A Conformationally Stable π-Expanded X-Type Double Helicene Comprising Dihydropyracylene Units with Multistage Redox Behavior.

A π-expanded X-type double [5]helicene comprising dihydropyracylene moieties was synthesized from commercially available acenaphthene. X-ray crystallographic analysis revealed the unique highly twisted structure of the compound resulting in the occurrence of two enantiomers which were separated by chiral HPLC, owing to their high conformational stability. The compound shows strongly bathochromically shifted UV/vis absorption and emission bands with small Stokes shift and considerable photoluminescence quantum yield and circular polarized luminescence response. The electrochemical studies revealed five facilitated reversible redox events, including three reductions and two oxidations, thus qualifying the compound as chiral multistage redox amphoter. The experimental findings are in line with the computational studies based on density functional theory pointing towards increased spatial extension of the frontier molecular orbitals over the polycyclic framework and a considerably narrowed HOMO-LUMO gap.

Tweaking the Optoelectronic Properties of S-Doped Polycyclic Aromatic Hydrocarbons by Chemical Oxidation.

Peri-thiaxanthenothiaxanthene, an S-doped analog of peri-xanthenoxanthene, is used as a polycyclic aromatic hydrocarbon (PAH) scaffold to tune the molecular semiconductor properties by editing the oxidation state of the S-atoms. Chemical oxidation of peri-thiaxanthenothiaxanthene with H2 O2 led to the relevant sulfoxide and sulfone congeners, whereas electrooxidation gave access to sulfonium-type derivatives forming crystalline mixed valence (MV) complexes. These complexes depicted peculiar molecular and solid-state arrangements with face-to-face π-π stacking organization. Photophysical studies showed a widening of the optical bandgap upon progressive oxidation of the S-atoms, with the bis-sulfone derivative displaying the largest value (E00 =2.99 eV). While peri-thiaxanthenothiaxanthene showed reversible oxidation properties, the sulfoxide and sulfone derivatives mainly showed reductive events, corroborating their n-type properties. Electric measurements of single crystals of the MV complexes exhibited a semiconducting behavior with a remarkably high conductivity at room temperature (10-1 -10-2  S cm-1 and 10-2 -10-3  S cm-1 for the O and S derivatives, respectively), one of the highest reported so far. Finally, the electroluminescence properties of the complexes were tested in light-emitting electrochemical cells (LECs), obtaining the first S-doped mid-emitting PAH-based LECs.

Supramolecular Chalcogen-Bonded Semiconducting Nanoribbons at Work in Lighting Devices.

This work describes the design and synthesis of a π-conjugated telluro[3,2-ß][1]-tellurophene-based synthon that, embodying pyridyl and haloaryl chalcogen-bonding acceptors, self-assembles into nanoribbons through chalcogen bonds. The ribbons π-stack in a multi-layered architecture both in single crystals and thin films. Theoretical studies of the electronic states of chalcogen-bonded material showed the presence of a local charge density between Te and N atoms. OTFT-based charge transport measurements showed hole-transport properties for this material. Its integration as a p-type semiconductor in multi-layered CuI -based light-emitting electrochemical cells (LECs) led to a 10-fold increase in stability (38 h vs. 3 h) compared to single-layered devices. Finally, using the reference tellurotellurophene congener bearing a C-H group instead of the pyridyl N atom, a herringbone solid-state assembly is formed without charge transport features, resulting in LECs with poor stabilities (<1 h).

White-emitting Protein-Metal Nanocluster Phosphors for Highly Performing Biohybrid Light-Emitting Diodes.

This work presents a simple in situ synthesis and stabilization of fluorescent gold nanoclusters (AuNCs) with different sizes using engineered protein scaffolds in water. The protein-AuNC hybrids show a dual emission (450 and 700 nm) with a record photoluminescence quantum yield of 20%. These features impelled us to apply them to biohybrid light-emitting diodes as color down-converting filters or biophosphors. Efficient white emission (x/y CIE color coordinates of 0.31/0.29) and stabilities of more than 800 h were achieved. This represents a 2 orders of magnitude enhancement compared to the prior art. Besides the outstanding performance, the protein scaffold also infers a unique anisotropic emission character that is considered as a proof-of-concept of high interest for single-point lighting and display.

Polypyridyl ligands as a versatile platform for solid-state light-emitting devices.

The replacement of inorganic semiconductors with molecule-based compounds for applications in current-to-light conversion has led to a significant increase in interdisciplinary collaborations worldwide, affording new improved organic-light emitting diodes (OLEDs) ripe for commercial applications, as well as light-emitting electrochemical cells (LECs) that have recently started to head to the market. This review highlights the role that transition metal coordination complexes (TMCs) have played in advancing the field of molecular electronics, from early conception to the advanced development of several polypyridyl complexes currently pursued for both OLED and LEC concepts. In this context, the design and synthesis of Ir(iii), Pt(ii), Cu(i) and Ag(i) complexes as the emissive components of OLEDs and LECs are thoughtfully presented. We discuss how molecular design is pivotal for fine-tuning color and optimizing power efficiencies, highlighting the key roles of the metal, cyclometalate, and ancillary polypyridyl ligands. We provide insight into the strategies exploited for the development of new, improved emitters and their fabrication into OLEDs/LECs with high external quantum efficiencies and stabilities. In addition, we have surveyed the remarkable photophysical properties of third generation TMCs capable of undergoing thermally activated delayed fluorescence (TADF). Since previous reviews of TADF materials are strongly biased towards organic-based systems, this overview compliments other synopses of light emitting TADF materials. Finally, we shed light onto the conceptual challenges that still need to be overcome to advance the rational design of TMC-based TADF emitters with tunable ligands and the subsequent fabrication of OLEDs/LECs, which are tailor-made for each specific application.

Controlling Interfacial Charge Transfer and Fill Factors in CuO-based Tandem Dye-Sensitized Solar Cells.

We designed and synthesized a series of novel electron-accepting zinc(II)phthalocyanines (ZnPc) and probed them in p-type dye sensitized solar cells (p-DSSCs) by using CuO as photocathodes. By realizing the right balance between interfacial charge separation and charge recombination, optimized fill factors (FFs) of 0.43 were obtained. With a control over fill factors in p-DSSCs in hand we turned our attemtion to t-DSSCs, in which we combined for the first time CuO-based p-DSSCs with TiO2 -based n-DSSCs using ZnPc and N719. In the resulting t-DSSCs, the VOC of 0.86 V is the sum of those found in p- and n-DSSCs, while the FF remains around 0.63. It is only the smaller Jsc s in t-DSSCs that limits the efficiency to 0.69 %.

Synergy of Catechol-Functionalized Zinc Oxide Nanorods and Porphyrins in Layer-by-Layer Assemblies.

Catechol-functionalized, positively charged ZnO nanorods (NRs) and anionic porphyrins were integrated into layer-by-layer (LbL) assemblies. In general, this study focuses on the impact that different porphyrins, varying in size and number of negative charges, exert on the LbL architecture in terms of morphology and spectroscopy. In particular, through a combination of analytical methods, including UV/Vis spectroscopy, SEM, and profilometry, valuable insights into LbL assembly formation were gathered. A key feature was the surface coverage in the resulting films. Denser films and surface coverages were realized when highly negatively charged and sterically demanding porphyrins were employed. As a complement to basic characterization, the LbL assembled films were used to fabricate proof-of-concept solar cells.

Novel Ligand and Device Designs for Stable Light-Emitting Electrochemical Cells Based on Heteroleptic Copper(I) Complexes.

This work reports on the positive impact of (i) attaching methoxy groups at the ortho position of the bipyridine ligand (6,6'-dimethoxy-2,2'-bipyridine) in heteroleptic copper(I) complexes belonging to the [Cu(bpy)(POP)]+ family, and (ii) a new device design comprising a multilayered architecture to decouple hole/electron injection and transport processes on the performance of light-emitting electrochemical cells (LECs). In short, the substituted complex showed enhanced thermal- and photostability, photoluminescence, and ionic conductivity features in thin films compared to those of the archetypal complex without substitution. These beneficial features led to LECs outperforming reference devices in terms of luminance, stability, and efficacy. Furthermore, a new device design resulted in a 10-fold enhancement of the stability without negatively affecting the other figures of merit. Here, hole/electron injection and transport processes are performed at two different layers, while electron injection and electron-hole recombination occur at the copper(I) complex layer. As such, this work provides further insights into a smart design of N^N ligands for copper(I) complexes, opening the path to a simple device architecture toward an enhanced electroluminescence response.

When Fluorescent Proteins Meet White Light-Emitting Diodes.

Over the last decades, fluorescent proteins (FPs) have been extensively employed for imaging and tracing in cell biology and medicine. However, their application for lighting devices like light-emitting diodes (LEDs) and lasers has recently started. The interest of FPs is the result of their good photoluminescence features (high emission efficiency with a narrow spectrum and a high photon-flux saturation), good photostability, sustainable production by bacteria, and eco-friendly recycling. Their low stability at high temperatures as well as the need for an aqueous environment have, however, strongly limited their use in optoelectronics. This has recently been circumvented with new coating systems that are paving the way for the entrance of FPs into the LED field. In this Minireview, we summarize the first steps taken by a few groups towards the development of bio-hybrid white LEDs (Bio-HWLEDs) with a focus on using FPs as color down-converters, highlighting the state of the art and challenges associated with this emerging field.

Role of the Bridging Group in Bis-Pyridyl Ligands: Enhancing Both the Photo- and Electroluminescent Features of Cationic (IPr)CuI Complexes.

We report on the benefits of changing the bridging group X of bis-pyridyl ligands, that is, Py-X-Py where X is NH, CH2 , C(CH3 )2 , or PPh, on the photo- and electroluminescent properties of a new family of luminescent cationic H-heterocyclic carbene (NHC) copper(I) complexes. A joint experimental and theoretical study demonstrates that the bridging group affects the molecular conformation from a planar-like structure (X is NH and CH2 ) to a boat-like structure (X is C(CH3 )2 and PPh), leading to i) four-fold enhancement of the photoluminescence quantum yield (ϕem ) without affecting the thermally activated delayed fluorescence mechanism, and ii) one order of magnitude reduction of the ionic conductivity (σ) of thin films. This leads to an overall enhancement of the device efficacy and luminance owing to the increased ϕem and the use of low applied driving currents.

Benzoporphyrins: Selective Co-sensitization in Dye-Sensitized Solar Cells.

A novel class of dyes, namely benzoporphyrins, was synthesized and implemented into dye-sensitized solar cells. They feature complementary absorptions compared to N719, which renders them promising candidates for co-sensitization in DSSCs. Notably, metallated benzoporphyrins reveal a TiO2 -nanoparticle attachment that is size and aggregation dependent. Therefore, unproductive energy-transfer events between the selectively attached dyes can be prevented. In light of the latter, an efficiency improvement of 39 % has been achieved upon selective adsorption of benzoporphyrins and N719 onto different layers of TiO2 photoelectrode.

Layer-by-layer assemblies of catechol-functionalized TiO2 nanoparticles and porphyrins through electrostatic interactions.

In the current work, we present the successful functionalization and stabilization of P-25 TiO2 nanoparticles by means of N1,N7-bis(3-(4-tert-butyl-pyridium-methyl)phenyl)-4-(3-(3-(4-tert-butyl-pyridinium-methyl)phenylamino)-3-oxopropyl)-4-(3,4-dihydroxybenzamido)heptanediamide tribromide (1). The design of the latter is aimed at nanoparticle functionalization and stabilization with organic building blocks. On one hand, 1 features a catechol anchor to enable its covalent grafting onto the TiO2 surface, and on the other hand, positively charged pyridine groups at its periphery to prevent TiO2 agglomeration through electrostatic repulsion. The success of functionalization and stabilization was corroborated by thermogravimetric analysis, dynamic light-scattering, and zeta potential measurements. As a complement to this, the formation of layer-by-layer assemblies, which are governed by electrostatic interactions, by alternate deposition of functionalized TiO2 nanoparticles and two negatively charged porphyrin derivatives, that is, 5,10,15,20-(phenoxyacetic acid)-porphyrin (2) and 5,10,15,20-(4-(2-ethoxycarbonyl)-4-(2-phenoxyacetamido)heptanedioic acid)-porphyrin (3), is documented. To this end, the layer-by-layer deposition is monitored by UV/Vis spectroscopy, scanning electron microscopy, ellipsometry, and profilometry techniques. The resulting assemblies are utilized for the construction and testing of novel solar cells. From stable and repeatable photocurrents generated during several "on-off" cycles of illumination, we derive monochromatic incident photo-to-current conversion efficiencies of around 3 %.

Combining electron-accepting phthalocyanines and nanorod-like CuO electrodes for p-type dye-sensitized solar cells.

A route is reported for the synthesis of two electron-accepting phthalocyanines featuring linkers with different lengths as sensitizers for p-type dye-sensitized solar cells (DSSCs). Importantly, our devices based on novel nanorod-like CuO photocathodes showed high efficiencies of up to 0.191 %: the highest value reported to date for CuO-based DSSCs.

Tuning the self-assembly of rectangular amphiphilic cruciforms.

The self-assembly of a series of nonionic amphiphilic cruciforms based on the 1,2,4,5-tetrakis(phenylethynyl)benzene (TPEB) skeleton, in which the peripheral substituents have been modified to modulate the morphology of the supramolecular structures, is reported. The presence of linear paraffinic and hydrophilic chains in TPEBs 1 and 2 gives rise to two-dimensional structures of high aspect ratio. In contrast, the incorporation of dendronized hydrophilic chains results in the formation of twisted ribbons in amphiphile 3 and impedes the organized self-assembly of TPEB 4. Theoretical calculations show that the self-assembly of these amphiphiles might be initiated with the formation of π-stacked dimeric units. Compound 2, which self-assembles into different morphologies depending on the solvent, interacts by π-stacking and also by the interdigitation of the peripheral decyl tails to generate bidimensional supramolecular structures. The steric demand exerted by the dendronized polar wedges in 3 and 4 strongly conditions their supramolecular organization. This steric demand together with the interdigitation of the decyl chains results in the self-assembly of cruciform 3 into helical aggregates. However, the lack of the paraffinic chains in 4 impedes this helical organization, and the formation of amorphous material is visualized. The joint experimental and theoretical study presented herein provides relevant guidelines for the modulated self-assembly of nonionic amphiphilic molecules.

[Ag(IPr)(bpy)][PF6]: brightness and darkness playing with aggregation induced phosphorescence for light-emitting electrochemical cells.

Heteroleptic silver(I) complexes have recently started to attract attention in thin-film lighting technologies as an alternative to copper(I) analogues due to the lack of flattening distortion upon excitation. However, the interpretation of their photophysical behavior is challenging going from traditional fluorescence/phosphorescence to a temperature-dependent dual emission mechanism and ligand-lock assisted thermally activated delayed fluorescence. Herein, we unveil the photoluminescence behavior of a three-coordinated Ag(I) complex with the N-heterocyclic carbene (NHC) ligand and 2,2'-bipyridine (bpy) as the N^N ligand. In contrast to its low-emissive Cu(I) complex structural analogues, a strong greenish emission was attributed to the presence of aggregates formed by π-π intermolecular interactions as revealed by the X-ray structure and aggregation induced emission (AIE) studies in solution. In addition, the temperature-dependent time-resolved spectroscopic and computational studies demonstrated that the emission mechanism is related to a phosphorescence emission mechanism of two very close lying (ΔE = 0.08 eV) excited triplet states, exhibiting a similar delocalized nature over the bipyridine ligands. Unfortunately, this favourable AIE is lost upon forming homogeneous thin films suitable for lighting devices. Though the films showed very poor emission, the electrochemical stability under device operation conditions is remarkable compared to the prior-art, highlighting the potential of [Ag(NHC)(N^N)][X] complexes in thin-film lighting.

Stable and efficient rare-earth free phosphors based on an Mg(II) metal-organic framework for hybrid light-emitting diodes.

Stable and efficient green hybrid light-emitting diodes (HLEDs) were fabricated from a highly emissive Mg(II)-tetraphenyl ethylene derivative metal-organic framework embedded in a polystyrene matrix (Mg-TBC MOF@PS). The photoluminescence quantum yield (ϕ) of the material, >80%, remains constant upon polymer embedment. The resulting HLEDs featured high luminous efficiencies of >50 lm W-1 and long lifetimes of >380 h, making them among the most stable MOF-based HLEDs. The significance of this work relies on the combination of many features, such as the abundance of the metal ion, the straightforward scalability of the synthetic protocol, the great ϕ reached upon phosphor fabrication, and the state-of-the-art HLED performances.

Simple Sol-Gel Protein Stabilization toward Rainbow and White Lighting Devices.

Fluorescent proteins (FPs) are heralded as a paradigm of sustainable materials for photonics/optoelectronics. However, their stabilization under non-physiological environments and/or harsh operation conditions is the major challenge. Among the FP-stabilization methods, classical sol-gel is the most effective, but less versatile, as most of the proteins/enzymes are easily degraded due to the need of multi-step processes, surfactants, and mixed water/organic solvents in extreme pH. Herein, sol-gel chemistry with archetypal FPs (mGreenLantern; mCherry) is revisited, simplifying the method by one-pot, surfactant-free, and aqueous media (phosphate buffer saline pH = 7.4). The synthesis mechanism involves the direct reaction of the carboxylic groups at the FP surface with the silica precursor, generating a positively charged FP intermediate that acts as a seed for the formation of size-controlled mesoporous FP@SiO2 nanoparticles. Green-/red-emissive (single-FP component) and dual-emissive (multi-FPs component; kinetic studies not required) FP@SiO2 are prepared without affecting the FP photoluminescence and stabilities (>6 months) under dry storage and organic solvent suspensions. Finally, FP@SiO2 color filters are applied to rainbow and white bio-hybrid light-emitting diodes featuring up to 15-fold enhanced stabilities without reducing luminous efficacy compared to references with native FPs. Overall, an easy, versatile, and effective FP-stabilization method is demonstrated in FP@SiO2 toward sustainable protein lighting.

VARPA: In Silico Additive Screening for Protein-Based Lighting Devices.

Protein optoelectronics is an emerging field facing implementation and stabilization challenges of proteins in harsh non-natural environments, such as dry polymers, inorganic materials, etc., operating at high temperatures/irradiations. In this context, additives promoting structural and functional protein stabilization are paramount to realize highly performing devices. On one hand, trial-error experimental assays based on previous knowledge of classical additives in aqueous solutions are effort/time-consuming, while their translation to water-less matrices is uncertain. On the other hand, computational simulations (molecular dynamics, electronic structure methods, etc.) are limited by the system size and time. Herein, ligand-binding affinity and atomic perturbations to create a day-fast computational method combining Vina And Rosetta for Protein Additives (VARPA) to simulate the stabilization effect of sugars for the archetypal enhanced green fluorescent protein embedded in a standard dry polymer color-converting filter for bio-hybrid light-emitting diodes is merged. The VARPA's sugar additive prediction trend for protein stabilization is nicely validated by thermal and photophysical studies as well as lighting device analysis. The device stability followed the predicted enhanced stability trend, reaching a 40-fold improvement compared to reference devices. Overall, VARPA can be adapted to a myriad of additives and proteins, driving first-step experimental efforts toward highly performing protein devices.

Controlling aggregation-induced emission by supramolecular interactions and colloidal stability in ionic emitters for light-emitting electrochemical cells.

Chromophores face applicability limitations due to their natural tendency to aggregate, with a subsequent deactivation of their emission features. Hence, there has been a fast development of aggregation induced emission (AIE) emitters, in which non-radiative motional deactivation is inhibited. However, a fine control of their colloidal properties governing the emitting performance is fundamental for their application in thin film optoelectronics. In addition, ion-based lighting devices, such as light emitting electrochemical cells (LECs), requires the design of ionic AIE emitters, whose structure allows (i) an easy ion polarizability to assist charge injection and (ii) a reversible electrochemical behavior. To date, these fundamental questions have not been addressed. Herein, the hydrophilic/hydrophobic balance of a family of cationic tetraphenyl ethene (TPE) derivatives is finely tuned by chemical design. The hydrophilic yet repulsive effect of pyridinium-based cationic moieties is balanced with hydrophobic variables (long alkyl chains or counterion chemistry), leading to (i) a control between monomeric/aggregate state ruling photoluminescence, (ii) redox behavior, and (iii) enhanced ion conductivity in thin films. This resulted in a LEC enhancement with the first ionic AIE emitters, reaching values of 0.19 lm W-1 at ca. 50 cd m-2. Overall, this design rule will be key to advance ionic active species for optoelectronics.

Investigations on the Surface Integrity and Wear Mechanisms of TiAlYN-Coated Tools in Inconel 718 Milling Operations.

Inconel 718 is a Ni superalloy with superior mechanical properties, even at high temperatures. However, due to its high hardness and low thermal conductivity, it is considered a difficult-to-machine material. This material is widely used in applications that require good dimensional stability, making the milling process the most used in machining this alloy. The wear resulting from this process and the quality of the machined surface are still challenging factors when it comes to Inconel 718. TiAlN-based coating has been used on cutting tools with Yttrium as a doping element to improve the process performance. Based on this, this work evaluated the machined surface integrity and wear resistance of cutting tools coated using Physical Vapor Deposition (PVD) HiPIMS with TiAlYN in the end milling of Inconel 718, varying the process parameters such as cutting speed (vc), feed per tooth (fz), and cutting length (Lcut). It was verified that the Lcut is the parameter that exerts the most significant influence since, even at small distances, Inconel 718 already generates high tool wear (TW). Furthermore, the main wear mechanisms were abrasive and adhesive wear, with the development of a built-up edge (BUE) under a125 m/min feed rate (f) and a Lcut = 15 m. Chipping, cracking, and delamination of the coating were also observed, indicating a lack of adhesion between the coating and the substrate, suggesting the need for a good interlayer or the adjustment of the PVD parameters.