 =3.05 eV) strongly electron-accepting boracycle was successfully utilised in thermally activated delayed fluorescence (TADF) emitters PXZ-Dipp-SO2B and CZ-Dipp-SO2B. We demonstrate the near-complete separation of highest occupied and lowest unoccupied molecular orbitals leading to a low oscillator strength of the S1 →S0 CT transition, resulting in very long ca. 83 ns and 400 ns prompt fluorescence lifetimes for CZ-Dipp-SO2B and PXZ-Dipp-SO2B, respectively, but retaining near unity photoluminescence quantum yield. OLEDs using CZ-Dipp-SO2B as the luminescent dopant display high external quantum efficiency (EQE) of 23.3 % and maximum luminance of 18600 cd m-2 with low efficiency roll off at high brightness. For CZ-Dipp-SO2B, reverse intersystem crossing (rISC) is mediated through the vibronic coupling of two charge transfer (CT) states, without involving the triplet local excited state (3 LE), resulting in remarkable rISC rate invariance to environmental polarity and polarisability whilst giving high organic light-emitting diode (OLED) efficiency. This new form of rISC allows stable OLED performance to be achieved in different host environments.

Heavy-Atom Free spiro Organoboron Complexes As Triplet Excited States Photosensitizers for Singlet Oxygen Activation.

Herein, we present a new strategy for the development of efficient heavy-atom free singlet oxygen photosensitizers based on rigid borafluorene scaffolds. Physicochemical properties of borafluorene complexes can be easily tuned through the choice of ligand, thus allowing exploration of numerous organoboron structures as potent 1O2 sensitizers. The singlet oxygen generation quantum yields of studied complexes vary in the range of 0.55-0.78. Theoretical calculations reveal that the introduction of the borafluorene moiety is crucial for the stabilization of a singlet charge transfer state, while intersystem crossing to a local triplet state is facilitated by orthogonal donor-acceptor molecular architecture. Our study shows that quantitative oxidation of selected organic substrates can be achieved in 20-120 min of irradiation with only 0.05 mol % loading of a photocatalyst.

Experimental and Theoretical Insights into Molecular and Solid-State Properties of Isomeric Bis(salicylaldehydes).

A series of five bis(salicylaldehydes), including four isomeric compounds based on a benzene scaffold and a closely related naphthalene derivative, were investigated in order to elucidate the impact of resonance effects and intramolecular hydrogen bonds (HBs) on the macroscopic properties of these systems. Density functional theory (DFT) computations revealed important differences between isomers on the molecular level, which was reflected in different charge distributions, aromatic C-C bond orders, and aromaticity characters. The consequences of these features were evidenced by the UV-vis absorption spectra: for 1,3-diformyl-4,6-dihydroxybenzene (2), the longest wavelength absorption band is observed at 285 nm, while its isomers 1,4-diformyl-2,5-dihydroxybenzene (1), 1,4-diformyl-2,3-dihydroxybenzene (3), and 1,2-diformyl-3,6-dihydroxybenzene (4) are characterized by absorption in the visible range (379-407 nm). The specificity of 2 results from simultaneous lowering and elevation of HOMO and LUMO energy levels, respectively. We have found that the HOMO/LUMO energy variations follow trends observed in isomeric dihydroxybenzenes (HOMO) and phthalaldehydes (LUMO), and these effects operate separately to some extent. Furthermore, theoretical calculations indicate that the UV-vis spectral properties of bis(salicylaldehydes) are directly transferable to the corresponding bis(salicylaldimines) and their boron complexes. Finally, the influence of structural and molecular stabilization effects was analyzed by means of X-ray structural analysis and periodic DFT computations.

At Long Last: Olefin Metathesis Macrocyclization at High Concentration.

Macrocyclic lactones, ketones, and ethers can be obtained in the High-Concentration Ring-Closing Metathesis (HC-RCM) reaction in high yield and selectivity at concentrations 40 to 380 times higher than those typically used by organic chemists for similar macrocyclizations. The new method consists of using tailored ruthenium catalysts together with applying vacuum to distill off the macrocyclic product as it is formed by the metathetical backbiting of oligomers. Unlike classical RCM, no large quantities of organic solvents are used, but rather inexpensive nonvolatile diluents, such as natural or synthetic paraffin oils. Moreover, use of a protecting atmosphere or a glovebox is not needed, as the new catalysts are perfectly moisture and air stable. In addition, some other cyclic compounds previously reported as unobtainable by RCM in neat conditions, or in high dilutions even, can be formed with the help of the HC-RCM method.

Highly Fluorescent Red-Light Emitting Bis(boranils) Based on Naphthalene Backbone.

Ten bis(boranils) differently substituted at the boron atom and iminophenyl groups were synthesized from 1,5-dihydroxynaphthalene-2,6-dicarboxaldehyde using a simple one-pot protocol. Their photophysical properties can be easily tuned in a wide range by the variation of substituents. Their absorption and emission spectral bands are significantly red-shifted (λmax = 495-590 nm, λem = 533-683 nm) when compared with simple boranils, whereas fluorescence quantum yields are strongly improved to reach 83%. The attachment of pendant NO2 and NEt2 groups at the opposite positions of the π-conjugated bis(boranil) scaffold resulted in the formation of an unprecedented system featuring push-pull architecture.

Tuning of the colour and chemical stability of model boranils: a strong effect of structural modifications.

A series of diarylborinic complexes with salicydeneaniline ligands bearing various functional groups at the 6-position have been synthesized in high yields by applying a straightforward one-pot multicomponent protocol. UV-Vis measurements revealed the influence of electronic character of substituents on the observed maximum of emission (λem). This has been confirmed by a relatively strong linear correlation (R(2) = 0.92) of λem with Hammett σp(+) constants. Such a correlation was investigated using a QTAIM analysis of the charge density distribution. Absorption and emission bands for the obtained systems span between 390-437 nm and between 506-590 nm, respectively, with quantum yields reaching 17%. Time-dependent UV-Vis absorption measurements revealed that diphenylborinic salicydeneaniline complexes undergo slow degradation in solution under ambient conditions. In contrast, the use of a naphthalene-based chromophore or the introduction of fluorinated phenyl groups at the boron atom resulted in stable systems.

Cationic and Betaine-Type Boronated Acridinium Dyes: Synthesis, Characterization, and Photocatalytic Activity.

A series of isomeric boronated acridinium dyes were obtained by reactions of 10-(4'-octyloxyphenyl) functionalized 9(10H)-acridanone derivative with lithiated phenylboronic azaesters followed by aromatization with perchloric acid. The effect of the position of boronic group attached at ortho, meta, and para positions of the 9-phenyl ring on the photophysical properties was investigated. Conversion to related betaine trifluoroborato-substituted compounds was successfully performed, and the effect of this structural change on UV-vis absorption and fluorescence spectroscopy characteristics was established. Furthermore, cyclic voltammetry studies revealed that electrochemical behavior of cationic versus betaine structures is different in terms of redox potential values as well as stability. The theoretical calculations revealed a different scheme for molecular excitation processes in B(OH)2 versus BF3 --substituted compounds as charge transfer to acridinium core is observed from N-aryl or B-aryl moiety, respectively. Obtained compounds were active as photocatalysts in selected visible-light-promoted addition reactions to unsaturated substrates.

Antimicrobial and KPC/AmpC inhibitory activity of functionalized benzosiloxaboroles.

A series of 22 benzosiloxaboroles, silicon analogues of strong antimicrobial agents - benzoxaboroles, have been synthesized and tested against ß-lactamases KPC- and pAmpC-producing strains of Gram-negative rods. Comprehensive structural-property relationship studies supported by molecular modelling as well as biological studies reveal that 6-B(OH)2-substituted derivative 27 strongly inhibits the activity of cephalosporinases (chromosomally encoded AmpC and plasmid encoded CMY-2) and KPC carbapenemases. It also shows strong ability to inhibit growth of the strains producing KPC-3 when combined with meropenem. In addition, halogen-substituted (mono-, di- or tetra-) benzosiloxaboroles demonstrate high antifungal activity (MIC 1.56-6.25 mg/L) against C. tropicalis, C. guilliermondii and S. cerevisiae. The highest activity against pathogenic yeasts (C. albicans, C. krusei and C. parapsilosis - MICs 12.5 mg/L) and against Gram-positive cocci (S. aureus and E. faecalis - 6.25 mg/L and 25 mg/L respectively) was displayed by 6,7-dichloro-substituted benzosiloxaborole. The studied systems exhibit low cytotoxity toward human lung fibroblasts.

The effect of locking π-conjugation in organoboron moieties in the structures of luminescent tetracoordinate boron complexes.

A series of 8 luminescent borafluorene complexes were extensively studied both experimentally and theoretically in order to elucidate the effect of organoboron moiety rigidification on the physicochemical properties of these compounds. Due to the spiro geometry of the boron atom, borafluorene and ligand units are perpendicularly aligned, which considerably affects the flexibility of the molecule as well as its solid-state structure. Through comparative analysis with close diphenyl analogues, we show how these structural features influence the thermal, photoluminescent and charge mobility behaviour of the studied compounds. Crystal structural analysis revealed that the molecules are connected mostly through C-HO and C-Hπ interactions formed between perpendicularly aligned borafluorene and ligand moieties from neighboured molecules, serving as a complementary donor and acceptor of electron density, respectively. This also efficiently prevents molecules from engaging in unfavoured π-stacking contact. Furthermore, structural analysis suggests that borafluorene complexes possess a considerable degree of flexibility due to OBN heterocycle distortions and mutual borafluorene-ligand plane movements. The magnitude of these effects strictly depends on the ligand structure and may lead either to enhancing or lowering the quantum yield value with respect to BPh2 analogues, while the absorption and emission wavelength are slightly affected. The measured photophysical parameters for solid-state samples showed that the studied complexes are much better emitters in their crystalline states that in amorphous films. The TD-DFT and NTO calculations revealed a significant change in frontier molecular distribution, with the HOMO localized on the borafluorene moiety. However, as the HOMO-LUMO transition is geometrically not favoured, excitation occurred from HOMO-1 localized on the ligand. Finally, aggregation effects were discussed based on supramolecular arrangements in crystal structures and charge transfer rates obtained from theoretical calculations in the framework of the Marcus-Hush approximation. They suggest that borafluorene complexes are much better electron carriers with respect to non-annulated BPh2 complexes.

The study of interactions with a halogen atom: influence of NH2 group insertion on the crystal structures of meta-bromonitrobenzene derivatives.

Halogen atoms in molecular crystals may be involved in various interactions, often playing a very important role in structure stabilization. By introducing electron-donating groups, such as NH2, the electron density of the molecule is changed and thus interactions with the bromine substituent may alter. Herein, the crystal structures of meta-bromonitrobenzene and its NH2-substituted derivatives are analyzed. In all four described structures, namely m-bromonitrobenzene [Charlton & Trotter (1963). Acta Cryst. 16, 313], 4-bromo-2-nitroaniline (C6H5BrN2O2, 1), 2-bromo-6-nitroaniline (2) and 2-bromo-4-nitroaniline [Arshad et al. (2009). Acta Cryst. E65, o480], the Br atom is engaged in different interactions (Br...π, Br...O, Br...Br and C-H...Br, respectively). The Hirshfeld surface analysis (HS) and Reduced Density Gradient NonCovalent Interaction (RDG NCI) plots are used to prove the relevance, directionality and stabilizing nature of these interactions. Their modifications have been associated with the position of the amino group in the molecular structure and its influence on charge distribution analyzed with electrostatic potential surfaces (EPS). The diversification of the interactions has been correlated with a σ-hole potential value that enables a switching of the Br-atom character from electrophilic to nucleophilic.

The effect of conformational isomerism on the optical properties of bis(8-oxyquinolato) diboron complexes with a 2,2'-biphenyl backbone.

A fluorescent bis(8-oxyquinolato) diborinic complex with a central 2,2'-biphenyl backbone 1 and its octafluoro analogue 2 were synthesized to study the optical-structural relationship of sterically encumbered molecules featuring close intramolecular π-stacking interactions involving chromophore units. The crystal structure of 1 revealed a unique π-stacked arrangement of two pendant phenyl groups and two 8-oxyquinolato ligands (Q) located in the inner part of the complex. Unlike 1, the closely related complex 2 features conformational isomerism, and two major forms, namely 2-syn and 2-anti, are observed in solution to a varying extent depending on the solvent polarity. Form 2-syn, a geometrical analogue of 1, is preferable in polar solutions, whereas its rotational isomer 2-anti featuring π-stacking interactions between the terminal phenyl group and Q ligand dominates in benzene and chloromethane solutions. The observed conformational equilibria strongly affect the optical properties of the system, specifically leading to a significant increase of the quantum yield of emission (from 22% in MeCN to 38% in benzene) accompanied by a bathochromic shift (Δλ = 10 nm) of absorption and hypsochromic shifts (Δλ = -8 nm) of emission spectra with decreasing solvent polarity. This effect was ascribed to the variation in frontier orbital distributions.

An intramolecular ortho-assisted activation of the silicon-hydrogen bond in arylsilanes: an experimental and theoretical study.

An intramolecular activation of the Si-H bond in arylsilanes by selected ortho-assisting functional groups based on boron, carbon and phosphorus was investigated experimentally and by means of theoretical calculations. The major conclusion drawn is that the presence of a negatively charged oxygen atom in the functional group is essential for providing effective chelation to the silicon atom which in turn results in the increased hydridic character of a resulting five-coordinated species. In contrast, an intermolecular attack of hydroxide on the silicon atom in aryldimethylsilane results in the activation of the silicon-aryl bond. This increased reactivity of the Si-H bond in intramolecularly coordinated arylsilanes can be ascribed to a significant trans effect which operates in the preferred configuration. Hydrolytic cleavage of the Si-H bond results in dihydrogen elimination and the formation of various silicon heterocyclic systems such as benzosiloxaboroles, spiro-bis(siloxa)borinate, benzosilalactone and benzophosphoxasilole. In addition, intermolecular reduction of benzaldehydes with ortho-boronated arylsilane was observed whereas compounds bearing other reducible functional groups (COMe, COOEt, CN and NO2) were inert under comparable conditions. Specifically, an intramolecular reduction of the CN group in an ortho-silylated benzonitrile derivative was observed. The mechanism of Si-H bond activation was investigated by the DFT theoretical calculations. The calculations showed that the intramolecular coordination of the silicon atom effectively prevents the cleavage of the Si-aryl bond. Furthermore, the reaction is favored in anionic systems bearing COO-, B(OH)3- or CH2O- groups, while in the case of neutral functional groups such as PO(OEt)2 the process is much slower.