Rhodium-catalysed ortho-alkynylation of nitroarenes

The ortho-alkynylation of nitro-(hetero)arenes takes place in the presence of a Rh(iii) catalyst to deliver a wide variety of alkynylated nitroarenes regioselectively. These interesting products could be further derivatized by selective reduction of the nitro group or palladium-catalysed couplings. Experimental and computational mechanistic studies demonstrate that the reaction proceeds via a turnover-limiting electrophilic C–H metalation ortho to the strongly electron-withdrawing nitro group.

Rh(iii)-catalyzed ortho-alkynylation of nitro-(hetero)arenes leads to a wide variety of alkynylated nitroarenes via a turnover-limiting electrophilic C–H ortho-metalation.     

Highly efficient carbazolylgold(iii) dendrimers based on thermally activated delayed fluorescence and their application in solution-processed organic light-emitting devices

A new class of C^C^N ligand-containing carbazolylgold(iii) dendrimers has been designed and synthesized. High photoluminescence quantum yields of up to 82% in solid-state thin films and large radiative decay rate constants in the order of 10⁵ s⁻¹ are observed. These gold(iii) dendrimers are found to exhibit thermally activated delayed fluorescence (TADF), as supported by variable-temperature emission spectroscopy, time-resolved photoluminescence decay and computational studies. Solution-processed organic light-emitting diodes (OLEDs) based on these gold(iii) dendrimers have been fabricated, which exhibit a maximum current efficiency of 52.6 cd A⁻¹, maximum external quantum efficiency of 15.8% and high power efficiency of 41.3 lm W⁻¹. The operational stability of these OLEDs has also been recorded, with the devices based on zero- and second-generation dendrimers showing maximum half-lifetimes of 1305 and 322 h at 100 cd m⁻², respectively, representing the first demonstration of operationally stable solution-processed OLEDs based on gold(iii) dendrimers.

A new class of carbazolylgold(iii) C^C^N dendrimers with thermally activated delayed fluorescence properties has been designed and synthesized for the realzaqtion of operationally stable solution-processed organic light-emitting devices.     

Enhanced photoreduction of water catalyzed by a cucurbit[8]uril-secured platinum dimer

A cucurbit[8]uril (CB[8])-secured platinum terpyridyl chloride dimer was used as a photosensitizer and hydrogen-evolving catalyst for the photoreduction of water. Volumes of produced hydrogen were up to 25 and 6 times larger than those obtained with the corresponding free and cucurbit[7]uril-bound platinum monomer, respectively, at equal Pt concentration. The thermodynamics of the proton-coupled electron transfer from the Pt(ii)–Pt(ii) dimer to the corresponding Pt(ii)–Pt(iii)–H hydride key intermediate, as quantified by density functional theory, suggest that CB[8] secures the Pt(ii)–Pt(ii) dimer in a particularly reactive conformation that promotes hydrogen formation.

The cucurbit[8]uril macrocycle can secure a platinum terpyridyl complex into a particularly reactive dimer that catalyzes the photoreduction of water.     

Accessing lanthanide-based,in situ illuminated optical turn-on probes by modulation of the antenna triplet state energy

Luminescent lanthanides possess ideal properties for biological imaging, including long luminescent lifetimes and emission within the optical window. Here, we report a novel approach to responsive luminescent Tb(iii) probes that involves direct modulation of the antenna excited triplet state energy. If the triplet energy lies too close to the ⁵D₄ Tb(iii) excited state (20 500 cm⁻¹), energy transfer to ⁵D₄ competes with back energy transfer processes and limits lanthanide-based emission. To validate this approach, a series of pyridyl-functionalized, macrocyclic lanthanide complexes were designed, and the corresponding lowest energy triplet states were calculated using density functional theory (DFT). Subsequently, three novel constructs L3 (nitro-pyridyl), L4 (amino-pyridyl) and L5 (fluoro-pyridyl) were synthesized. Photophysical characterization of the corresponding Gd(iii) complexes revealed antenna triplet energies between 25 800 and 30 400 cm⁻¹ and a 500-fold increase in quantum yield upon conversion of Tb(L3) to Tb(L4) using the biologically relevant analyte H₂S. The corresponding turn-on reaction can be monitored using conventional, small-animal optical imaging equipment in presence of a Cherenkov radiation emitting isotope as an in situ excitation source, demonstrating that antenna triplet state energy modulation represents a viable approach to biocompatible, Tb-based optical turn-on probes.

The rational, analyte-mediated modulation of the relative energy of the lanthanide-sensitizing triplet state produces Tb-based luminescence, observable by a conventional optical imager in presence of the Cherenkov radiation emitting radioisotope ¹⁸F.     

Epoc group: transformable protecting group with gold(iii)-catalyzed fluorene formation

This study presents the novel concept of a transformable protecting group, which changes its properties through structural transformation. Based on this concept, we developed a 2-(2-ethynylphenyl)-2-(5-methylfuran-2-yl)-ethoxycarbonyl (Epoc) group. The Epoc group was transformed into an Fmoc-like structure with gold(iii)-catalyzed fluorene formation and was removable under Fmoc-like mild basic conditions post-transformation even though it was originally stable under strongly basic conditions. As an application for organic synthesis, the Epoc group provides the novel orthogonality of gold(iii)-labile protecting groups in solid-phase peptide synthesis. In addition, the high turnover number of fluorene formation in aqueous media is suggestive of the applicability of the Epoc group to biological systems.

A protecting group removable with gold(iii)-catalyzed fluorene formation and the subsequent addition of piperidine was developed.     

Complexation and redox chemistry of neptunium,plutonium and americium with a hydroxylaminato ligand

There is significant interest in ligands that can stabilize actinide ions in oxidation states that can be exploited to chemically differentiate 5f and 4f elements. Applications range from developing large-scale actinide separation strategies for nuclear industry processing to carrying out analytical studies that support environmental monitoring and remediation efforts. Here, we report syntheses and characterization of Np(iv), Pu(iv) and Am(iii) complexes with N-tert-butyl-N-(pyridin-2-yl)hydroxylaminato, [2-(^tBuNO)py]⁻(interchangeable hereafter with [(^tBuNO)py]⁻), a ligand which was previously found to impart remarkable stability to cerium in the +4 oxidation state. An[(^tBuNO)py]₄ (An = Pu, 1; Np, 2) have been synthesized, characterized by X-ray diffraction, X-ray absorption, ¹H NMR and UV-vis-NIR spectroscopies, and cyclic voltammetry, along with computational modeling and analysis. In the case of Pu, oxidation of Pu(iii) to Pu(iv) was observed upon complexation with the [(^tBuNO)py]⁻ ligand. The Pu complex 1 and Np complex 2 were also isolated directly from Pu(iv) and Np(iv) precursors. Electrochemical measurements indicate that a Pu(iii) species can be accessed upon one-electron reduction of 1 with a large negative reduction potential (E_1/2 = −2.26 V vs. Fc^+/0). Applying oxidation potentials to 1 and 2 resulted in ligand-centered electron transfer reactions, which is different from the previously reported redox chemistry of U^IV[(^tBuNO)py]₄ that revealed a stable U(v) product. Treatment of an anhydrous Am(iii) precursor with the [(^tBuNO)py]⁻ ligand did not result in oxidation to Am(iv). Instead, the dimeric complex [Am^III(μ₂-(^tBuNO)py)((^tBuNO)py)₂]₂ (3) was isolated. Complex 3 is a rare example of a structurally characterized non-aqueous Am-containing molecular complex prepared using inert atmosphere techniques. Predicted redox potentials from density functional theory calculations show a trivalent accessibility trend of U(iii) < Np(iii) < Pu(iii) and that the higher oxidation states of actinides (i.e., +5 for Np and Pu and +4 for Am) are not stabilized by [2-(^tBuNO)py]⁻, in good agreement with experimental observations.

The coordination modes and electronic properties of a strongly coordinating hydroxylaminato ligand with Np, Pu and Am were investigated.Complexes were characterized by a range of experimental and computational techniques.     

Label-free luminescence switch-on detection of hepatitis C virus NS3 helicase activity using a G-quadruplex-selective probe

A series of luminescent Ir(iii) complexes were synthesised and evaluated for their ability to act as luminescent G-quadruplex-selective probes. The Ir(iii) complex 9, [Ir(phq)₂(phen)]PF₆ (where phq = 2-phenylquinoline; phen = 1,10-phenanthroline), exhibited high luminescence in the presence of G-quadruplex DNA compared to dsDNA and ssDNA, and was employed to construct a label-free G-quadruplex-based assay for hepatitis C virus NS3 helicase activity in aqueous solution. Moreover, the application of the assay for screening potential helicase inhibitors was demonstrated. To our knowledge, this is the first G-quadruplex-based assay for helicase activity.     

Enhanced visible light absorption in layered Cs3Bi2Br9 through mixed-valence Sn(ii)/Sn(iv) doping

Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite Cs₃Bi₂Br₉, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr₂ to the solution-phase synthesis of Cs₃Bi₂Br₉ leads to substitution of up to 7% of the Bi(iii) ions by equal quantities of Sn(ii) and Sn(iv). The nature of the substitutional defects was studied by X-ray diffraction, ¹³³Cs and ¹¹⁹Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations. The resulting mixed-valence compounds show intense visible and near infrared absorption due to intervalence charge transfer, as well as electronic transitions to and from localised Sn-based states within the band gap. Sn(ii) and Sn(iv) defects preferentially occupy neighbouring B-cation sites, forming a double-substitution complex. Unusually for a Sn(ii) compound, the material shows minimal changes in optical and structural properties after 12 months storage in air. Our calculations suggest the stabilisation of Sn(ii) within the double substitution complex contributes to this unusual stability. These results expand upon research on inorganic mixed-valent halides to a new, layered structure, and offer insights into the tuning, doping mechanisms, and structure–property relationships of lead-free vacancy-ordered perovskite structures.

Mixed valence Sn doping of Cs₃Bi₂Br₉ leads to broad visible light absorption.     

Genomics-driven discovery of chiral triscatechol siderophores with enantiomeric Fe(iii) coordination

Ferric complexes of triscatechol siderophores may assume one of two enantiomeric configurations at the iron site. Chirality is known to be important in the iron uptake process, however an understanding of the molecular features directing stereospecific coordination remains ambiguous. Synthesis of the full suite of (DHB^L/DLys^L/DSer)₃ macrolactone diastereomers, which includes the siderophore cyclic trichrysobactin (CTC), enables the effects that the chirality of Lys and Ser residues exert on the configuration of the Fe(iii) complex to be defined. Computationally optimized geometries indicate that the Λ/Δ configurational preferences are set by steric interactions between the Lys sidechains and the peptide backbone. The ability of each (DHB^L/DLys^L/DSer)₃ diastereomer to form a stable Fe(iii) complex prompted a genomic search for biosynthetic gene clusters (BGCs) encoding the synthesis of these diastereomers in microbes. The genome of the plant pathogen Dickeya chrysanthemi EC16 was sequenced and the genes responsible for the biosynthesis of CTC were identified. A related but distinct BGC was identified in the genome of the opportunistic pathogen Yersinia frederiksenii ATCC 33641; isolation of the siderophore from Y. frederiksenii ATCC 33641, named frederiksenibactin (FSB), revealed the triscatechol oligoester, linear-(DHB^LLys^LSer)₃. Circular dichroism (CD) spectroscopy establishes that Fe(iii)–CTC and Fe(iii)–FSB are formed in opposite enantiomeric configuration, consistent with the results of the ferric complexes of the cyclic (DHB^L/DLys^L/DSer)₃ diastereomers.

Synthesis and genome mining leverage access to diastereomers of the siderophore cyclic trichrysobactin. Computational modeling and CD spectroscopy address effects that ligand-based stereochemistry exerts on the configuration at Fe(iii).     

An effective and versatile strategy for the synthesis of structurally diverse heteroarylsilanes via Ir(iii)-catalyzed C–H silylation

A versatile silylation of heteroaryl C–H bonds is accomplished under the catalysis of a well-defined spirocyclic NHC Ir(iii) complex (SNIr), generating a variety of heteroarylsilanes. A significant advantage of this catalytic system is that multiple types of intermolecular C–H silylation can be achieved using one catalytic system at α, β, γ, or δ positions of heteroatoms with excellent regioselectivities. Mechanistic experiments and DFT calculations indicate that the polycyclic ligand of SNIr can form an isolable cyclometalated intermediate, which leaves a phenyl dentate free and provides a hemi-open space for activating substrates. In general, favorable silylations occur at γ or δ positions of chelating heteroatoms, forming 5- or 6-membered C–Ir–N cyclic intermediates. If such an activation mode is prohibited sterically, silylations would take place at the α or β positions. The mechanistic studies would be helpful for further explaining the reactivity of the SNIr system.

A versatile silylation of heteroaryl C–H bonds is accomplished under the catalysis of a well-defined spirocyclic NHC Ir(iii) complex (SNIr), generating a variety of heteroarylsilanes.     

Hydrophilic sulfonated bis-1,2,4-triazine ligands are highly effective reagents for separating actinides(iii) from lanthanides(iii) via selective formation of aqueous actinide complexes

We report the first examples of hydrophilic 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands, and their applications as actinide(iii) selective aqueous complexing agents. The combination of a hydrophobic diamide ligand in the organic phase and a hydrophilic tetrasulfonated bis-triazine ligand in the aqueous phase is able to separate Am(iii) from Eu(iii) by selective Am(iii) complex formation across a range of nitric acid concentrations with very high selectivities, and without the use of buffers. In contrast, disulfonated bis-triazine ligands are unable to separate Am(iii) from Eu(iii) in this system. The greater ability of the tetrasulfonated ligands to retain Am(iii) selectively in the aqueous phase than the corresponding disulfonated ligands appears to be due to the higher aqueous solubilities of the complexes of the tetrasulfonated ligands with Am(iii). The selectivities for Am(iii) complexation observed with hydrophilic tetrasulfonated bis-triazine ligands are in many cases far higher than those found with the polyaminocarboxylate ligands previously used as actinide-selective complexing agents, and are comparable to those found with the parent hydrophobic bis-triazine ligands. Thus we demonstrate a feasible alternative method to separate actinides from lanthanides than the widely studied approach of selective actinide extraction with hydrophobic bis-1,2,4-triazine ligands such as CyMe₄-BTBP and CyMe₄-BTPhen.     

Mg(ii) heterodinuclear catalysts delivering carbon dioxide derived multi-block polymers

Carbon dioxide derived polymers are emerging as useful materials for applications spanning packaging, construction, house-hold goods and automotive components. To accelerate and broaden their uptake requires both more active and selective catalysts and greater structural diversity for the carbon dioxide derived polymers. Here, highly active catalysts show controllable selectivity for the enchainment of mixtures of epoxide, anhydride, carbon dioxide and lactone. Firstly, metal dependent selectivity differences are uncovered using a series of dinuclear catalysts, Mg(ii)Mg(ii), Zn(ii)Zn(ii), Mg(ii)Zn(ii), and Mg(ii)Co(ii), each exposed to mixtures of bio-derived tricyclic anhydride, cyclohexene oxide and carbon dioxide (1 bar). Depending upon the metal combinations, different block structures are possible with Zn(ii)Zn(ii) yielding poly(ester-b-carbonate); Mg(ii)Mg(ii) or Mg(ii)Co(ii) catalysts delivering poly(carbonate-b-ester); and Mg(ii)Zn(ii) furnishing a random copolymer. These results indicate that carbon dioxide insertion reactions follow the order Co(ii) > Mg(ii) > Zn(ii). Using the most active and selective catalyst, Mg(ii)Co(ii), and exploiting reversible on/off switches between carbon dioxide/nitrogen at 1 bar delivers precision triblock (ABA), pentablock (BABAB) and heptablock (ABABABA) polymers (where A = poly(cyclohexylene oxide-alt-tricyclic anhydride), PE; B = poly(cyclohexene carbonate), PCHC). The Mg(ii)Co(ii) catalyst also selectively polymerizes a mixture of anhydride, carbon dioxide, cyclohexene oxide and ε-caprolactone to deliver a CBABC pentablock copolymer (A = PE, B = PCHC C = poly(caprolactone), PCL). The catalysts combine high activity and selectivity to deliver new polymers featuring regularly placed carbon dioxide and biomass derived linkages.

Carbon dioxide-based multiblock polymers are synthesised, in one-pot, from a mixture of monomers using a highly selective and active heterodinuclear Co(ii)Mg(ii) catalyst.     

Development of a panchromatic photosensitizer and its application to photocatalytic CO2 reduction

We designed and synthesized a heteroleptic osmium(ii) complex with two different tridentate ligands, Os. Os can absorb the full wavelength range of visible light owing to S–T transitions, and this was supported by TD-DFT calculations. Excitation of Os using visible light of any wavelength generates the same lowest triplet metal-to-ligand charge-transfer excited state, the lifetime of which is relatively long (τ_em = 40 ns). Since excited Os could be reductively quenched by 1,3-dimethyl-2-(o-hydroxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole, Os displays high potential as a panchromatic photosensitizer. Using a combination of Os and a ruthenium(ii) catalyst, CO₂ was photocatalytically reduced to HCOOH via irradiation with 725 nm light, and the turnover number reached 81; irradiation with light at λ_ex > 770 nm also photocatalytically induced HCOOH formation. These results clearly indicate that Os can function as a panchromatic redox photosensitizer.

The osmium(ii) complex functioned as a panchromatic photosensitizer and drove CO₂ reduction.     

Molecular design of efficient yellow- to red-emissive alkynylgold(iii) complexes for the realization of thermally activated delayed fluorescence (TADF) and their applications in solution-processed organic light-emitting devices

Here, we report the design and synthesis of a new class of fused heterocyclic alkynyl ligand-containing gold(iii) complexes, which show tunable emission colors spanning from the yellow to red region in the solid state and exhibit thermally activated delayed fluorescence (TADF) properties. These complexes display high photoluminescence quantum yields of up to 0.87 and short excited-state lifetimes in sub-microsecond timescales, yielding high radiative decay rate constants on the order of up to 10⁶ s⁻¹. The observation of the drastic enhancement in the emission intensity of the complexes with insignificant change in the excited-state lifetime upon increasing the temperature from 200 to 360 K indicates an increasing radiative decay rate. The experimentally estimated energy splitting between the lowest-lying singlet excited state (S₁) and the lowest-lying triplet excited state (T₁), ΔE_S1–T1, is found to be as small as ∼0.03 eV (250 cm⁻¹), comparable to the value of ∼0.05 eV (435 cm⁻¹) obtained from computational studies. The delicate choice of the cyclometalating ligand and the fused heterocyclic ligand is deemed the key to induce TADF through the control of the energy levels of the intraligand and the ligand-to-ligand charge transfer excited states. This work represents the realization of highly emissive yellow- to red-emitting gold(iii) TADF complexes incorporated with fused heterocyclic alkynyl ligands and their applications in organic light-emitting devices.

We report the design of a new class of fused heterocyclic alkynyl ligand-containing gold(iii) complexes, which shows tunable emission colors spanning yellow to red region and exhibits thermally activated delayed fluorescence (TADF) properties.     

Sensitization of wide band gap photocatalysts to visible light by molten CuCl treatment

Cu(i)-substituted metal oxide photocatalysts were prepared using molten CuCl treatment of wide band gap photocatalysts. The Cu(i)-substituted metal oxide photocatalysts possessed a new absorption band in the visible light region and showed photocatalytic activity for hydrogen evolution from an aqueous solution containing sulfur sacrificial reagents under visible light irradiation. Notably, the Cu(i)–K₂La₂Ti₃O₁₀ and Cu(i)–NaTaO₃ photocatalysts showed relatively high activities for hydrogen evolution and gave apparent quantum yields of 0.18% at 420 nm. These photocatalysts responded up to 620 nm. Thus, Cu(i)-substitution using a molten CuCl treatment was an effective strategy for sensitizing a metal oxide photocatalyst with a wide band gap to visible light.     

Stoichiometric to catalytic reactivity of the aryl cycloaurated species with arylboronic acids: insight into the mechanism of gold-catalyzed oxidative C(sp2)–H arylation

Based on the well-defined five-membered aryl gold(iii) complexes, [Au(tpy)X₂] (3a and 3b) and [AuBr(Ph)(tpy)] (7), as well as the aryl gold(iii) complex [AuCl₂(Ph)(tpy)] (8) (tpy = 2-(o-tolyl)pyridine) as reliable models, we present a detailed study of the mechanism for gold(iii)-catalyzed oxidative cross-coupling reactions between cycloaurable arenes and arylboronic acids. Here we report the direct evidence for a mechanistic proposal including arene C–H activation, transmetallation and biaryl reductive elimination. The chelation-assisted C–H activation strategy has been used for the development of the gold(iii)-catalyzed C–H bond arylation of arenes with aryl reagents to forge extended π-conjugated systems.     

Mechanism,reactivity, and selectivity of the iridium-catalyzed C(sp3)–H borylation of chlorosilanes

The iridium-catalyzed C(sp³)–H borylation of methylchlorosilanes is investigated by means of density functional theory, using the B3LYP and M06 functionals. The calculations establish that the resting state of the catalyst is a seven-coordinate Ir(v) species that has to be converted into an Ir(iii)tris(boryl) complex in order to effect the oxidative addition of the C–H bond. This is then followed by a C–B reductive elimination to yield the borylated product, and the catalytic cycle is finally completed by the regeneration of the active catalyst over two facile steps. The two employed functionals give somewhat different conclusions concerning the nature of the rate-determining step, and whether reductive elimination occurs directly or after a prior isomerization of the Ir(v) hydride intermediate complex. The calculations reproduce quite well the experimentally-observed trends in the reactivities of substrates with different substituents. It is demonstrated that the reactivity can be correlated to the Ir–C bond dissociation energies of the corresponding Ir(v) hydride intermediates. The effect of the chlorosilyl group is identified to originate from the α-carbanion-stabilizing effect of the silicon, which is further reinforced by the presence of an electron-withdrawing chlorine substituent. Furthermore, the source of selectivity for the borylation of primary over secondary C(sp³)–H can be explained on a steric basis, by repulsion between the alkyl group and the Ir/ligand moiety. Finally, the difference in the reactivity between C(sp³)–H and C(sp²)–H borylation is investigated and rationalized in terms of distortion/interaction analysis.     

Influence of the primary and secondary coordination spheres on nitric oxide adsorption and reactivity in cobalt(ii)–triazolate frameworks

Nitric oxide (NO) is an important signaling molecule in biological systems, and as such, the ability of porous materials to reversibly adsorb NO is of interest for potential medical applications. Although certain metal–organic frameworks are known to bind NO reversibly at coordinatively unsaturated metal sites, the influence of the metal coordination environment on NO adsorption has not been studied in detail. Here, we examine NO adsorption in the frameworks Co₂Cl₂(bbta) (H₂bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) and Co₂(OH)₂(bbta) using gas adsorption, infrared spectroscopy, powder X-ray diffraction, and magnetometry. At room temperature, NO adsorbs reversibly in Co₂Cl₂(bbta) without electron transfer, with low temperature data supporting spin-crossover of the NO-bound cobalt(ii) centers of the material. In contrast, adsorption of low pressures of NO in Co₂(OH)₂(bbta) is accompanied by charge transfer from the cobalt(ii) centers to form a cobalt(iii)–NO⁻ adduct, as supported by diffraction and infrared spectroscopy data. At higher pressures of NO, characterization data indicate additional uptake of the gas and disproportionation of the bound NO to form a cobalt(iii)–nitro (NO₂⁻) species and N₂O gas, a transformation that appears to be facilitated by secondary sphere hydrogen bonding interactions between the bound NO₂⁻ and framework hydroxo groups. These results provide a rare example of reductive NO binding in a cobalt-based metal–organic framework, and they demonstrate that NO uptake can be tuned by changing the primary and secondary coordination environment of the framework metal centers.

Nitric oxide (NO) shows differences in adsorption and reactivity in two related cobalt(ii)–triazolate frameworks, demonstrating how the primary and secondary coordination sphere of metal centers in adsorbents can be designed for targeted delivery.     

Flow electrochemistry: a safe tool for fluorine chemistry

The heightened activity of compounds containing fluorine, especially in the field of pharmaceuticals, provides major impetus for the development of new fluorination procedures. A scalable, versatile, and safe electrochemical fluorination protocol is conferred. The strategy proceeds through a transient (difluoroiodo)arene, generated by anodic oxidation of an iodoarene mediator. Even the isolation of iodine(iii) difluorides was facile since electrolysis was performed in the absence of other reagents. A broad range of hypervalent iodine mediated reactions were achieved in high yields by coupling the electrolysis step with downstream reactions in flow, surpassing limitations of batch chemistry. (Difluoroiodo)arenes are toxic and suffer from chemical instability, so the uninterrupted generation and immediate use in flow is highly advantageous. High flow rates facilitated productivities of up to 834 mg h⁻¹ with vastly reduced reaction times. Integration into a fully automated machine and in-line quenching was key in reducing the hazards surrounding the use of hydrofluoric acid.

A scalable, efficient and safe electrochemical fluorination protocol is conferred. A broad range of iodine(iii) mediated transformations were performed in high yields without exposure to toxic HF.     

The switchable phosphorescence and delayed fluorescence of a new rhodamine-like dye through allenylidene formation in a cyclometallated platinum(ii) system

A new rhodamine-like alkyne-substituted ligand (Rhodyne) was designed to coordinate a cyclometallated platinum(ii) system. The chemo-induced “ON–OFF” switching capabilities on the spirolactone ring of the Rhodyne ligand with an end-capping platinum(ii) metal centre can modulate the interesting acetylide–allenylidene resonance. The long-lived ³IL excited state of Rhodyne in its ON state as an optically active opened form was revealed via steady-state and time-resolved spectroscopy studies. Exceptional near-infrared (NIR) phosphorescence and delayed fluorescence based on a rhodamine-like structure were observed at room temperature for the first time. The position of the alkyne communication bridge attached to the platinum(ii) unit was found to vary the lead(ii)-ion binding mode and also the possible resonance structure for metal-mediated allenylidene formation. The formation of a proposed allenylidene resonance structure was suggested to rationalize these phenomena.

A new rhodamine-like ligand (Rhodyne) was designed to coordinate a cyclometallated platinum(ii) system. Allenylidene formation could trigger NIR phosphorescence at 740 nm originating from Rhodyne ³IL, as well as delayed fluorescence at 620 nm.