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.     

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.     

Lanthanide-mediated tuning of electronic and magnetic properties in heterotrimetallic cyclooctatetraenyl multidecker self-assemblies

The synthesis of a novel family of homoleptic COT-based heterotrimetallic self-assemblies bearing the formula [LnKCa(COT)₃(THF)₃] (Ln(iii) = Gd, Tb, Dy, Ho, Er, Tm, and Yb) is reported followed by their X-ray crystallographic and magnetic characterization. All crystals conform to the monoclinic P2₁/c space group with a slight compression of the unit cell from 3396.4(2) ų to 3373.2(4) ų along the series. All complexes exhibit a triple-decker structure having the Ln(iii) and K(i) ions sandwiched by three COT²⁻ ligands with an end-bound {Ca²⁺(THF)₃} moiety to form a non-linear (153.5°) arrangement of three different metals. The COT²⁻ ligands act in a η⁸-mode with respect to all metal centers. A detailed structural comparison of this unique set of heterotrimetallic complexes has revealed consistent trends along the series. From Gd to Yb, the Ln to ring-centroid distance decreases from 1.961(3) Å to 1.827(2) Å. In contrast, the separation of K(i) and Ca(ii) ions from the COT-centroid (2.443(3) and 1.914(3) Å, respectively) is not affected by the change of Ln(iii) ions. The magnetic property investigation of the [LnKCa(COT)₃(THF)₃] series (Ln(iii) = Gd, Tb, Dy, Ho, Er, and Tm) reveals that the Dy, Er, and Tm complexes display slow relaxation of their magnetization, in other words, single-molecule magnet (SMM) properties. This behaviour is dominated by thermally activated (Orbach-like) and quantum tunneling processes for [DyKCa(COT)₃(THF)₃] in contrast to [ErKCa(COT)₃(THF)₃], in which the thermally activated and Raman processes appear to be relevant. Details of the electronic structures and magnetic properties of these complexes are further clarified with the help of DFT and ab initio theoretical calculations.

A new class of heterotrimetallic COT-based self-assemblies accommodates metals from groups I–III in three different oxidation states and enables tuning of electronic and magnetic properties.     

Luminescent zinc(ii) and copper(i) complexes for high-performance solution-processed monochromic and white organic light-emitting devices

The synthesis and spectroscopic properties of luminescent tetranuclear zinc(ii) complexes of substituted 7-azaindoles and a series of luminescent copper(i) complexes containing 7,8-bis(diphenylphosphino)-7,8-dicarba-nido-undecaborate ligand are described. These complexes are stable towards air and moisture. Thin film samples of the luminescent copper(i) complexes in 2,6-dicarbazolo-1,5-pyridine and zinc(ii) complexes in poly(methyl methacrylate) showed emission quantum yields of up to 0.60 (for Cu-3) and 0.96 (for Zn-1), respectively. Their photophysical properties were examined by ultrafast time-resolved emission spectroscopy, temperature dependent emission lifetime measurements and density functional theory calculations. Monochromic blue and orange solution-processed OLEDs with these Zn(ii) and Cu(i) complexes as light-emitting dopants have been fabricated, respectively. Maximum external quantum efficiency (EQE) of 5.55% and Commission Internationale de l''Eclairage (CIE) coordinates of (0.16, 0.19) were accomplished with the optimized Zn-1-OLED while these values were, respectively 15.64% and (0.48, 0.51) for the optimized Cu-3-OLED. Solution-processed white OLEDs having maximum EQE of 6.88%, CIE coordinates of (0.42, 0.44), and colour rendering index of 81 were fabricated by using these luminescent Zn(ii) and Cu(i) complexes as blue and orange light-emitting dopant materials, respectively.     

Oxovanadium(<Emphasis Type="SmallCaps">iv</Emphasis>) cations in heterometallic and heteroligand complex formation

The formation of heterometallic oxovanadium(iv) diethylenetriaminepentaacetates with titanium(iii), chromium(iii), cobalt(ii), nickel(ii), and manganese(ii) cations in aqueous solutions was studied by spectrophotometry and pH-metry. The stabilizing influence of heterometallic chelation on an unstable oxidation state of Ti ⁱⁱⁱ and the labilizing effect of oxovanadium(iv) cations on the coordination of Cr ⁱⁱⁱ cations by the carboxylate ligand anions in the heterometallic complex were shown. The optimum conditions for the formation of the heterometallic dtpa complexes were selected and their thermodynamic stability was estimated. The states of the oxovanadium(iv) cations in the monoand heteroligand systems involving polyamine, polyaminopolycarboxylate, and alkylpolyphosphonate ligands were studied. Specific features of ligand coordination and formation of the mixed-ligand chelates were investigated. A variety of molecular compositions of complex oxovanadium(iv) oxyethylenediphosphonate particles formed in ranges of pH 2.2—3.0, 4.5—5.5, and 6.3—6.4 was found. The preferability of formation of polynuclear oxovanadium(iv) oxyethylidenediphosphonates, viz., binuclear particles with oxovanadium(iv) cation to ligand molar ratios of 2 : 1 and 2 : 5 and trinuclear particles with a molar ratio of components of 3 : 2, was shown.     

Hemilabile MIC^N ligands allow oxidant-free Au(i)/Au(iii) arylation-lactonization of γ-alkenoic acids

Oxidant-free Au-catalyzed reactions are emerging as a new synthetic tool for innovative organic transformations. Oxidant-free Au-catalyzed reactions are emerging as a new synthetic tool for innovative organic transformations. Still, a deeper mechanistic understanding is needed for a rational design of these processes. Here we describe the synthesis of two Au(i) complexes bearing bidentated hemilabile MIC^N ligands, [Au^I(MIC^N)Cl], and their ability to stabilize square-planar Au(iii) species (MIC = mesoionic carbene). The presence of the hemilabile N-ligand contributed to stabilize the ensuing Au(iii) species acting as a five-membered ring chelate upon its coordination to the metal center. The Au(iii) complexes can be obtained either by using external oxidants or, alternatively, by means of feasible oxidative addition with strained biphenylene C_sp²–C_sp² bonds as well as with aryl iodides. Based on the fundamental knowledge gained on the redox properties on these Au(i)/Au(iii) systems, we successfully develop a novel Au(i)-catalytic procedure for the synthesis of γ-substituted γ-butyrolactones through the arylation-lactonization reaction of the corresponding γ-alkenoic acid. The oxidative addition of the aryl iodide, which in turn is allowed by the hemilabile nature of the MIC^N ligand, is an essential step for this transformation.

A novel hemilabile MIC^N ligand-based Au(i)-catalytic procedure for the synthesis of γ-substituted γ-butyrolactones through the arylation-lactonization reaction of the corresponding γ-alkenoic acid is presented.     

Ruthenaelectro-catalyzed C–H acyloxylation for late-stage tyrosine and oligopeptide diversification

Ruthenaelectro(ii/iv)-catalyzed intermolecular C–H acyloxylations of phenols have been developed by guidance of experimental, CV and computational insights. The use of electricity bypassed the need for stoichiometric chemical oxidants. The sustainable electrocatalysis strategy was characterized by ample scope, and its unique robustness enabled the late-stage C–H diversification of tyrosine-derived peptides.

Ruthenaelectro(ii/iv)-catalyzed intermolecular C–H acyloxylations of oligopeptides have been developed by the guidance of key experimental, CV and computational insights.     

Kinetic trapping of a cobalt(ii) metallocage using a carbazole-containing expanded carbaporphyrinoid ligand

The meso-unsubstituted expanded porphyrinoid 3, incorporating two carbazole moieties, acts as an effective ligand for Co(ii) and permits the isolation and X-ray diffraction-based characterization of a 6 : 3 metal-to-ligand metallocage complex that converts spontaneously to the constituent 2 : 1 metal-to-ligand metalloring species in chloroform solution. The discrete metalloring is formed directly when the Co(ii) complex is crystallized from supersaturated solutions, whereas crystallization from more dilute solutions favors the metallocage. Studies with two other test cations, Pd(ii) and Zn(ii), revealed exclusive formation of the monomeric metalloring complexes with no evidence of higher order species being formed. Structural, electrochemical and UV-vis-NIR absorption spectral studies provide support for the conclusion that the Pd(ii) complex is less distorted and more effectively conjugated than its Co(ii) and Zn(ii) congeners, an inference further supported by TD-DFT calculations. The findings reported here underscore how expanded porphyrins can support coordination modes, including bimetallic complexes and self-assembled cage structures, that are not necessarily easy to access using more traditional ligand systems.

Carbazole containing expanded carbaporphyrinoid ligand supports the formation of 2 : 1 metal-to-ligand complexes with Pd, Co, and Zn. Solid-state studies also revealed formation of a 6 : 3 metal-to-ligand metallocage in the case of Co complexation.     

Encapsulation of Pt(iv) prodrugs within a Pt(ii) cage for drug delivery

This report presents a novel strategy that facilitates delivery of multiple, specific payloads of Pt(iv) prodrugs using a well-defined supramolecular system. This delivery system comprises a hexanuclear Pt(ii) cage that can host four Pt(iv) prodrug guest molecules. Relying on host–guest interactions between adamantyl units tethered to the Pt(iv) molecules and the cage, four prodrugs could be encapsulated within one cage. This host–guest complex, exhibiting a diameter of about 3 nm, has been characterized by detailed NMR spectroscopic measurements. Owing to the high positive charge, this nanostructure exhibits high cellular uptake. Upon entering cells and reacting with biological reductants such as ascorbic acid, the host–guest complex releases cisplatin, which leads to cell cycle arrest and apoptosis. The fully assembled complex displays cytotoxicity comparable to that of cisplatin against a panel of human cancer cell lines, whereas the cage or the Pt(iv) guest alone exhibit lower cytotoxicity. These findings indicate the potential of utilising well-defined supramolecular constructs for the delivery of prodrug molecules.     

Albumin-targeting of an oxaliplatin-releasing platinum(iv) prodrug results in pronounced anticancer activity due to endocytotic drug uptake in vivo

Oxaliplatin is a very potent platinum(ii) drug which is frequently used in poly-chemotherapy schemes against advanced colorectal cancer. However, its benefit is limited by severe adverse effects as well as resistance development. Based on their higher tolerability, platinum(iv) prodrugs came into focus of interest. However, comparable to their platinum(ii) counterparts they lack tumor specificity and are frequently prematurely activated in the blood circulation. With the aim to exploit the enhanced albumin consumption and accumulation in the malignant tissue, we have recently developed a new albumin-targeted prodrug, which supposed to release oxaliplatin in a highly tumor-specific manner. In more detail, we designed a platinum(iv) complex containing two maleimide moieties in the axial position (KP2156), which allows selective binding to the cysteine 34. In the present study, diverse cell biological and analytical tools such as laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS), isotope labeling, and nano-scale secondary ion mass spectrometry (NanoSIMS) were employed to better understand the in vivo distribution and activation process of KP2156 (in comparison to free oxaliplatin and a non-albumin-binding succinimide analogue). KP2156 forms very stable albumin adducts in the bloodstream resulting in a superior pharmacological profile, such as distinctly prolonged terminal excretion half-life and enhanced effective platinum dose (measured by ICP-MS). The albumin-bound drug is accumulating in the malignant tissue, where it enters the cancer cells via clathrin- and caveolin-dependent endocytosis, and is activated by reduction to release oxaliplatin. This results in profound, long-lasting anticancer activity of KP2156 against CT26 colon cancer tumors in vivo based on cell cycle arrest and apoptotic cell death. Summarizing, albumin-binding of platinum(iv) complexes potently enhances the efficacy of oxaliplatin therapy and should be further developed towards clinical phase I trials.

Albumin-targeting of a maleimide-containing oxaliplatin-releasing platinum(iv) prodrug results in tumor-specific drug delivery and activity as shown by LA-ICP-MS, isotope-labeling and NanoSIMS in cell culture and in vivo.     

Photoredox catalysis via consecutive 2LMCT- and 3MLCT-excitation of an Fe(iii/ii)–N-heterocyclic carbene complex

Fe–N-heterocyclic carbene (NHC) complexes attract increasing attention as photosensitisers and photoredox catalysts. Such applications generally rely on sufficiently long excited state lifetimes and efficient bimolecular quenching, which leads to there being few examples of successful usage of Fe–NHC complexes to date. Here, we have employed [Fe(iii)(btz)₃]³⁺ (btz = (3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene))) in the addition of alkyl halides to alkenes and alkynes via visible light-mediated atom transfer radical addition (ATRA). Unlike other Fe–NHC complexes, [Fe(iii/ii)(btz)₃]^3+/2+ benefits from sizable charge transfer excited state lifetimes ≥0.1 ns in both oxidation states, and the Fe(iii) ²LMCT and Fe(ii) ³MLCT states are strong oxidants and reductants, respectively. The combined reactivity of both excited states enables efficient one-electron reduction of the alkyl halide substrate under green light irradiation. The two-photon mechanism proceeds via reductive quenching of the Fe(iii) ²LMCT state by a sacrificial electron donor and subsequent excitation of the Fe(ii) product to its highly reducing ³MLCT state. This route is shown to be more efficient than the alternative, where oxidative quenching of the less reducing Fe(iii) ²LMCT state by the alkyl halide drives the reaction, in the absence of a sacrificial electron donor.

An iron complex with N-heterocyclic carbene ligands engages in efficient photoredox catalysis via excited state electron transfer reactions of its Fe(ii) and Fe(iii) oxidation states.     

Induction of targeted necrosis with HER2-targeted platinum(iv) anticancer prodrugs

It is well-recognized that the failure of many chemotherapeutics arises due to an inability to induce apoptosis. Most cancers acquire a myriad of pro-survival adaptations, and the vast heterogeneity and accumulation of multiple often unrelated anti-apoptotic signaling pathways have been a major stumbling block towards the development of conventional chemotherapeutics, which can overcome drug resistance. We have developed highly potent and selective HER2-targeted Pt(iv) prodrugs bearing anti-HER2/neu peptides that induce targeted necrosis as a novel strategy to circumvent apoptosis-resistance. These Pt(iv)–peptide conjugates exhibit a unique biphasic mode of cytotoxicity comprising rapid killing of cancer cells via necrosis in the first phase followed by an extended and gradual phase of delayed cell death. We demonstrate that these Pt(iv)–peptide prodrugs are more potent than their Pt(ii) congeners in direct cell-killing and exhibit comparable long-term inhibition of proliferative capacity and with greater selectivity against HER2-positive cancer cells.     

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.     

Diastereoselective and enantioselective photoredox pinacol coupling promoted by titanium complexes with a red-absorbing organic dye

The pinacol coupling reaction, a reductive coupling of carbonyl compounds that proceeds through the formation of ketyl radicals in the presence of an electron donor, affords the corresponding 1,2-diols in one single step. The photoredox version of this transformation has been accomplished using different organic dyes or photoactive metal complexes in the presence of sacrificial donors such as tertiary amines or Hantzsch''s ester. Normally, the homo-coupling of such reactive ketyl radicals is neither diastereo- nor enantio-selective. Herein, we report a highly diastereoselective pinacol coupling reaction of aromatic aldehydes promoted by 5 mol% of the non-toxic, inexpensive and available Cp₂TiCl₂ complex. The key feature that allows the complete control of diastereoselectivity is the employment of a red-absorbing organic dye in the presence of a redox-active titanium complex. Taking advantage of the well-tailored photoredox potential of this organic dye, the selective reduction of Ti(iv) to Ti(iii) is achieved. These conditions enable the formation of the d,l (syn) diastereoisomer as the favored product of the pinacol coupling (d.r. > 20 : 1 in most of the cases). Moreover, employing a simply prepared chiral SalenTi complex, the new photoredox reaction gave a complete diastereoselection for the d,l diastereoisomer, and high enantiocontrol (up to 92% of enantiomeric excess).

A metallaphotoredox, diastereoselective and enantioselective pinacol coupling reaction promoted by titanium complexes with the use of a red-absorbing organic dye was developed.     

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.     

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.     

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.     

Mixed lead–tin perovskite films with >7 μs charge carrier lifetimes realized by maltol post-treatment

Mixed lead–tin (Pb–Sn) halide perovskites with optimum band gaps near 1.3 eV are promising candidates for next-generation solar cells. However, the performance of solar cells fabricated with Pb–Sn perovskites is restricted by the facile oxidation of Sn(ii) to Sn(iv), which induces self-doping. Maltol, a naturally occurring flavor enhancer and strong metal binding agent, was found to effectively suppress Sn(iv) formation and passivate defects in mixed Pb–Sn perovskite films. When used in combination with Sn(iv) scavenging, the maltol surface treatment led to high-quality perovskite films which showed enhanced photoluminescence intensities and charge carrier lifetimes in excess of 7 μs. The scavenging and surface treatments resulted in highly reproducible solar cell devices, with photoconversion efficiencies of up to 21.4% under AM1.5G illumination.

Maltol, a metal binding agent, effectively passivates defects on the surface of mixed lead–tin perovskite films. The carrier lifetimes of the resultant perovskite films are over 7 μs. The solar cell devices exhibit efficiencies of up to 21.4%.     

Carbazolylgold(iii) complexes with thermally activated delayed fluorescence switched on by ligand manipulation as high efficiency organic light-emitting devices with small efficiency roll-offs

A series of carbazolyl ligands has been designed and synthesized through the integration of various electron-donating and electron-accepting motifs, including electron-donating 4-(diphenylamino)aryl and electron-accepting cyano and diphenylphosphine oxide moieties, for the development of a new class of gold(iii) complexes, where the energies of their triplet intraligand and ligand-to-ligand charge transfer excited states can be manipulated for the activation of thermally activated delayed fluorescence (TADF). Upon excitation, these complexes show high photoluminescence quantum yields of up to 80% in solid-state thin films, with short excited state lifetimes down to 1 μs. Vacuum-deposited and solution-processed organic light-emitting devices based on these complexes demonstrate promising electroluminescence (EL) performance with maximum external quantum efficiencies of 15.0% and 11.7%, respectively, and notably small efficiency roll-off values of less than 1% at the practical luminance brightness level of 1000 cd m⁻². These distinct EL performances are believed to be due to the occurrence of multichannel radiative decay pathways via both phosphorescence and TADF that significantly shorten the emission lifetimes and hence reduce the occurrence of the detrimental triplet–triplet annihilation in the gold(iii) complexes.

Switch on of TADF can be achieved by tuning the excited state energy levels via ligand manipulation of the carbazolylgold(iii) C^C^N complexes. The resulting OLEDs show maximum EQEs of over 11% and efficiency roll-offs of down to less than 1%.     

Luminescent monomeric and dimeric Ru(ii) acyclic carbene complexes as selective sensors for NH3/amine vapor and humidity

A new class of luminescent bis(bipyridyl) Ru(ii) pyridyl acyclic carbene complexes with environmentally-sensitive dimerization equilibrium have been developed. Owing to the involvement of the orbitals of the diaminocarbene ligand in the emissive excited state, the phosphorescence properties of these complexes are strongly affected by H-bonding interactions with various H-bonding donor/acceptor molecules. With the remarkable differences in the emission properties of the monomer, dimer, and H-bonded amine adducts together with the change of the dimerization equilibrium, these complexes can be used as luminescent gas sensors for humidity, ammonia, and amine vapors. With the responses to amines and humidity and the corresponding change in the luminescence properties, a proof-of-principle for binary optical data storage with a reversible concealment process has been described.

A new class of selective ammonia/amine vapor and humidity sensors have been developed from the luminescent bis(bipyridyl) Ru(ii) pyridyl acyclic carbene complexes with environmentally-sensitive dimerization equilibrium.