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Three multi-dentate coordinated chelates L

Weak light absorption of common Ir(III) complexes (e. g., using phenylpyridine as the ligand) has hindered their applications in photocatalytic hydrogen generation from water as an efficient photosensitizer. To address this issue, a series of cyclometalated Ir(III) complexes (Ir1-Ir5), featuring different electron-donating substituents to enhance the absorptivity, have been synthesized and studied as photosensitizers (PSs) for light-driven hydrogen production from water. Ir6-Ir7 were prepared as fundamental systems for comparisons. Electron donors, including 9-phenylcarbazole, triphenylamine, 4,4'-dimethoxytriphenylamine, 4,4'-di(N-hexylcarbazole)triphenylamine moieties were introduced on 6-(thiophen-2-yl)phenanthridine-based cyclometalating (C^N) ligands to explore the donor effect on the hydrogen evolution performance of these cationic Ir(III) complexes. Remarkably, Ir4 with 4,4'-dimethoxytriphenylamine achieved the highest turn-over number (TON) of 12 300 and initial turnover frequency (TOF

It is one of the most difficult and challenging targets to achieve blue phosphorescent organic light-emitting diodes. Herein, we employ tetrafluorinated 2-phenylpyridine (F4ppy) as a cyclometalated ligand, in which the tetrafluorophenyl group contributes to the stabilization of the highest occupied molecular orbital (HOMO) of its iridium(III) complex. Meanwhile, N-heterocyclic carbene (NHC) and acidic pyrazolyl-pyridine (fppz) moieties as ancillary ligands are used to keep the lowest unoccupied molecular orbitals (LUMOs) of the phosphors relatively unchanged. Therefore, the energy gap between the HOMO and LUMO is enlarged and two sky blue emissive iridium(III) phosphors, named (F4ppy)2Ir(CF3-pei) (Ir-1) and (F4ppy)2Ir(fppz) (Ir-2), are achieved. Strong phosphorescent emission at a wavelength of around 460 nm with a photoluminescence quantum yield of around 60% is observed in solution for these two phosphors. Moreover, the organic light-emitting devices made from Ir-1 and Ir-2 exhibit high-efficiencies, affording peak current efficiencies (CEs) of 47.6 and 45.5 cd A−1 with external quantum efficiencies (EQEs) of 20.6% and 19.6%, respectively.

Pseudocapacitance boosts the capacitance of supercapacitors by introducing additional redox sites with fast faradaic reactions. Here, we demonstrate the preparation of pseudocapacitive electrodes by inkjet printing bis-terpyridyl based molecular cobalt complexes as pseudocapacitive additives on laser induced graphene films. The substrate temperature during inkjet printing can effectively tune the morphology of the pseudocapacitive additives by overcoming the influence of coffee ring effect. Under optimum conditions, the capacitance of the pseudocapacitive electrodes was enhanced for 75 times over pristine graphene films. This approach can also be employed for the deposition of other functional materials via inkjet printing.

Phase-separated block copolymers (BCPs) that function as precursors to arrays of FePt nanoparticles (NPs) are of potential interest for the creation of media for the next-generation high-density magnetic data storage devices. A series of bimetallic BCPs has been synthesized by incorporating a complex containing Fe and Pt centers into the coordinating block of four different poly(styrene-b-4-vinylpyridine)s (PS-b-P4VPs, P1-P4). To facilitate phase separation for the resulting metalated BCPs (PM1-PM4), a loading of the FePt-bimetallic complex corresponding to ca. 20% was used. The bulk and thin-film self-assembly of these BCPs was studied by transmission electron microscopy (TEM) and atomic force microscopy, respectively. The spherical and cylindrical morphologies observed for the metalated BCPs corresponded to those observed for the metal-free BCPs. The products from the pyrolysis of the BCPs in bulk were also characterized by TEM, powder X-ray diffraction, and energy-dispersive X-ray spectroscopy, which indicated that the FePt NPs formed exist in an fct phase with average particle sizes of ca. 4-8 nm within a carbonaceous matrix. A comparison of the pyrolysis behavior of the metalated BCP (PM3), the metalated P4VP homopolymer (PM5), and the molecular model organometallic complex revealed the importance of using a nanostructured BCP approach for the synthesis of ferromagnetic FePt NPs with a smaller average NP size and a close to 1:1 Fe/Pt stoichiometric ratio.

Organic luminogens with aggregation-induced emission (AIE) characteristics have recently attracted great research interest due to their excellent luminescence behavior in the aggregate state. Cyanostilbene is a well-known AIE-active moiety due to its unique luminescence mechanism and widespread use in the design of optical materials. In this work, we report two symmetrical imidazole-containing cyanostilbene derivatives with AIE activity, abbreviated as TPIA and PPIA, whose chemical structures only differ by a C–C bond. Both molecules are thermally stable and fabricated as electroluminescent (EL) devices. On one hand, the study of their photophysical properties confirms that the restricted intramolecular rotation (RIR) effect is still the dominant factor for the AIE effect in these two cyanostilbene-based molecules. On the other hand, the EL results reveal that a more conjugated molecular structure is beneficial for the EL properties. Moreover, the optimization of the device configuration with an electron-blocking layer significantly improves the EL performance. The orange-emissive PPIA-based device shows a high external quantum efficiency of 1.02% with a small efficiency roll-off.

Two bottom-up Co(II) complex nanosheets Co-S1 and Co-S2 were prepared by coordination of trifunctional terpyridine-based triphenylamine derivatives (L1 and L2) and a cobalt(II) ion, in order to demonstrate the structural flexibility and functional tunability of these nanosheets over the top-down type. A liquid–liquid interface-assisted synthesis was employed, which is a facile method to generate multi-layer nanosheets. The nanosheets formed were characterized, revealing the proposed sheet morphology and uniform composition. They have large size domains and good mechanical strength. Besides, both Co-S1 and Co-S2 show reversible electrochromism. The color of Co-S1 was switched from red to green while that of Co-S2 was changed from light red to orange when a positive voltage was applied. An electrochromic device was also fabricated with Co-S1, indicating the promising application of these kinds of structurally tunable, easy-processable and stable nanosheets as low-cost and solid-state electrochromic materials.

Three greenish-blue iridium (III) phosphorescent complexes with the molecular structure of [Ir(pppy)2(PPh3)L] (Hpppy = 2-(4-phenoxyphenyl)pyridine; L = Cl−, NCS−, NCO−) were synthesized and characterized. Their photoluminescence spectra are significantly blue-shifted after introducing the strong-field ancillary ligand triphenylphosphine. These compounds exhibit emission peaks in the range of 474–479 nm in solutions at 298 K with quantum yields up to 0.33. The organic light-emitting diodes (OLEDs) were fabricated by thermal evaporation with complex 3. The best OLED D3 was obtained with turn-on voltage of 4.3 V, maximum luminance of 11931 cd m−2 under 15.7 V, highest luminance efficiency (ηL) as 16.6 cd A−1, power efficiency (ηP) as 12.2 lm W−1 and external quantum efficiency (EQE) as 5.6%.

A terpyridine-substituted cyanostilbene derivative ( Z )-2-(4 ¢ -([2,2 ¢ :6 ¢ ,2 ² -terpyridin]-4 ¢ -yl)-[1,1 ¢ -biphenyl]-4-yl)-3-phenylacrylonitrile ( CNSTPy ) was synthesized and characterized. The compound exhibits remarkable aggregation-induced emission phenomenon and its single crystal shows a blue emission with fluorescent efficiency as high as 45%. Based on its aggregation state behavior, multiple applications towards exploring its lasing, fluorescence switching and electroluminescence properties were realized. Amplified spontaneous emission (ASE) was observed from the crystal and verified by the variable pump strip method, with a threshold value of ~1.5 mJ cm−2. The protonation/deprotonation processes accompanied by the formation of different molecular aggregation structure result in the distinct blue and yellow emissions. Additionally, the molecule also shows a moderate electroluminescence performance.

A great deal of research effort has been put in green energy applications in the past few decades based on organic optoelectronics. Compared with conventional inorganic semiconductors, organic counterparts offer a much simpler strategy for low-cost mass production and structural modification. Hence, continuous and intensive academic and industrial research works have been done in these areas. In terms of the materials used, transition-metal complexes with the unique features of the transition metal centers represent a large group of candidates, showing high performance in energy conversion technologies. However, the commonly used transition metals, like Pt(II), Ir(III) and Ru(II), are expensive and of relatively low abundance. Concerning elemental sustainability and marketability, some abundant and cheaper metals should be investigated and further developed to replace these precious metals. Cu(I) complexes have shown their potentiality in solar energy harvesting and light emitting applications, due to their well-studied photophysics and structural diversity. In addition, copper is one of the earth-abundant metals with less toxicity, which makes it competitive to precious transition metals. As a result, a series of rational molecular engineering has been developed to boost the device performance of copper complexes. In this review, the recent progress of copper complexes in the fields of organic light emitting devices (OLEDs), photovoltaic cells (dye-sensitized solar cells (DSSCs) and bulk heterojunction solar cells (BHJSCs)) in the past two decades will be presented. Representative examples are chosen for discussion.

Energy remains one of the great challenges for the world. There is a considerable interest in developing renewable energy resources and improving the technologies for energy conversion. In this context, solar energy is a source with the proven capacity to meet the increasing global energy needs. In recent years, efficient organic solar cells (OSCs) have been fabricated using organic polymers and small molecules. Metalated conjugated organic molecules have also been shown to be good alternatives to the all-organic congeners and have demonstrated good promise as solar cell materials in OSCs and dye-sensitized solar cells (DSSCs). Among these, soluble molecular/polymeric metallaynes and their acetylide-functionalized metalloporphyrins show promising results in much of these investigations with the best power conversion efficiencies of 9.06% (for single-layer OSC), 12.5% (for tandem OSC) and 13.2% (for co-sensitized DSSC) to date. This review summarizes the recent advances of this field. Various factors influencing the device performance such as the nature of metal center and organic spacer, absorption coefficient, bandgap energy, charge carrier mobility, accessibility of triplet excitons and blend film morphology of these materials will be discussed. Given the diversity of transition metals available (for example, Pt, Zn, Ru) and structural versatility of the organic components, it is anticipated that this nascent field using metalated organic materials would continue to lead to exciting prospects in the near future.

Patterning of L10 FePt nanoparticles (NPs) with high coercivity offers a promising route to develop bit-patterned media (BPM) for the next generation magnetic data recording system, but the synthesis of monodisperse FePt NPs and mass production of their nanopatterns has been a long-standing challenge. Here, highly efficient nanoimprint lithography was applied for large-scale universal patterning, which was achieved by imprinting the solution of a single-source bimetallic precursor. The rigid coplanar metallic cores and the surrounding flexible tails in the bimetallic complex permit the spontaneous molecular arrangements to form the highly ordered negative morphology replicated from the soft template. In-situ pyrolysis study was then investigated by one-pot pyrolysis of the precursor under an Ar/H2 atmosphere, and the resultant NPs were fully characterized to identify the phase, morphology and magnetic properties. Finally, highly-ordered patterns on certain substrates were preserved perfectly after pyrolysis and could be potentially utilized in magnetic data recording media.

Three molecular photosensitizers (PSs) with carboxylic acid anchors for attachment to platinized titanium dioxide nanoparticles were studied for light-driven hydrogen production from a fully aqueous medium with ascorbic acid (AA) as the sacrificial electron donor. Two zinc(II) porphyrin (ZnP)-based PSs were used to examine the effect of panchromatic sensitization on the photocatalytic H2 generation. A dyad molecular design was used to construct a difluoro boron-dipyrromethene (bodipy)-conjugated ZnP PS (ZnP-dyad), whereas the other one featured an electron-donating diarylamino moiety (YD2-o-C8). To probe the use of the ZnP scaffold in this particular energy conversion process, an organic PS without the ZnP moiety (Bodipy-dye) was also synthesized for comparison. Ultrafast transient absorption spectroscopy was adopted to map out the energy transfer processes occurring in the dyad and to establish the bodipy-based antenna effect. In particular, the systems with YD2-o-C8 and ZnP-dyad achieved a remarkable initial activity for the production of H2 with an initial turnover frequency (TOFi ) higher than 300 h-1 under white light irradiation. The use of ZnP PSs in dye-sensitized photocatalysis for the H2 evolution reaction in this study indicated the importance of the panchromatic sensitization capability for the development of light absorbing PSs.

Correction for ‘Electrochromic triphenylamine-based cobalt(ii) complex nanosheets’ by Yurong Liu et al., J. Mater. Chem. C, 2019, 7, 9159–9166, DOI: 10.1039/C9TC02257K.

A series of non-conjugated ferrocene-containing copolymers FcCP1–FcCP3 with a triphenylamine (TPA), benzothiazole (BT) or phenothiazine (PHZ) unit has been designed and synthesized via a facile radical polymerization protocol. The structural, photophysical, electrochemical and memory characteristics of these polymers were systematically studied. All the copolymers exhibited flash memory behaviour with a bistable conductive process, where FcCP1 showed a large ON/OFF current ratio of 103 to 104 with a low threshold voltage of −0.6 V. Such remarkable results suggest that non-conjugated ferrocene-containing copolymers are promising active materials for memory applications.

In this study, we report the synthesis and characterization of a new bis(pyridyl)-coordinated platinum(II)-containing metallopolyyne polymer. It is found that this metallopolymer can act as a precursor towards the synthesis of Pt nanoparticles upon pyrolysis (600 °C, 5 h). The resultant nanoparticles were characterized by transmission electron microscope (TEM), energy-dispersive X-ray analysis (EDXA) and powder X-ray diffraction (PXRD). The results verify that monodisperse Pt nanoparticles with defined morphology can be obtained. This pilot study reveals the potential of fabricating patterned Pt nanoparticles by using various lithographic methods in the future.

The accurate regulation of the size of the ferromagnetic nanoparticle synthesized from the one-pot pyrolysis of metallopolymer is a challenging topic to date. A bimetallic complex TPy-FePd-1 was prepared and used as a single-source precursor to synthesize ferromagnetic FePd nanoparticles (NPs) by one-pot pyrolysis. The resultant FePd NPs have a mean particle size of 19.8 nm and show a coercivity of 1.02 kOe. In addition, the labile ligand NCMe in TPy-FePd-1 was easily substituted by a pyridyl group. A random copolymer PS-P4VP was used to coordinate with TPy-FePd-1, and the as-synthesized metallopolymer made the metal fraction disperse evenly along the flexible chain. Investigation of FePd NPs from the bimetallic polymers with different metal fractions was also made, and the size of the resultant nanoparticles could be easily controlled by tuning the metal fraction in the polymer.

Two novel platinum(II) donor-acceptor (D-A) naphthalene diimide (NDI)-based copolymers have been designed and synthesized. The effects of thiophene numbers on the thermal, optical, electronic and charge transport properties of the polymers have been investigated. These solution processable polymers exhibit p-channel field-effect charge transport characteristics, unlike other organic NDI-based polymeric analogues. All the results indicated that they have potential applications in high-performance organic field-effect transistors (OFETs).

A new series of small-molecular ruthenium(II)-diynes trans-Ru(dppe)2(C≡CAr)2 (D1−D4) (dppe = Ph2CH2CH2Ph2; Ar = aromatic moiety) have been successfully designed, synthesized and characterized by photophysical, electrochemical and computational methods, and complexes D1 and D3 were crystallographically characterized. The optical and time-dependent density functional theory studies showed that the absorption ability of these complexes was significantly enhanced by incorporating the stronger electron-donor groups. The effect of different electron-donor groups in these metallo-organic complexes on the optoelectronic and photovoltaic properties was also examined. In this work, benzothiadiazole as the electron acceptor and triphenylamine and/or thiophene as the electron donor were introduced in these complexes, which were found to have optimal energy bandgaps spanning from 1.70 to 1.83 eV and broad absorption bands within 300–700 nm, rendering them good electron donor materials to blend with [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM) in the fabrication of the solution-processed bulk heterojunction (BHJ) solar cells. The best power conversion efficiency (PCE) of 0.66% was achieved, which is the highest PCE in ruthenium(II)-containing BHJ solar cells to date.

A new series of bimetallic Cu(I) complexes 1–5 triply bridged by a monoanionic or charge-neutral functionalized 3-(2′-pyridyl)-1,2,4-triazole in a μ–η1(N),η2(N,N) tridentate binding mode and two bis(diphenylphosphino)methane (dppm) ligands have been synthesized. Complexes 1–5 are singly or doubly charged dinuclear Cu(I) species with an eight-membered Cu2C2P4 ring of {Cu(μ-dppm)2Cu} unit, in which 3 and 4 adopt the boat–boat conformation, while 1, 2, and 5 display the chair–boat form. In these dimeric copper(I) complex cations, one of the two Cu(I) ions is four-coordinated, in a highly distorted N2P2 tetrahedral environment and the other is three-coordinated, in a distorted NP2 trigonal planar arrangement. All these Cu(I) complexes exhibit a comparatively weak low-energy absorption in CH2Cl2 solution, ascribed to the charge-transfer transitions with appreciable 1MLCT contribution, as suggested by time-dependent density functional theory (TDDFT) analyses. Complexes 1–5 display good emission properties in bo...

A tetraphenylethene-containing dipyrrin (TPEpy) has been synthesized and its photophysical properties and metal detecting properties have been investigated. TPEpy displays a high selectivity and sensitivity with a detection limit of 8.96 × 10−8 M for Zn2+ in aqueous media.

Keratin 1 (KRT1) is overexpressed in squamous carcinomas and associated with aggressive pathologies in breast cancer. Herein we report the design and preparation of the first Trp-based red fluorogenic amino acid, which is synthetically accessible in a few steps and displays excellent photophysical properties, and its application in a minimally-disruptive labelling strategy to prepare a new fluorogenic cyclopeptide for imaging of KRT1+ cells in whole intact tumour tissues., Trp(redBODIPY) is the first red-emitting Trp-based amino acid for the preparation of fluorogenic peptides with retention of target binding affinity.

White organic light-emitting diodes (WOLEDs) are superior to traditional incandescent light bulbs and compact fluorescent lamps in terms of their merits in ensuring pure white-light emission, low-energy consumption, large-area thin-film fabrication, etc. Unfortunately, WOLEDs based on multilayered or multicomponent (red, green, and blue (RGB)) emissive layers can suffer from some remarkable disadvantages, such as intricate device fabrication and voltage-dependent emission color, etc. Single molecules, which can emit white light, can be used to replace multiple emitters, leading to a simplified fabrication process, stable and reproducible WOLEDs. Recently, the performance of WOLEDs by using single molecules is catching up with that of the state-of-the-art devices fabricated by multicomponent emitters. Therefore, an increasing attention has been paid on single white-light-emitting materials for efficient WOLEDs. In this review, different mechanisms of white-light emission from a single molecule and the performance of single-molecule-based WOLEDs are collected and expounded, hoping to light up the interesting subject on single-molecule white-light-emitting materials, which have great potential as white-light emitters for illumination and lighting applications in the world.

Three metal-free molecular photosensitizers (S1–S3) featuring a starburst triarylamine donor moiety have been synthesized. They show attractive photocatalytic performance in visible light-driven H2 production from water in their platinized TiO2 composites. A remarkable H2 turnover number (TON) of 10 200 (48 h) was achieved in an S1-anchored system.

With respect to the commonly used electron-deficient pyridyl group in the benchmark dopant Ir(ppy)3, incorporating the electron-rich thiazolyl group with different chromophores have not been extensively studied. In this paper, some iridium(III) complexes bearing functional ligands with the thiazolyl moiety were synthesized and characterized by 1H and 13C NMR, UV–Vis absorption and photoluminescence spectroscopy. The emission color of these thiazole-based Ir(III) complexes can be tuned from yellow to red and the best phosphorescent organic light-emitting device exhibited the maximum external quantum efficiency of 11.1%, current efficiency of 35.8 cd/A and power efficiency of 21.9 lm/W.

L10-ordered FePt nanoparticles (NPs) with ultra-high coercivity were directly prepared from a new metallopolyyne using a one-step pyrolysis method. The chemical ordering, morphology and magnetic properties of the as-synthesized FePt NPs have been studied. Magnetic measurements show the coercivity of these FePt NPs is as high as 3.6 T. Comparison of NPs synthesized under the Ar and Ar/H2 atmospheres shows that the presence of H2 in the annealing environment influences the nucleation and promotes the growth of L10-FePt NPs. Application of this metallopolymer for bit-patterned media was also demonstrated using nanoimprint lithography.

A new building block ATVTA that uses stiff carbon-carbon triple bonds (A) on 1,2-di(2-thienyl)-ethene (TVT) has been developed. Oligothiophene derivatives S-01 with a TVT unit, S-02 with a 5,5'-diethynyl-2,2'-dithienyl (AT2) unit and S-03 with ATVTA were synthesized to compare their effects in a systematic study. Due to the better π-conjugation extension of the TVT unit, S-01 exhibits the most red-shifted absorption profile among them, whereas S-02 possesses the deepest HOMO level. While the HOMO level of S-03 is down-shifted by 0.02 eV relative to that of S-01, the alkyne linkages can effectively down-shift the HOMO level. By replacing the terminal units of S-03 with stronger electron acceptors, S-04 and S-05 exhibited broader absorption profiles and lower HOMO levels than those of S-03. Organic solar cells based on these molecules were fabricated and an S-03:PC60 BM (1:1, w/w) based device afforded the highest Voc value of 0.96 V and a power conversion efficiency (PCE) of 2.19 %.

Increasing energy demands and environmental concerns about global warming have led to a greater focus on the development of renewable energy sources. Dye-sensitized solar cells (DSSCs) have attracted considerable attention in recent years as they offer the possibility of low-cost conversion of photovoltaic energy. In particular, triarylamine functionalized organic photosensitizers show high molar absorption coefficients in the visible spectral region, good dye aggregation resistance and reliable electrochemical and thermal stabilities. This review emphasizes the recent developments and strategies employed in the structural design of arylamine-based metallated and metal-free organic photosensitizers. The influences of molecular structural engineering on photophysical and electrochemical properties along with photovoltaic parameters and the efficiency of DSSCs are presented. Hence, by drawing a correlation among the structures of arylamine-derived photosensitizers, their properties and photovoltaic parameters of DSSCs, it will be useful in optimizing new dyes for the generation of efficient photovoltaic cells for energy production.

Two new iridium(III) cyclometalates (A and B) based on 2-[5-(9,9′-diethyl-9H-fluoren-7-yl)thienyl]-pyridine were synthesized, characterized and applied in bulk-heterojunction solar cells (BHJSCs). Their absorption, electrochemical, thermal and photovoltaic properties have been investigated. The results reveal that the replacement of phenyl ring by thienyl one can extend the absorption wavelength up to 530 nm, thus narrowing the energy gap (Eg) to 2.93 eV and 2.81 eV for A and B, respectively. These complexes exhibit excellent thermal stability with the onset decomposition temperature at 5% weight-loss (Td) of over 370 °C. The BHJSC device with A as donor blended with [6,6]-phenyl C61-butyric acid methyl ester (PCBM) gave the best power conversion efficiency (η) of 0.51%, with a short-circuit photocurrent density (Jsc) of 2.68 mA cm−2, an open-circuit photovoltage (Voc) of 0.66 V and a fill factor (ff) of 0.28 under illumination of an AM 1.5 solar cell simulator.

Six new solution processable platinum(II) acetylide donor-acceptor (D-A) triads end-capped by 4,7-di-2-thienyl-2,1,3-benzothiadiazole (DTBT) have been synthesized and characterized by photophysical and electrochemical methods. All these materials possess low bandgaps and strong UV/Vis absorption between 400 and 700 nm. Bulk heterojunction (BHJ) solar cells based on these molecules as donor materials were fabricated. The best power conversion efficiency (PCE) of 1.46% with the open-circuit voltage (Voc) of 0.70 V, short-circuit current density (Jsc) of 6.17 mA cm−2 and fill factor (FF) of 0.33 was achieved under illumination of an AM 1.5 solar cell simulator. These results suggest the potential use of solution-processable small molecular platinum(II)-acetylides for efficient generation in organic photovoltaic implementation.

Two bis(acetylide)-functionalized platinum(II) polymers containing ferrocenyl pendant ligands, trans-[{-Pt(PBun3)2-C≡CRC≡C-}n P1 (R = 9-ferrocenylmethylene-2,7-diethynylfluorene) and P2 (R = ferrocenylmethylene-2,5-diethynylbenzene), were prepared in good yields and were characterized by NMR spectroscopy and GPC. Electrochemical characteristics with copolymers P1 and P2 as the cathode active materials for rechargeable lithium batteries showed chemical and electrochemical reversibility. The thin layer polymer electrodes of P1 and P2 exhibited reversible redox peaks at the potentials of 0.54 and 0.64 V (vs. Ag/AgCl), respectively. The P1 or P2/carbon composites are also used as cathode-active materials to enhance the conductivity and durability. The electrodes exhibited good cycle life of over 50 charging/discharging cycles and no reversible n-type redox abilities seemed to be available.

In the last decade, the number of applications of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in bioimaging has been increasing. To further extend its capability in drug development, in this study, we used this bioimaging tool to visualize deposition behavior of chemically different metallo-complexes, including two that differed only subtly in structure. A systematic approach with in vitro study and ICP-MS elemental analysis were included to supplement the findings. Two chemically distinct platinum complexes (Pt-1 and Pt-2) were synthesized; their potencies were investigated first on different healthy and cancer cell lines and then on mice. The commercialized anti-cancer drug, cis-platin was used as a reference. In animal studies, the mice were given 4 mg/kg of the complex via intraperitoneal injection and sacrificed 24 h post-injection. ICP-MS analysis was performed on six organs to study the bioavailability of the complexes. Pt accumulated in the organs, from greatest to least, from liver > kidney > lung > testis > heart > brain. Among the complexes, the bioavailability showed a general trend of Pt–2 > cis-platin > Pt-1. In LA-ICP-MS bioimaging analysis of paraffin-embedded mouse liver and kidney sections, a spatial resolution of 50 μm was adopted. Deposition trends matched the findings obtained in elemental analysis. In addition, differential deposition of Pt was observed in the kidney sections of mice treated with different complexes. The LA biomaps successfully distinguished the differential distribution of two structurally similar platinum complexes (Pt-1 and Pt-2) in mice liver and kidney. This information is of particular interest because these two Pt-based complexes can potentially be developed into anti-cancer drugs. This work demonstrates that LA-ICP-MS imaging is a valuable tool for therapeutic drug development, especially in assisting molecular modification of metal-containing complexes.

Six donor−π−acceptor (D–π–A) organic dyes based on thieno[3,2-b]thiophene π-linker comprising different alkyl side chains were synthesized and characterized. Their photophysical and electrochemical properties were studied and their corresponding performances as photosensitizers (PSs) in dye-sensitized solar cells (DSSCs) and photocatalytic hydrogen production systems were also investigated. A power conversion efficiency (PCE) of 5.25 % in DSSCs and a decent H2 turnover number (TON) of 5170 (48 h) in platinized TiO2 hydrogen production system were demonstrated. The results indicated that alkyl chain engineering is one of the crucial steps in designing a superior photosensitizer.

Phosphorescent transition metal complexes have been intensively investigated, since these luminophores are distinctively different from fluorescent chromophores in terms of the nature and lifetime scale of photoluminescence (PL). Owing to the inherent differences in the light emission, these metal complexes have been successfully exploited for a variety of optical applications, and some of the studies revealed that phosphorescence is fundamentally important to the experimental results and target performances. Encouragingly, cyclometalated iridium(III) complex is one of the rare entities which shows great potential in various biological and analytical applications, such as luminescent assays, cellular imaging, in vivo imaging and even theranostics. This review article collects the most recent papers on health-related applications by exploiting phosphorescent cyclometalated Ir(III) complexes. At the same time, the structure–property relationships of these Ir(III) complexes will be emphasized throughout the article.

Three molecular photosensitizers (PSs) with carboxylic acid anchors for attachment to platinized titanium dioxide nanoparticles were studied for light-driven hydrogen production from a fully aqueous medium with ascorbic acid (AA) as the sacrificial electron donor. Two zinc(II) porphyrin (ZnP)-based PSs were used to examine the effect of panchromatic sensitization on the photocatalytic H

In recent years, metallopolymers have attracted much attention as precursors to generate magnetic metal/metal alloy nanoparticles (NPs) through pyrolysis or photolysis because they offer the advantages of ease of solution processability, atomic level mixing and stoichiometric control over composition. The as-generated NPs usually possess narrow size distributions with precise control of composition and density per unit area. Moreover, patterned NPs can be achieved on various substrates in this way owing to the good film-forming property of metallopolymers and such work is important for many applications based on metal nanostructures. By combining the merits of both the solution processability of metallopolymers and nanoimprint lithography (NIL), a new platform can be created for fabricating bit-patterned media (BPM) and the next-generation of nanoscale ultra-high-density magnetic data storage devices. Furthermore, most of these metallopolymers can be used directly as a negative-tone resist to generate magnetic metallic nanostructures by electron-beam lithography and UV photolithography. Self-assembly and subsequent pyrolysis of metalloblock copolymers can also afford well-patterned magnetic metal or metal alloy NPs in situ with periodicity down to dozens of nanometers. In this review, we highlight the use of metallopolymer precursors for the synthesis of magnetic metal/metal alloy NPs and their nanostructures and the related applications.

Two new organometallic copolymers (PVFVM1 and PVFVM1-1) bearing different molar ratios of ferrocene and triphenylamine pendants were successfully designed and synthesized as cathode active materials for organic-battery applications. Their structural and thermal characteristics were determined by 1H NMR spectroscopy, Fourier transform infrared (FTIR) spectroscopy, size exclusion chromatography (SEC), and thermogravimetric analysis (TGA). Cyclic voltammograms of the as-prepared polymers show that the electrochemical reactions of the ferrocene and triphenylamine moieties are reversible after the first cycle. A composite electrode based on copolymer PVFVM1 exhibits an initial specific discharge capacity of 102 mA h g–1, which corresponds to 98 % of its theoretical capacity (104 mA h g–1). The cycle endurances for both polymers have been evaluated for over 50 cycles. Our results show that both copolymers are good candidates as a new class of cathode active materials and charge-storage materials for rechargeable batteries.

Phosphorescent dinuclear iridium(III) complexes that can show high luminescent efficiencies and good electroluminescent abilities are very rare. In this paper, highly phosphorescent 2-phenylpyrimidine-based dinuclear iridium(III) complexes have been synthesized and fully characterized. Significant differences of the photophysical and electrochemical properties between the mono- and dinuclear complexes are observed. The theoretical calculation results show that the dinuclear complexes adopt a unique molecular orbital spatial distribution pattern, which plays the key role of determining their photophysical and electrochemical properties. More importantly, the solution-processed organic light-emitting diode (OLED) based on the new dinuclear iridium(III) complex achieves a peak external quantum efficiency (η(ext)) of 14.4%, which is the highest η(ext) for OLEDs using dinuclear iridium(III) complexes as emitters. Besides, the efficiencies of the OLED based on the dinuclear iridium(III) complex are much higher that those of the OLED based on the corresponding mononuclear iridium(III) complex.

A novel soft salt based phosphorescent probe has been successfully developed for ratiometric and lifetime imaging of intracellular pH variations in real time., In contrast to traditional short-lived fluorescent probes, long-lived phosphorescent probes based on transition-metal complexes can effectively eliminate unwanted background interference by using time-resolved luminescence imaging techniques, such as photoluminescence lifetime imaging microscopy. Hence, phosphorescent probes have become one of the most attractive candidates for investigating biological events in living systems. However, most of them are based on single emission intensity changes, which might be affected by a variety of intracellular environmental factors. Ratiometric measurement allows simultaneous recording of two separated wavelengths instead of measuring mere intensity changes and thus offers built-in correction for environmental effects. Herein, for the first time, a soft salt based phosphorescent probe has been developed for ratiometric and lifetime imaging of intracellular pH variations in real time. Specifically, a pH sensitive cationic complex (C1) and a pH insensitive anionic complex (A1) are directly connected through electrostatic interaction to form a soft salt based probe (S1), which exhibits a ratiometric phosphorescent response to pH with two well-resolved emission peaks separated by about 150 nm (from 475 to 625 nm). This novel probe was then successfully applied for ratiometric and lifetime imaging of intracellular pH variations. Moreover, quantitative measurements of intracellular pH fluctuations caused by oxidative stress have been performed for S1 based on the pH-dependent calibration curve.

Four new conjugated ferrocene-containing poly(fluorenylethynylene)s (PFcFE1–PFcFE4) with triphenylamine, carbazole or thiophene moieties in the main chain have been designed and synthesized via a Sonogashira coupling reaction. Their structures, molecular weights, optical features, thermal properties and memory performance were well studied. Two terminal single layer devices (ITO/polymer/Al) based on PFcFE1, PFcFE2 and PFcFE3 exhibited flash memory behaviours, while PFcFE4 shared the common characteristics of the “write-once read-many times” (WORM) memory effect. These results would provide a new series of ferrocene-containing conjugated polymers with further opportunities for memory applications.

Otomycosis is a superficial infection of the ear caused by fungi. The disease may occur in the pinna, external auditory canal and tympanic membrane of humans and animals. Aspergillus niger and Candida albicans are the most prevalent fungal species responsible for otomycosis. In our study, the potential antifungal properties of a series of Schiff bases was examined. The synthesized compounds (1–14) were investigated for their minimum inhibitory concentration, minimum fungicidal concentration and zone of clearance against Aspergillus niger and Candida albicans. Compounds 5 and 6 with alkyl chain containing 6 or 7 carbon atoms exhibited an obvious fungicidal activity with the MIC/MFC ratio of 2. Zone of clearance study also demonstrated that both compounds 5 and 6 produced noticeable clear zones against the tested fungi as compared to fluconazole. The time-kill kinetic study showed that Candida albicans colonies were reduced by more than 3 logs after 24 h exposure to compound 5 at 4 and 8 × MIC levels. Both compounds 5 and 6 at a concentration of 50 μg mL−1 exhibited satisfactory cell viability towards human skin keratinocytes. Our results suggest that these compounds may be considered as potential drug candidates for the treatment of Aspergillus niger and Candida albicans ear infections.

A series of new D–π–A organic photosensitizers 7a–7d featuring a novel starburst electron donor unit and uncommon selenophene containing π-linker were synthesized, characterized, and applied for fabrication of dye-sensitized solar cells (DSSCs). Dyes 11d–13d with thiophene or phenyl ring as the π-linker also were synthesized for comparison. The best power conversion efficiency (PCE) of 6.67% was attained for 11d with a relatively high open-circuit voltage (Voc) of 0.825 V using conventional I−/I3− redox electrolyte in DSSCs, and this value reaches about 84% of the device based on standard dye N719 (7.91%) under the same device fabrication conditions. Electrochemical impedance spectroscopy (EIS) and open-circuit voltage decay (OCVD) were applied to verify the findings. All the results suggest that starburst electron donor design strategy can be used to minimize dye aggregation on TiO2 and to slow down the charge recombination kinetics in DSSCs to improve the photovoltaic performance. Effects of using selenophene as the π-linker building block on the photovoltaic parameters also were explored and evaluated.

Ferromagnetic (L10 phase) CoPt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are promising candidates for the next generation of ultrahigh-density data storage systems. It is a challenge to generate L10 CoPt NPs with high coercivity, controllable size, and a narrow size distribution. We report here the fabrication of L10 CoPt NPs by employing a heterobimetallic CoPt-containing polymer as a single-source precursor. The average size of the resulting L10 CoPt NPs is 3.4 nm with a reasonably narrow size standard deviation of 0.58 nm. The coercivity of L10 CoPt NPs is 0.54 T which is suitable for practical application. We also fabricated the L10 CoPt NP-based nanoline and nanodot arrays through nanoimprinting the polymer blend of CoPt-containing metallopolymer and polystyrene followed by pyrolysis. The successful transfer of the pre-defined patterns of the stamps onto the surface of the polymer blend implies that this material holds great application potential as a data storage medium.

Two phosphorescent platinum(II) cyclometallated complexes with phenoxy groups (1 and 2) have been developed. The modified organic ligands derived by combining the phenoxy moiety and 2-phenylpyridine conferred them with a more flexible structure, leading to superior intermolecular interaction properties of the resulting Pt(II) metallophosphors. Because of the excimer formation induced by Pt(II) complexes 1 and 2, the emission color can be tuned over a wide range from cyan to orange by simply increasing the concentration of the Pt(II) metallophosphors. Inspired by their broad emission band, color tunability and outstanding electroluminescence (EL) performance, these two Pt(II) phosphors complemented with blue fluorescent emitter 4,4′-bis(9-ethyl-3-carbazovinylene)-1,1′-biphenyl (BCzVBi) were employed in manufacturing high color-rendering white organic light-emitting devices (WOLEDs). In such simple two-emitter systems, 1-based WOLEDs exhibited reasonable EL performance with an external quantum efficiency (ηext) of 11.7%, luminance efficiency (ηL) of 29.1 cd A−1, power efficiency (ηp) of 16.9 lm W−1 and color rendering index (CRI) of 77, whereas 2-based WOLEDs demonstrated an ηext of 10%, ηL of 21.7 cd A−1, ηp of 10.7 lm W−1 and CRI of 88.

Bit-patterned media (BPM) with a precise stoichiometry ratio of Fe and Pt atoms are promising for future high areal density magnetic recording. Here, we report a new FePt-containing metallopolymer P as the single-source precursor for the synthesis of magnetic metal alloy nanoparticles. This polymer was synthesized from a random copolymer poly(styrene-4-ethynylstyrene) PES-PS and the bimetallic precursor TPy-FePt ([Pt(4′-ferrocenyl-(N^N^N))Cl]Cl) by the CuI-catalyzed dehydrohalogenation. After pyrolysis of P, the stoichiometry of Fe and Pt atoms in the synthesized nanoparticles is nearly close to 1 : 1, which is more precise than that by using TPy-FePt as the precursor. Also, polymer P is more suitable for patterning by high-throughput nanoimprint lithography (NIL) compared to TPy-FePt. Ferromagnetic nanolines, potentially useful for fabricating bit-patterned magnetic recording media, were successfully obtained from P and fully characterized.