Piezoelectric property improvement of polyethylene ferroelectrets using postprocessing thermal‐pressure treatment

In this work, biaxially stretched polymer foams with well‐defined cellular structures were prepared from polyethylene via blown‐film extrusion and subjected to corona charging to produce a piezoelectric response. The charging parameters were first optimized in terms of charging voltage and needle distance, as well as the gas type and pressure to investigate their effect on the piezoelectric coefficient (d₃₃). The results show that samples charged under nitrogen (N₂) at 100 kPa had better d₃₃ coefficient than those charged under ambient air or N₂ at 20 kPa. Moreover, 2 different thermal pressure treatments were imposed to obtain an optimized eye‐like cellular structure with different cell aspect ratios (AR). The results showed that when the cells were elongated in both the longitudinal and transverse directions (higher AR), higher d₃₃ coefficients were achieved. From all the samples produced, the best results were obtained for a longitudinal aspect ratio (AR‐L) of 7.1, a transversal aspect ratio (AR‐T) of 4.6, and a relative foam density of 0.52 leading to a d₃₃ coefficient of 935 pC/N. This coefficient was further increased using reverse charging and multilayered films, reaching a maximum of 2550 pC/N. This value is much higher than typical ones reported so far for any polyethylene and polypropylene ferroelectrets. These results could increase the use of polyethylene in piezoelectric applications as these materials are very attractive for the large‐scale production of electret‐based sensors and transducers due to their low cost and easy processing.     

Transparent Electronic Skin Device Based on Microstructured Silver Nanowire Electrode

Transparent, flexible electronic skin holds a wide range of applications in robotics, humanmachine interfaces, artificial intelligence, prosthetics, and health monitoring. Silver nanowire are mechanically flexible and robust, which exhibit great potential in transparent and electricconducting thin film. Herein, we report on a silver-nanowire spray-coating and electrodemicrostructure replicating strategy to construct a transparent, flexible, and sensitive electronic skin device. The electronic skin device shows highly sensitive piezo-capacitance response to pressure. It is found that micropatterning the surface of dielectric layer polyurethane elastomer by replicating from microstructures of natural-existing surfaces such as lotus leaf, silk, and frosted glass can greatly enhance the piezo-capacitance performance of the device. The microstructured pressure sensors based on silver nanowire exhibit good transparency, excellent flexibility, wide pressure detection range (0-150 kPa), and high sensitivity (1.28 kPa^-1).     

Trends in the formation of aggregates and crystals from M@Si<Subscript>16</Subscript> clusters: a study from first principle calculations

We have shown recently that the ground state and low-lying energy isomers of the endohedral M@Si₁₆ clusters (M = Sc⁻, Ti, V⁺) have a nearly spherical cage-like symmetry with a closed shell electronic structure which conforms them as exceptional stable entities. This is manifested, among other properties, by a large Homo–Lumo gap about 2 eV which suggest the possibility of using these clusters as basic units (superatoms) to construct optoelectronic materials. As a first step in that direction, we have studied in this work, by means of first principles calculations, the trends in the formation of [Ti@Si₁₆] _n , [Sc@Si₁₆K] _n , and [V@Si₁₆F] _n aggregates as their size increases, going from linear to planar to three dimensional arrangements. The most favorable configurations for n ≥ 2 are those formed from the fullerene-like D_4d isomer of M@Si₁₆, instead of the ground state Frank–Kasper T _d structure of the isolated M@Si₁₆ unit, joined by Si–Si bonds between the Si atoms of the square faces. In all cases the Homo–Lumo gap for the most favorable structure decrease with the size n. Trends for the binding energy, dipole moment, and other electronic properties are also discussed. Several crystal structures constructed from these superatom, supermolecules, and aggregates have been tested and preliminary results are summarily commented.     

Non‐oxidized graphene/elastomer composite films for wearable strain and pressure sensors with ultra‐high flexibility and sensitivity

It remains challenging to prepare wearable strain and pressure sensors with excellent mechanical properties, ultra‐high flexibility and sensitivity. Electrically conductive graphene platelets (GnPs) with high structural integrity are used in making a composite film fabricated using robust fabrication techniques. The gauge factor for the strain is up to 100 at 0%‐5% strain and 50 at 5%‐30% strain, and the sensitivity to pressure is 2.7×10^‐2 kPa^‐1 between 0 and 10 kPa and 1.5×10^‐4 kPa^‐1 between 300 and 1000 kPa. In addition, the flexible sensor demonstrates good repeatability and durability after 1000 cycles of tensile and compression tests. The flexible sensor has fast response ability and a wide operating temperature range, suggesting the excellent response to temperature. The flexible sensor is applied in monitoring several human motions as a wearable device with high accuracy. The ability to detect strain, pressure and temperature of the flexible sensor extends its applications to multifunctional wearable devices.     

Development and investigation of the flexible hydrogen sensor based on ZnO-decorated Sb2O3 nanobelts

Hydrogen is regarded as the next-gen fuel for vehicles to avoid the emission of toxic gases, which needs a continuous monitoring of the concentration level. In the design of the H₂ sensor, especially of flexible type, a sensing layer will be blended, which affects the sensing performance of the device. Based on this concern, the present investigation is carried out to understand the effect of the bending angle toward the sensing performance of bare and ZnO (n-type)-decorated Sb₂O₃ (p-type) nanobelt–based sensors for hydrogen gas. The sensing element was prepared by the thermal chemical vapor deposition followed by the drop-casting method. Furthermore, the role of the zinc precursor (molar concentration—1 M–3 M) on the preparation of ZnO-decorated Sb₂O₃ nanobelts was studied. Various techniques were used to confirm the formation of ZnO-decorated nanobelts such as X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), and Fourier transform infrared spectroscopy (FTIR). From these analyses, 1 M concentration of the zinc precursor shows uniform distribution of nanoparticles over the surface of Sb₂O₃ nanobelts. However, agglomeration was observed when the concentration of the zinc precursor increases from 1 M to 3 M. Later, the prepared nanobelts were deposited on the OverHead Projector (OHP) sheet by the doctor blade method for sensing hydrogen gas at 100 °C at a concentration of 1000–3000 ppm. In addition to it, the effect of the substrate bending angle (0°, 45°, 60°, and 90°) was analyzed at a fixed concentration of H₂ gas (1000 ppm). From this study, it is clear that the highest sensing response was achieved for 1 M decorated nanobelts compared with bare as well as other concentrations because of uniform distribution of nanoparticles on the surface of nanobelts. Moreover, the prepared sample demonstrates better sensing performance with the bending of substrates, which suggests that the prepared sensor could be used for flexible electronic devices. The prepared nanobelts show a good H₂ gas–sensing response even with bending of the substrates. The work suggests that the prepared sensor is applicable for flexible electronic devices.     

CN bond rotation and E–Z isomerism in some N-benzyl-N-methylcarbamoyl chlorides: A DFT study

The electronic and geometrical structures of thiosulfinic acids, RSSOH, 1, (1a, R = H; 1b, R = CH₃; 1c, R = t-C₄H₉; 1d, R = C₆H₅; 1e, R = F) and their anions have been investigated by the ab initio and density functional methods. The calculations show that the stability of the thiolo-tautomers of 1, RS(O)SH, and the thiono-tautomers, RS(S)OH, is almost the same in the gas phase, the energy of the thiolo-tautomers being slightly lower. The tautomers of 1 having the thiosulfone structure, RS(O)(S)H, were found to be the least stable. The thiosulfinate anions show ambident character with the negative charge dispersed over terminal O and S atoms and are stabilized by electronegative substituents.     

Surface structure for Au on (0 0 1) SrTiO3

First-principle calculations are performed to study the crystal structure, formation energies, and electronic structures of (0 0 1) SrTiO₃ surfaces with/without Au covered. The initiative Au additive layer is crystallized in a fcc structure with (0 0 1) face on SrO-terminated surface. The bimodal growth trend of Au on TiO₂-terminated surface is qualitatively consistent with the experimental observations. The defect structure of Au occupying the oxygen (O) vacancies of TiO₂-terminated surface is energetically favorable under oxygen-poor conditions, and a feature corresponding to gap states appear and the occupied Ti 3d states disappear.     

Hydrophobic association and ionic coordination dual crossed-linked conductive hydrogels with self-adhesive and self-healing virtues for conformal strain sensors

As a promising functional material, conductive hydrogel has attracted extensive attention, especially in flexible sensor field. Despite the recent developments, current hydrogels still experience several issues, such as limited stretchability, lack of self-recovery and self-healing capability, and insufficient self-adhesion. Herein, dual cross-linked (DC) poly (AA-co-LMA)_SDS/Fe³⁺ hydrogels are fabricated subtly on the basis of ionic coordination interactions and the poly (AA-co-LMA)_SDS hydrophobic association networks, which may provide one plausible routine to compensate the mentioned drawback of hydrogels. The hydrophobic association and ionic coordination networks work synergistically to endow the hydrogels remarkable stretchability (>1200%), high-fracture strength (≈ 820 kPa), and excellent self-healing capability. In addition, the DC hydrogel-based strain sensors displayed a broad sensing range (0 ∼ 900%), conspicuous sensitivity (strain 0% ∼ 200%, gauge factor = 0.53; strain 200% ∼ 500%, gauge factor = 1.23; strain 500% ∼ 900%, gauge factor = 2.09), and pronounced durability. What's more, the self-adhesive feature ensures the strain sensor always forming a good conformal contact with the skin during human movements and displaying remarkable bidirectional detection capability.     

Inert effects on the flammability characteristics of methanol by nitrogen or carbon dioxide

Knowledge of material safety properties is critical for safe handing in the chemical process industries, especially for flammable chemicals that might result in serious fires and explosions. This study investigated the flammability characteristics of methanol under working conditions during the process. The targeted fire and explosion properties, like explosion limits (UEL and LEL), vapor deflagration index (K _g), maximum explosion pressure (P _max), and maximum explosion pressure rise [(dP dt ⁻¹)_max], were deliberately obtained via a 20-L-Apparatus in 101 kPa (i.e., 760 mmHg/1 atm), 150 and 200 °C, along with various experimental arrangements containing nitrogen (N₂) or carbon dioxide (CO₂) as inert component. Particularly, this study discussed and elucidated the inert influence on the above safety-related parameters by two different inerting gases of N₂ and CO₂. The results indicated that adding an inert component to fuel–inert gas mixtures determined the decrease of explosion range and flammability hazard degree. The results also demonstrated that CO₂ possessed higher inerting capability than N₂ in this study.     

The influence of ZnO-Sensor modification by porphyrins on to the character of sensor response to volatile organic compounds

The influence of modification of semi conductive ZnO and SnO₂ sensors by porphyrins and their metal complexes on the parameters of sensor response to volatile organic compounds, ethanol, acetone and benzene, was analyzed. The concentration of volatile organic compounds (c _i ) varied in the range of 1–200 ppm. The sensor response was characterized by specific sensitivity γ _i = 100ΔR _i /R ₀ c _i , where ΔR _i = R _i − R ₀, R _i and R ₀ are measurable and initial resistance of the sensitive sensor layer correspondingly. It was established that the modification of sensors by porphyrins caused changes in sensor response and first of all decrease of ZnO sensor temperature at which the threshold of sensitivity is achieved (as used at this method c _i ^min = 0.1 ppm) from 300 to 100°C. It also caused a change in sing of the parameter γ, which was of importance for creating “electronic nose” sensor systems. It was shown also, that the modification of ZnO sensor by metal complexes of porphyrin did not change sensor response parameters.     

Bioinspired design of highly sensitive flexible tactile sensors for wearable healthcare monitoring

The design of microscale architectures integrated with low-dimensional nanomaterials for tactile sensors has attracted considerable attention owing to their high performance for various potential applications, especially in the field of healthcare monitoring. However, there still remains a critical challenge to achieve high sensitivity in response to different magnitude external pressure. Herein, we introduce a high performance capacitive tactile sensor based on Silver nanowires coated biomimetic hierarchical array architecture, which consists of mini-domes by the way of vacuum adsorption from through-hole arrays and micro-cones by duplicating Calathea zebrina leaf, respectively. This hybrid graded microstructure as electrode exhibits remarkably improved sensitivity and stimulus responding range when compared with the other monotonous counterparts. Moreover, an optimized ionic gel film with remarkable interfacial capacitance is sandwiched by microstructured electrodes as the dielectric layer, further boosting the performance of the tactile sensor. As a result, the obtained sensor demonstrates a board detection range from 24 Pa to 90 kPa with a maximum sensitivity of 37.8 kPa^?1, and a fast response time (<78 ms). These superior performances of our tactile sensor lay a foundation for various applications in healthcare monitoring. It can not only sense and distinguish subtle arterial pulse signals even under different ages, genders and states of motion but also monitor physiological activity with large pressure as well, such as breathing, plantar pressure, and so on. We envision this bionic tactile sensor holds great potential in wearable electronics.     

Novel optical trace oxygen sensors based on platinum(II) and palladium(II) complexes with 5,10,15,20-meso-tetrakis-(2,3,4,5,6-pentafluorphenyl)-porphyrin covalently immobilized on silica-gel particles

New optical sensors for trace amounts of oxygen are based on platinum(II) and palladium(II) complexes of 5,10,15,20-meso-tetrakis-(2,3,4,5,6-pentafluorphenyl)-porphyrin covalently attached to the surface of amino-modified silica-gel particles. The dye-doped silica-gel particles are dispersed in silicone rubber. The Stern–Volmer plots show linear response and are virtually identical for either luminescence intensity and decay time. Other features include high photostability and rapid response times (∼150 ms in gas phase). The sensors based on the palladium(II) complex show significantly higher sensitivity (K_SV about 67 kPa⁻¹ at 25 °C) with the dynamic range from 0.02 to 100 Pa. The sensitivity of the platinum(II) complexes is significantly lower (K_SV = 3.7–4.2 kPa⁻¹, dynamic range 0.3–1000 Pa). The sensors can be suitable for application in breweries, water boilers and for marine research (monitoring of oxygen minimum zones).     

Kinetics of gas-phase decomposition of oxetan and oxetan-2,2-d2

The pressure dependence of the first-order rate coefficient of oxetan and oxetan-2,2-d₂ decomposition has been studied in the pressure range from about 7 kPa down to 0.01 kPa at various temperatures between 673 and 758 K. Experimental data were analyzed using RRKM theory. Interpretation of the fall-off curves lends support to the high-pressure Arrhenius parameters A = 10^15.42s^?1 and E_A = 259.5 kJ/mol derived from measurements made in the pressure-independent range. Decomposition of oxetan is found to occur via biradical intermediates. Data for the kinetic isotope effect were used to derive kinetic parameters for the ring-opening elementary steps in oxetan and oxetan-d₂ decomposition.     

Fire and explosion properties examinations of toluene–methanol mixtures approached to the minimum oxygen concentration

The minimum oxygen concentration (MOC) is an important safety parameter of safety for fire/explosion prevention of practical processes with fuel-air-inert mixtures. In this study, the critical fire and explosion properties stand for the explosion sensitivity (lower explosion limit (LEL), upper explosion limit (UEL)), explosion maximum indices (maximum explosion pressure (P _max), maximum rate of explosion pressure rise (dP dt ⁻¹)_max) and explosion damage degree (gas or vapor deflagration index (K _g)/St Class). These imperative parameters of various toluene/methanol mixing solvents (100/0, 75/25, 50/50, 25/75 and 0/100 vol.%) were experimentally determined within a closed spherical vessel of 20 L (20-L-Apparatus) at 101 kPa and 150 °C. Particularly, we discussed the variations both on the above characteristics and implied flammability hazard degree within different initial oxygen circumstances; the specific effects on toluene/methanol mixing solvents were to be clarified accompanied with reducing loading oxygen concentrations, gradually approaching up to the MOC in this present work. Finally, a triangle flammability diagram with the five toluene/methanol components in our testing arrangements and conditions was established for graphically indicating the dangerous fire/explosion hazard region. It has been confirmed that this study would be very useful in relevant industrial processes for a proactive loss prevention program. The experimentally derived outcomes are recommended for the inherently safer design (ISD) for forestalling any accidents from fires and explosions.     

Bioconversion of <Emphasis Type="SmallCaps">d</Emphasis>-glucose into <Emphasis Type="SmallCaps">d</Emphasis>-glucosone by Glucose 2-oxidase from <Emphasis Type="Italic">Coriolus versicolor</Emphasis> at Moderate Pressures

Glucose 2-oxidase (pyranose oxidase, pyranose:oxygen-2-oxidoreductase, EC 1.1.3.10) from Coriolus versicolor catalyses the oxidation of d-glucose at carbon 2 in the presence of molecular O₂ producing d-glucosone (2-keto-glucose and d-arabino-2-hexosulose) and H₂O₂. It was used to convert d-glucose into d-glucosone at moderate pressures (i.e. up to 150 bar) with compressed air in a modified commercial batch reactor. Several parameters affecting biocatalysis at moderate pressures were investigated as follows: pressure, [enzyme], [glucose], pH, temperature, nature of fluid and the presence of catalase. Glucose 2-oxidase was purified by immobilized metal affinity chromatography on epoxy-activated Sepharose 6B-IDA-Cu(II) column at pH 6.0. The rate of bioconversion of d-glucose increased with the pressure since an increase in the pressure with compressed air resulted in higher rates of conversion. On the other hand, the presence of catalase increased the rate of reaction which strongly suggests that H₂O₂ acted as inhibitor for this reaction. The rate of bioconversion of d-glucose by glucose 2-oxidase in the presence of either nitrogen or supercritical CO₂ at 110 bar was very low compared with the use of compressed air at the same pressure. The optimum temperature (55°C) and pH (5.0) of d-glucose bioconversion as well as kinetic parameters for this enzyme were determined under moderate pressure. The activation energy (E _a) was 32.08 kJ mol⁻¹ and kinetic parameters (V _max, K _m, K _cat and K _cat/K _m) for this bioconversion were 8.8 U mg⁻¹ protein, 2.95 mM, 30.81 s⁻¹ and 10,444.06 s⁻¹ M⁻¹, respectively. The biomass of C. versicolor as well as the cell-free extract containing glucose 2-oxidase activity were also useful for bioconversion of d-glucose at moderate pressures. The enzyme was apparently stable at moderate pressures since such pressures did not affect significantly the enzyme activity.     

Theoretical study on dithieno[3,2-b:2′,3′-d]phosphole derivatives: high-efficiency blue-emitting materials with ambipolar semiconductor behavior

Phosphole-based systems due to the unique electronic and optical properties have recently been paid much attention as optoelectronic materials. In this work, the relationship among the electronic structure, charge injection, and transport was investigated for five derivatives of dithieno[3,2-b:2′,3′-d]phosphole (systems 1–5). The structures of systems 1–5 in the ground (S₀) and the lowest singlet excited (S₁) states were optimized at the HF/6-31G* and CIS/6-31G* levels of theory, respectively. Based on these structures, electronic spectra were calculated by time-dependent density functional theory. The simulated emission peaks of five phosphole derivatives locating at the blue–green region (448–516 nm), are in good agreement with the experimental data. Compared with tris-(8-quinolinolate) aluminum (III) (Alq₃), normally used as an excellent electron transporter, systems 1–5 show a significant improvement in electron affinity (EA) due to σ*–π* hyperconjugation, which can effectively promote ability of electron injection. The small differences between λ _h and λ _e for systems 1–5 (0.06–0.14 eV) facilitate charge transfer balance, which suggests systems 1–5 can act as potential ambipolar materials. Owing to good rigidity, low-lying LUMO levels, delocalized frontier molecular orbitals, and the small reorganization energies, the five derivatives of dithieno[3,2-b:2′,3′-d]phosphole are expected to be high-efficiency blue materials in single-layer OLEDs.     

PMMA-SiO<Subscript>2</Subscript> organic–inorganic hybrid films: determination of dielectric characteristics

Organic–inorganic hybrid thin films have been prepared by a modified sol–gel route using tetraethyl orthosilicate as the inorganic (silica) source, methyl methacrylate (MMA) as the organic source, and 3-trimetoxysilylpropyl methacrylate as the coupling agent. The films were prepared by spin coating on Si (100) p-type substrates and subsequently heat-treated at 90 °C. Fourier transform infrared results reveal a set of absorption bands associated with the formation of both PMMA and SiO₂ phases in the hybrid films. Capacitance–voltage (C–V) characterization was carried out on metal-insulator-metal (MIM) and metal-insulator-semiconductor (MIS) structures, with the hybrid films as the insulator layer to evaluate the electrical properties. We present a detailed comparative analysis of the dielectric constant obtained from C–V characterization in the frequency range of 1 kHz–1 MHz. For the PMMA-SiO₂ hybrid material the dielectric constant values obtained were around 9.5 at 1 MHz which is superior to the values reported for thermally grown SiO₂ and pure PMMA materials. The interface state density for PMMA-SiO₂ on Si was approximately 10¹⁰ cm⁻², which is comparable to the standard SiO₂/Si structures. Due to the electrical behavior and low processing temperatures this hybrid dielectric is a very promising candidate for flexible electronic devices and its subsequent implementation does not require complex equipment.     

Structural, electronic and elastic properties of MAX phases M2GaN (M = Ti, V and Cr)

Based on first-principles total energy calculations, we have investigated the systematic trends for structural, electronic and elastic properties of the MAX phases M₂GaN depending on the type of M transition metal (M are Ti, V and Cr). The optimized zero pressure geometrical parameters: the two unit cell lengths (a, c), the internal coordinate z and the bulk modulus are calculated. The results for the lattice constants are in agreement with the available experimental data. The band structures show that all studied materials are electrical conductors. The analysis of the site-projected l-decomposed density of states shows that bonding is due to M d-N p and M d-Ga p hybridizations. The elastic constants are calculated using the static finite strain technique. The shear modulus C₄₄, which is directly related to the hardness, reaches its maximum when the valence electron concentration is in the range 10.5–11.0. The isotropic elastic moduli, namely, bulk modulus (B), shear modulus (G), Young's modulus (E) and Poisson's ratio (σ) are calculated in framework of the Voigt–Reuss–Hill approximation for ideal polycrystalline M₂GaN aggregates. We estimated the Debye temperature of M₂GaN from the average sound velocity. This is the first quantitative theoretical prediction of the electronic structures, and elastic constants and related properties for Ti₂GaN, V₂GaN and Cr₂GaN compounds that require experimental confirmation.     

Highly Sensitive Flexible Pressure Sensors based on Graphene/Graphene Scrolls Multilayer Hybrid Films

In recent years, flexible pressure sensors have attracted much attention owing to their potential applications in motion detection and wearable electronics. As a result, important innovations have been reported in both conductive materials and the underlying substrates, which are the two crucial components of a pressure sensor. 1D materials like nanowires are being widely used as the conductive materials in flexible pressure sensors, but such sensors usually exhibit low performances mainly due to the lack of strong interfacial interactions between the substrates and 1D materials. In this paper, we report the use of graphene/graphene scrolls hybrid multilayers films as the conductive material and a micro-structured polydimethylsiloxane substrate using Epipremnum aureum leaf as the template to fabricate highly sensitive pressure sensors. The 2D structure of graphene allows to strongly anchor the scrolls to ensure the improved adhesion between the highly conductive hybrid films and the patterned substrate. We attribute the increased sensitivity (3.5 kPa\begin{document}$ ^{-1} $\end{document}), fast response time (\begin{document}$ < $\end{document}50 ms), and the good reproducibility during 1000 loading-unloading cycles of the pressure sensor to the synergistic effect between the 1D scrolls and 2D graphene films. Test results demonstrate that these sensors are promising for electronic skins and motion detection applications.     

Steric and electronic evaluations of P(o‐tol)R2, where R is phenyl or cyclohexyl: crystal structures of SeP(o‐tol)R2

The crystal structures of SeP(o‐tol)R₂, where o‐tol is ortho‐tolyl (2‐methylphenyl) and R is Ph (phenyl), namely (2‐methylphenyl)diphenylphosphane selenide, C₁₉H₁₇PSe, or Cy (cyclohexyl), namely dicyclohexyl(2‐methylphenyl)phosphane selenide, C₁₉H₂₉PSe, were determined to aid in the evaluation of the steric and electronic behaviour of these analogous phosphane compounds. The compounds crystallized in similar monoclinic crystal systems, but are differentiated in their unit cells by a doubling of the number of independent molecules for R = Cy (Z′ = 2) and the choice of glide plane by convention. The preferred orientation for the o‐tolyl substituent obtained from the X‐ray structural analysis is gauche for R = Ph and anti for R = Cy (using the Se—P—C_ipso—C_ortho torsion angles as reference). Density functional theory (DFT) calculations showed both conformations to be equally probable and indicate that the preferred solid‐state conformer is probably due to the minimization of repulsion energies, resulting in a packing arrangement primarily featuring weak C—H…Se interactions and additional C—H…π interactions in the R = Ph structure. A detailed electronic and steric analysis was conducted on both phosphanes using Se—P bond lengths, multinuclear NMR ¹J_Se–P coupling constants, theoretical topological evaluation and crystallographic and solid‐angle calculations, and compared to selected literature examples. The results indicate that the use of the o‐tolyl substituent increases both the electron‐donating capability and the steric size, but is also dependent on whether the o‐tolyl group adopts a gauche or anti conformation. The single‐crystal geometrical data are unable to detect electronic differences between these two structures due to the somewhat large displacement parameters observed for the Se atom in the R = Cy structure.