Low-energy Absorption Research Articles

A comparative study of surfactant-treated natural latex foam morphology, thermodynamic relationships and energy absorption: Talalay vs. dunlop processing

This study investigates the relationships between the morphology, energy absorption, and thermodynamic parameters of natural latex foams (NLFs) processed by the Dunlop and in-house Talalay methods, using different surfactant blends. Both methods involved mixing, moulding, and heating; the additional steps for the Talalay method involved cooling and gelation, a gel-freezing technique wherein the frozen foam is exposed to CO2 gas, inducing its transformation into a gel. The morphology of the internal structure of the NLFs was studied using 2D scanning electron micrographs and 3D micro- computerised tomography images. Two different surfactants, potassium laurate and pluronic, were used. Adding the blended surfactants reduced the porosity and increased the foam density of the NLF samples, improving mechanical properties. The cell size distribution of the NLF samples prepared using the Talalay method was broader than that of those prepared using the Dunlop method. In terms of the mechanical properties and energy absorption capabilities, the Talalay process resulted in samples with 20% lower compressive strength and 7% lower energy absorption than the control sample. A power-law relationship between the energy absorption per unit volume and the compression speed of the different foam samples was also observed. The ratio of the internal energy to the total compression force of the NLF samples prepared using the Talalay process was also lower than those prepared using the Dunlop process. The empirical insights derived from this study show how the mechanical properties and process technology associated with the producing of material foams could be improved.

Stable Near-Infrared Photoluminescence of Hexagonal-Shaped PbS Nanoparticles with 1-Dodecanethiol Ligands.

In this study, lead(II) sulphide (PbS) nanoparticles of varying particle sizes were synthesized using the hot injection method, employing 1-octadecene (ODE) as a coordinating ligand in conjunction with oleylamine (OAm). This synthesis approach was compared with the preparation of hexagonal-shaped nanoparticles through the ligand of 1-Dodecanethiol (DT), resulting in DT-capped PbS nanoparticles. The prepared nanoparticles were characterized using multiple techniques including photoluminescence (PL), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FT-IR). The condensation reaction of DT ligands led to various nanoparticles within the range of 34.87 nm to 35.87 nm across different synthesis temperatures (120 °C, 150 °C, 180 °C, 210 °C, and 240 °C). The PbS with DT ligands exhibited a highly crystalline and superhydrophilic structure. Interestingly, near-infrared (NIR)-PL analysis revealed peaks at 1100 nm, representing the lowest-energy excitonic absorption peak of PbS nanoparticles for both ligands. This suggests their potential utility in various applications, including IR photoreactors, as well as in the development of non-toxic nanoparticles for potential applications in in vivo bioimaging.

Mechanical characteristics of auxetic composite honeycomb sandwich structure under bending

Auxetic honeycomb sandwich structures (AHS) composed of a single material generally exhibit comparatively lower energy absorption (EA) and platform stress, as compared to traditional non-auxetic sandwich structures (TNS). To address this limitation, the present study examines the use of aluminum foam (AF) as a filling material in the re-entrant honeycomb sandwich structure (RS). Filling the AHS with AF greatly enhances both the EA and platform stress in comparison to filling the TNS with AF, while the auxetic composite honeycomb sandwich structure effectively addresses interface delamination observed in traditional non-auxetic composite sandwich structures. Subsequently, the positive–negative Poisson’s ratio coupling designs are proposed to strengthen the mechanical features of a single honeycomb sandwich structure. The analysis results show that the coupling structure optimizes the mechanical properties by leveraging the high bearing capacity of the hexagonal honeycomb and the great interaction between the re-entrant honeycomb and the filling material. In contrast with traditional non-auxetic sandwich structures, the proposed auxetic composite honeycomb sandwich structures demonstrate superior EA and platform stress performance, suggesting their immense potential for utilization in protective engineering.

Multi-feature bionic gradient hierarchical lattice metamaterials with multi-synergistic crushing mechanisms

A persistent challenge of the checkerboard lattice metamaterials has been the trade-off between the controllability in crushing process and the enhancement of mechanical properties, where high stability and customizability tend to yield relatively low energy absorption capacity. To breakthrough this challenge, a design strategy based on a multi-feature bio-inspired gradient hierarchical lattice is presented, drawing from the microstructure characteristics of biological tissue. Experimental results and finite element analysis demonstrate the efficient and strong crushing performances and low oscillatory responses of the proposed gradient hierarchical lattice structures, featured by the designable multi-plateau crushing characteristics due to the multi-synergistic mechanisms of multi-biomimetic incentives. Specifically, its initial peak crushing stress is reduced by 162.69 %, and the energy absorption efficiency is improved by 62.19 % relative to the original square lattice with the same relative density. Moreover, the 1st plateau width of multi-feature bio-inspired gradient hierarchical lattice is determined by the size ratio of the unit cells, while the 1st and 2nd plateau stresses are mainly tailored by the wall-thickness and the relative density, respectively. The multi-bionic gradient hierarchical design paves an exemplary pathway to enhance the crushing performance and mechanical controllability of the checkerboard lattices.

Metalla-Carbaporphyrinoids Consisting of an Acyclic N-Confused Tetrapyrrole Analogue Served as Stable Near-Infrared-II Dyes.

We present herein the synthesis of novel pseudo-metalla-carbaporphyrinoid species (1M: M=Pd and Pt) achieved through the inner coordination of palladium(II) and platinum(II) with an acyclic N-confused tetrapyrrin analogue. Despite their tetrapyrrole frameworks being small, akin to well-known porphyrins, these species exhibit an unusually narrow HOMO-LUMO gap, resulting in an unprecedentedly low-energy absorption in the second near-infrared (NIR-II) region. Density functional theory (DFT) calculations revealed unique dπ-pπ-conjugated electronic structures involving the metal dπ-ligand pπ hybridized molecular orbitals of 1M. Magnetic circular dichroism (MCD) spectroscopy confirmed distinct electronic structures. Remarkably, the complexes feature an open-metal coordination site in the peripheral NN dipyrrin site, forming hetero-metal complexes (1Pd-BF2 and 1Pt-BF2) through boron difluoride complexation. The resulting hetero metalla-carbaporphyrinoid species displayed further redshifted NIR-II absorption, highly efficient photothermal conversion efficiencies (η; 62-65 %), and exceptional photostability. Despite the challenges associated with the theoretical and experimental assessment of dπ-pπ-conjugated metalla-aromaticity in relatively larger (more than 18π electrons) polycyclic ring systems, these organometallic planar tetrapyrrole systems could serve as potential molecular platforms for aromaticity-relevant NIR-II dyes.

The effect of filler loading, biological treatment, and bioplastic blend ratio on flexural and impact properties of blended bioplastic reinforced with spent coffee ground

AbstractIn this study, the mechanical and morphological characteristics of poly(hydroxyalkanoate) (PHA)/poly(lactic acid) (PLA) blend matrix reinforced with spent coffee ground (SCG) were investigated across various weight ratios (100/0, 75/25, 50/50, 25/75, and 0/100) and SCG contents (10–40 wt%). SEM micrographs revealed a phase‐separated structure with cracks on the fracture surface, consistent with the lower flexural properties of biocomposites. The incorporation of SCG reduced mechanical properties, mainly due to its incompatibility with the PHA/PLA matrix. Biocomposites with high SCG content demonstrated lower energy absorption capabilities, likely due to SCG aggregates acting as stress concentrators and disrupting load‐transferring mechanisms. Moreover, increasing PHA content in the blends led to higher PLA crystallinity, as PHA acted as a nucleating agent for PLA. For biological treatment, biocomposites with PHA/PLA ratio (50/50) and SCG loading (20 wt%) were employed. The microscopic analysis highlighted well‐dispersed treated SCG within the matrix and improved interfacial contact. Biocomposites with treated SCG demonstrated remarkable enhancements of 52% and 113% in flexural strength and modulus, respectively. These findings proved the effectiveness of sustainable fungal treatment in enhancing interfacial adhesion and improving the mechanical performance of biocomposites.Highlights Percentage of SCG in bioplastic blend as a significant effect on the flexural properties and impact strength. The ratio of the bioplastic blend has the strong influence on the flexural properties and impact properties. Biological treatment of SCG has improved the interfacial interaction between SCG and bioplastic blend. The treated SCG has rougher surface which facilitates the interfacial locking between bioplastic blend and treated SCG. The biological treatment of SCG has improved the mechanical properties of the composites.

9-Borafluoren-9-yl and diphenylboron tetracoordinate complexes of 8-quinolinolato ligands with heavy-atoms substituents: Synthesis, fluorescence and application in OLED devices

This work describes the synthesis and characterisation of new tetrahedral boron complexes, incorporating bromine- or iodine-substituted 8-quinolinolato chelate chromophores connected to 9-borafluoren-9-yl or diphenylboron orthogonal fragments. The molecular features and photophysical properties of these complexes are analysed in both solution and solid state. Steady-state photophysical studies reveal photoluminescence quantum yields (Φf) ranging from 0.02 to 0.15 and prompt fluorescence (PF) lifetimes (τf) between 2 and 16 ns. Time-resolved photophysical experiments show the presence of delayed fluorescence (DF) and phosphorescence at both 77 K and room temperature. The DF intensity increases with a rise in temperature. This variation is ascribed to an enhancement in the intersystem crossing (ISC) process promoted by the bromine or iodine heavy-atom effect. Investigations into the dependence of DF intensity relative to the excitation dose indicate emissions stemming either from Triplet-Triplet Annihilation (TTA), Thermally Activated Delayed Fluorescence (TADF), or a combination of these competing mechanisms. The effect is related to the size and number of heavy-atom substituents in each boron complex. A study of the DF emission intensity as a function of the excitation dose reveals that diiodo-substituted 8-quinolinolato boron complexes, whether rigid or flexible, display TADF emission. Rigid 5,7-dibromo- and 5-chloro-7-iodo-substituted 8-quinolinolato complexes exhibit a combined TADF-TTA mechanism, whereas the other complexes predominantly demonstrate pure TTA emission. DFT and TDDFT calculations showed that the ground state structures reproduced the experimental geometries and only small increases in bond lengths were observed in the excited state geometries. The low energy absorption bands displayed mainly intra-ligand π→π* (8-quinolinato) character. The fluorescence emission energies were well reproduced, while the singlet-triplet energy gaps were relatively high and spin-orbit coupling was relevant for complexes with heavy-atoms. Ultimately, organic light-emitting diodes (OLEDs) are fabricated using the most luminescent boron complexes. The best OLED is obtained when using complex 3a, which displays green electroluminescence (EL) (λEL = 502 nm) with maximum external quantum efficiency (EQEmax) of 2.5% and maximum luminance (Lmax) of 2200 cd m−2.

Triosmium cluster bearing a metalated dibenzylideneacetone ligand: Synthesis, structure, redox and electronic properties

Dibenzylideneacetone (DBA) reacts with [Os3(CO)10(NCMe)2] in boiling benzene to afford the triosmium cluster [Os3(CO)10{κ2-(C,O)-C17H13O}(µ-H)] (1) formed through activation of one of the β-C–H bonds of the DBA ligand after initial coordination of the ketonic oxygen. The molecular structure of 1 has been determined unequivocally by single crystal X-ray diffraction analysis which reveals that the metalated DBA ligand formed a five-membered osmacycle by coordinating to a single osmium atom using its both donor atoms. Cluster 1 exhibits two closely spaced irreversible reduction peaks at –1.20 V and –1.30 V, respectively, together with an irreversible oxidation peak at 0.57 V. DFT calculations reveals the frontier orbitals are primarily either metal-based (HOMO) or ligand-based (LUMO) which suggests that the oxidation occurs from the metallic core while the first reduction is ligand-centered. Cluster 1 displays two absorption peaks at 337 nm and 477 nm in the UV-visible absorption spectrum. The lowest energy absorption at 477 nm can be attributed to the transition from HOMO to LUMO (MLCT) based on its frontier orbitals.

20π-Electron Antiaromatic Benziphthalocyanines with Absorption Reaching the Near-Infrared-II Region.

Although second near-infrared (NIR-II, 1000-1500 nm) light has attracted considerable attention, especially for life sciences applications, the development of organic dyes with NIR-II absorption remains a formidable challenge. Herein we report the design, synthesis, and electronic properties of 20π-electron antiaromatic benziphthalocyanines (BPcs) that exhibit intense absorption bands in the NIR region. The strong, low-energy absorption of the antiaromatic BPcs is attributed to electric-dipole-allowed HOMO-LUMO transitions with narrow band gaps, enabled by the reduced structural symmetry of BPc compared with regular porphyrins and phthalocyanines. The combination of peripheral substituents and a central metal decreases the HOMO-LUMO energy gaps, leading to the extension of the absorption bands into the NIR-II region (reaching 1100 nm) under reductive conditions.

Investigating the Impact Behavior of Carbon Fiber/Polymethacrylimide (PMI) Foam Sandwich Composites for Personal Protective Equipment.

To improve the shock resistance of personal protective equipment and reduce casualties due to shock wave accidents, this study prepared four types of carbon fiber/polymethacrylimide (PMI) foam sandwich panels with different face/back layer thicknesses and core layer densities and subjected them to quasi-static compression, low-speed impact, high-speed impact, and non-destructive tests. The mechanical properties and energy absorption capacities of the impact-resistant panels, featuring ceramic/ultra-high molecular-weight polyethylene (UHMWPE) and carbon fiber/PMI foam structures, were evaluated and compared, and the feasibility of using the latter as a raw material for personal impact-resistant equipment was also evaluated. For the PMI sandwich panel with a constant total thickness, increasing the core layer density and face/back layer thickness enhanced the energy absorption capacity, and increased the peak stress of the face layer. Under a constant strain, the energy absorption value of all specimens increased with increasing impact speed. When a 10 kg hammer impacted the specimen surface at a speed of 1.5 m/s, the foam sandwich panels retained better integrity than the ceramic/UHMWPE panel. The results showed that the carbon fiber/PMI foam sandwich panels were suitable for applications that require the flexible movement of the wearer under shock waves, and provide an experimental basis for designing impact-resistant equipment with low weight, high strength, and high energy absorption capacities.

Janus ACSP Nanoparticle for Synergistic Chemodynamic Therapy and Radiosensitization.

Protective autophagy and DNA damage repair lead to tumor radio-resistance. Some hypoxic tumors exhibit a low radiation energy absorption coefficient in radiation therapy. High doses of X-rays may lead to side effects in the surrounding normal tissues. In order to overcome the radio-resistance and improve the efficacy of radiotherapy based on the characteristics of the tumor microenvironment, the development of radiosensitizers has attracted much attention. In this study, a Janus ACSP nanoparticle (NP) was developed for chemodynamic therapy and radiosensitization. The reactive oxygen species generated by the Fenton-like reaction regulated the distribution of cell cycles from a radioresistant phase to a radio-sensitive phase. The high-Z element, Au, enhanced the production of hydroxyl radicals (•OH) under X-ray radiation, promoting DNA damage and cell apoptosis. The NP delayed DNA damage repair by interfering with certain proteins involved in the DNA repair signaling pathway. In vivo experiments demonstrated that the combination of the copper-ion-based Fenton-like reaction and low-dose X-ray radiation enhanced the effectiveness of radiotherapy, providing a novel approach for synergistic chemodynamic and radiosensitization therapy. This study provides valuable insights and strategies for the development and application of NPs in cancer treatment.

Node‐Reinforced Design and Selective Remanufacturing of Auxetic Lattice Structures

Auxetic structures have many potential applications due to their counterintuitive deformation behavior and desirable mechanical properties. However, auxetic structures have some drawbacks, such as bending or rotational deformation of ligaments, leading to relatively low energy absorption (EA) performance and stability. In this article, designing nodal reinforcement of the sinusoidal lattice is proposed, and silicone rubber is selectively 3D‐printed inside the structure. As a result, under quasi‐static loading, the nodes of the structure improve the EA performance by 214%; compared to resin reinforcement, silicone‐rubber gradient reinforcement not only continues to provide load‐bearing capacity to the structure but also improves EA by a significant 112%. The assignment of silicone‐rubber nodes is found to effectively prevent the lateral slip of the structure after ligament rupture, resulting in a more stable and controllable deformation of the sinusoidally auxetic structure. Under low‐velocity dynamic loading, silicone rubber's designed nodes improve the structure's deformation stability more significantly and enhance the EA performance, which increases with the strain rate. The design and fabrication techniques have the potential for the integrated fabrication of multi‐material lightweight structures with complex shapes, superior mechanical properties, and multifunctional attributes.

Multi-objective optimization and theoretical analysis of re-entrant structure with enhanced mechanical properties

In response to the challenge of low stiffness and energy absorption capacity, various designs of negative Poisson's ratio (NPR) structures have emerged. However, these designs often lack a comprehensive analysis of other mechanical properties, leading to subpar mechanical performance. Previous studies have explored the mechanical properties response of enhanced re-entrant honeycombs (ERH) under impact conditions, revealing limitations in optimizing the structure's performance with a single objective. Therefore, this study aims to enhance ERH structural parameters to achieve superior mechanical performance through theoretical derivations and geometric optimizations. The results demonstrate that the proposed theoretical model is consistent with finite element analysis and response surface (RS) predictions. Expressions for Young's modulus, specific energy absorption, and compressive strength are proposed, facilitating the identification of structural parameters that meet specific requirements during reverse design. Furthermore, a multi-objective optimization approach optimizes the geometric parameters based on maximum energy absorption and compressive strength. The mechanical behavior of the optimized ERH is investigated using the finite element method, revealing the energy absorption capacity of 13.78 J/g while maintaining Poisson's ratio at -1.06. Additionally, the deformation mode of the optimized structure showcases enhanced stability compared to traditional honeycomb structures. The theoretical model and RS method were used to guide the design of ERH and promote the application of NPR structures.

NIR-II Emission from Cyclometalated Dinuclear Pt(III) Complexes.

Half-lantern Pt(II) dinuclear complexes [{Pt(C∧Npz)(μ-S∧NR)}2] (HC∧Npz = 1-naphthalen-2-yl-1H-pyrazole; R = H, HS∧N: 2-mercaptopyrimidine 1; R = CF3, HS∧NF: 4-(trifluoromethyl)-2-mercaptopyrimidine 2) were selectively obtained as single isomers with the C∧N groups in an anti-arrangement and rather short metallophilic interactions (dPt-Pt = 2.8684(2) Å for 2). They reacted with haloforms in the air and sunlight to obtain the corresponding oxidized diplatinum(III) derivatives [{Pt(C∧Npz)(μ-S∧NR)X}2] (X = Cl (1-Cl), Br (1-Br), I (1-I, 2-I)). The single-crystal X-ray structures exhibit Pt-Pt distances typical for the existence of a metal-metal bond, which evidence fairly well the influence of the axial ligand (X). The reactions of 1 and 2 with CHI3 in the dark afforded mixtures of [IPt(C∧Npz)(μ-S∧N)2Pt(C∧Npz)CHI2] and 1-I or 2-I, with the former being the major species under an Ar atmosphere, while the reactions of 1 with CHBr3 and CHCl3 need light to occur. These Pt2(III,III) complexes display low-energy absorptions and emissions that strongly depend on the axial ligand. In the solid state, they show a broad NIR emission ranging from 985 to 1070 nm at RT that suffers a hypsochromic shift when cooling down to 77 K. The photoemissive behavior of the dinuclear Pt(II) and Pt(III) systems is disclosed with the aid of density functional theory calculations.

Impact Behavior and Residual Strength of PEEK/CF-Laminated Composites with Various Stacking Sequences.

Carbon fiber-reinforced composites are popular due to their high strength and light weight; thus, the structures demonstrate high performance and specific strength. However, these composites are susceptible to impact damage. The objective of this research was to study the behavior of carbon fiber-reinforced laminates based on a polyetheretherketone (PEEK) matrix with six stacking sequences under static and impact loading. Four-point bending, short-beam bending, drop weight impact, and compression after impact tests were carried out. The results were complemented with digital shearography to estimate the damaged areas. Finite element modeling served to assess the failure mechanisms, such as fiber and matrix failure, in different layers due to tension of compression. Three behavior pattern of layups under drop-weight impact were found: (i)-energy redistribution due to mostly linear behavior (like a trampoline) and thus lower kinetic energy absorption for damage initiation, (ii)-moderate absorption of energy with initiation and propagation of concentrated damage with depressed redistribution of energy in the material, (iii)-moderate energy absorption with good redistribution due to initiation of small, dispersed damage. The results can be used to predict the mechanical behavior of composites with different stacking sequences in materials for proper structural design.

Structural insights into the unusual core photocomplex from a triply extremophilic purple bacterium, Halorhodospira halochloris.

Halorhodospira (Hlr.) halochloris is a triply extremophilic phototrophic purple sulfur bacterium, as it is thermophilic, alkaliphilic, and extremely halophilic. The light-harvesting-reaction center (LH1-RC) core complex of this bacterium displays an LH1-Qy transition at 1,016 nm, which is the lowest-energy wavelength absorption among all known phototrophs. Here we report the cryo-EM structure of the LH1-RC at 2.42 Å resolution. The LH1 complex forms a tricyclic ring structure composed of 16 αβγ-polypeptides and one αβ-heterodimer around the RC. From the cryo-EM density map, two previously unrecognized integral membrane proteins, referred to as protein G and protein Q, were identified. Both of these proteins are single transmembrane-spanning helices located between the LH1 ring and the RC L-subunit and are absent from the LH1-RC complexes of all other purple bacteria of which the structures have been determined so far. Besides bacteriochlorophyll b molecules (B1020) located on the periplasmic side of the Hlr. halochloris membrane, there are also two arrays of bacteriochlorophyll b molecules (B800 and B820) located on the cytoplasmic side. Only a single copy of a carotenoid (lycopene) was resolved in the Hlr. halochloris LH1-α3β3 and this was positioned within the complex. The potential quinone channel should be the space between the LH1-α3β3 that accommodates the single lycopene but does not contain a γ-polypeptide, B800 and B820. Our results provide a structural explanation for the unusual Qy red shift and carotenoid absorption in the Hlr. halochloris spectrum and reveal new insights into photosynthetic mechanisms employed by a species that thrives under the harshest conditions of any phototrophic microorganism known.

A series of 2‐phenylbenzothiazole‐based iridium complexes with N‐H derivatives: synthesis, photophysics, DFT calculations and a preliminary exploration in fluoride ions sensing

AbstractA series of new pbt‐based Ir(III) complexes containing N−H derivatives ancillary ligands (piz/pbiz) were designed and synthesized rationally, naming [(CH3Opbt)2Ir(piz)][PF6] (Ir1), [(CF3pbt)2Ir(piz)][PF6] (Ir2), [(Fpbt)2Ir(piz)][PF6] (Ir3), [(CH3Opbt)2Ir(pbiz)][PF6] (Ir4), [(CF3pbt)2Ir(pbiz)][PF6] (Ir5) and [(Fpbt)2Ir(pbiz)][PF6] (Ir6) (where pbt=2‐phenylbenzothiazole, piz=2‐(1H‐imidazol‐2‐yl)pyridine, and pbiz=2‐(pyridin‐2‐yl)‐1H‐benzoimidazole). Combined with photophysical properties and theoretical calculations, their structure‐property relationships were systematically researched. These iridium(III) complexes are phosphorescent in the green and yellow‐green region with quantum yields of 14.1–28.7 % and lifetimes of 0.35–0.88 μs. Considering the relatively high quantum yield and imidazole group on ancillary ligands, [(CF3pbt)2Ir(pbiz)][PF6] (Ir5) was preliminary explored as the phosphorescent sensor toward F− ions. The results showed that the addition of fluoride ions to complex Ir5 in dichloromethane solution induced a red shift of the emission color, along with an enhancement in the luminescent intensity. Theoretical calculations were carried out to understand the mechanism, and the results reveal that the hydrogen bonding interaction of N−H bond with F− influence the electron transfer processes of the lowest energy absorption and emission, leading to a significant change in the photophysical properties.

1,3‐Diynes as Precursors for the Synthesis of Triazene‐ and Diethylaniline‐Bearing Push‐Pull NLOphores

AbstractWithin the scope of this study, a total of eight new NLOphores of the D‐π‐A‐π‐D type have been synthesized. This was achieved by applying click‐type [2+2] cycloaddition‐retroelectrocyclization reactions of unsymmetrical 1,3‐diynes with well‐known electron‐deficient alkenes, TCNE, and TCNQ. Furthermore, essential insights into the optical properties of the synthesized NLOphores were obtained from comparisons with four model compounds synthesized separately within this study. The thermal stability of the NLOphores was assessed through thermal gravimetric analysis (TGA). NLOphores synthesized using two distinct electron‐deficient alkenes exhibit low energy absorption bands covering most of the visible region with λmax values ranging from 466 nm to 723 nm. Theoretical studies, including time–dependent density functional theory (TD‐DFT) investigations, frontier orbital visualizations, and electrostatic potential maps, have been utilized to further investigate the intramolecular charge transfer properties of chromophores. The NLO responses of the chromophores were determined through DFT calculations. It is worth noting that the average polarizability and first hyperpolarizability values (α(tot)=106.392–159.709×10−24 esu; β(tot)=387.552–417.359×10−30 esu) obtained from these calculations show significant promise compared to literature data.

Phosphorescent fac-Bis(triarylisocyanide) W(0) and Mo(0) Complexes.

Homoleptic W(0) and Mo(0) complexes containing bis(triarylisocyanide) ligands with bulky substituents were synthesized and spectroscopically characterized. Crystallographically determined structures revealed that these complexes are hourglass-like in shape with the tridentate ligands adopting a facial coordination mode to the metal center. These complexes luminesce in fluid solutions and in the solid state. Typically in toluene at 298 K, the two W(0) complexes display the emission maximum (lifetime and quantum yield) at 591 nm (0.83 μs and 0.35) and 628 nm (1.04 μs and 0.39), and similarly, the two Mo(0) complexes display it at 575 nm (0.54 μs and 0.15) and 617 nm (0.56 μs and 0.23). DFT and TDDFT calculations indicated that the low-energy absorption bands of the W(0) and Mo(0) complexes could be metal-to-ligand charge transfer (MLCT) transitions in nature. These complexes exhibited a reversible M+/0 redox couple at -0.70 and -0.63 V vs Fc+/0 for the W(0) complexes and -0.86 and -0.67 V for the Mo(0) complexes. The excited-state reduction potentials were hence estimated to be -2.91 and -2.74 V vs Fc+/0 for the W(0) complexes and -3.10 and -2.81 V vs Fc+/0 for the Mo(0) complexes, indicating that they are potentially strong photoreductants.

Ligand Desorption and Fragmentation in Oleate-Capped CdSe Nanocrystals under High-Intensity Photoexcitation.

Semiconductor nanocrystals (NCs) offer prospective use as active optical elements in photovoltaics, light-emitting diodes, lasers, and photocatalysts due to their tunable optical absorption and emission properties, high stability, and scalable solution processing, as well as compatibility with additive manufacturing routes. Over the course of experiments, during device fabrication, or while in use commercially, these materials are often subjected to intense or prolonged electronic excitation and high carrier densities. The influence of such conditions on ligand integrity and binding remains underexplored. Here, we expose CdSe NCs to laser excitation and monitor changes in oleate that is covalently attached to the NC surface using nuclear magnetic resonance as a function of time and laser intensity. Higher photon doses cause increased rates of ligand loss from the particles, with upward of 50% total ligand desorption measured for the longest, most intense excitation. Surprisingly, for a range of excitation intensities, fragmentation of the oleate is detected and occurs concomitantly with formation of aldehydes, terminal alkenes, H2, and water. After illumination, NC size, shape, and bandgap remain constant although low-energy absorption features (Urbach tails) develop in some samples, indicating formation of substantial trap states. The observed reaction chemistry, which here occurs with low photon to chemical conversion efficiency, suggests that ligand reactivity may require examination for improved NC dispersion stability but can also be manipulated to yield desired photocatalytically accessed chemical species.