Nitrogen Pairs Research Articles

Customized Green Energetic Tetra(Imidazole)Copper(II) Nitrate (Cu-Im) Complex/Ammonium Nitrate Co-crystal: A Novel Reactive Halogen-Free Oxidizer with Superior Stability and Decomposition Kinetics

AbstractAmmonium nitrate (AN) is the most promising affordable green oxidizer for solid propellants; however, its endothermic phase transitions and endothermic decomposition restrict its applications. This work shaded the light on multifunctional energetic complex tetra(imidazole)copper (II) nitrate (Cu-Im) with combustion enthalpy of 15.57 KJ/g as a high energy dense material, phase stabilizer, and catalyst for AN-based propellant. The Cu-Im complex was synthesized via a green simple solvent-free melt-assisting technique. As-synthesized Cu-Im complex demonstrated a highly pure crystalline structure with thermal stability up to 200 °C. Cu-Im complex was integrated into AN via an evaporative crystallization technique. The phase transitions and the thermal behavior of the developed Cu-Im complex/AN cocrystal were investigated via DSC and TGA. The Cu-Im complex stabilized the phase transition of AN up to 88.48 °C via an evolved strong hydrogen bonding system within the Cu-Im complex/AN cocrystal. Moreover, the energetic Cu-Im complex offered a significant decrease in the endothermic phase transition peaks associated with IV↔II, and II↔I by 38.81%, and 25.28% respectively. Additionally, AN strong endothermic melting was decreased by 45.32%. The Cu-Im complex converts the AN endothermic thermal decomposition peak with + 1400 J/g into an intensive exothermic peak with the release of -2241 J/g. The Cu-Im complex exhibited a superior catalytic effect via the decrease in AN decomposition temperature by 48.85 °C. Cu-Im complex offered a remarkable reduction in apparent activation energy of AN decomposition by 56.24% and 48.12% via Kissinger’s model and integral iso-conversional nonlinear Vyazovkin method (VYA) respectively. The superior catalytic performance of the Cu-Im complex was attributed to the evolution of CuO nanoparticles during its decomposition. The electron-deficient Lewis acid copper ions have a large affinity to electron lone pair of nitrogen; this effect could support the conversion of NH3 to N2 and H2. This catalytic action could boost the decomposition enthalpy of AN. Consequently, the developed Cu-Im/AN cocrystal could be considered a potential green substitute for perchlorate-based oxidizers.

Crystal-field analysis of photoluminescence from orthorhombic Eu centers and energy transfer from host to Eu in GaN co-doped with Mg and Eu

Gallium nitride co-doped with magnesium and europium shows great potential for active layers in red light emitting diode structures due to strong and sharp luminescence emission around 620 nm. In this work, sharp and intense Eu3+ luminescence lines from the excited states of the 5DJ (J = 0, 1) multiplets to the ground states of the 7FJ (J = 0, 1, 2) multiplets have been analyzed using a C2v crystal-field equivalent operator Hamiltonian. A model of Eu centers with the C2v symmetry has been proposed to be an Eu3+ complex accompanied by either a pair of nitrogen and gallium vacancies (VN-VGa) or a pair consisting of a nitrogen vacancy and magnesium impurity (VN-MgGa) in the vicinity of the Eu ion based on the crystal-field analysis, the selection rules and the observed polarization of the Eu3+ luminescence lines. Energy transfer from the host to the Eu ions under band-to-band excitation occurs through electron-hole recombination between VN with the electron-like state and VGa or MgGa with the hole-like state; these may be associated with the shallow-trapped or deep-trapped states, respectively, proposed as the energy transfer mechanism in previous literature.

Formaldehyde-Mediated Hydride Liberation of Alkylamines for Intermolecular Reactions in Hexafluoroisopropanol.

The ability of alkylamines to spontaneously liberate hydride ions is typically restrained, except under specific intramolecular reaction settings. Herein, we demonstrate that this reactivity can be unlocked through simple treatment with formaldehyde in hexafluoroisopropanol (HFIP) solvent, thereby enabling various intermolecular hydride transfer reactions of alkylamines under mild conditions. Besides transformations of small molecules, these reactions enable unique late-stage modification of complex peptides. Mechanistic investigations uncover that the key to these intermolecular hydride transfer processes lies in the accommodating conformation of solvent-mediated macrocyclic transition states, where the aggregates of HFIP molecules act as dexterous proton shuttles. Importantly, negative hyperconjugation between the lone electron pair of nitrogen and the antibonding orbital of amine's α C-H bond plays a critical role in the C-H activation, promoting its hydride liberation.

Exclusive and Switchable Superoxide Radical Generation by O2-Capture-Based Electron Transfer and Supramolecular Assembly.

Type-I photosensitizers (PSs) can generate free radical anions with a broad diffusion range and powerful damage effect, rendering them highly desirable in various areas. However, it still remains a recognized challenge to develop pure Type-I PSs due to the inefficiency in producing oxygen radical anions through the collision of PSs with nearby substrates. In addition, regulating the generation of oxygen radical anions is also of great importance toward the control of photosensitizer (PS)activities on demand. Herein, a piperazine-based cationic Type-I PS (PPE-DPI) that exhibits efficient intersystem crossing and subsequently captures oxygen molecules through binding O2 to the lone pair of nitrogen in piperazine is reported. The close spatial vicinity between O2 and PPE-DPI strongly promotes the electron transfer reaction, ensuring the exclusive superoxide radical (O2 •-) generation via Type-I process. Particularly, PPE-DPI with cationic pyridine groups is able to associate with cucurbit[7]uril (CB[7]) through host-guest interactions. Thus, supramolecular assembly and disassembly are easily utilized to realize switchable O2 •- generation. This switchable Type-I PS is successfully employed in photodynamic antibacterial control.

Tuning the steric hindrance of alkylamines: a predictive model of steric editing of planar amines.

Amines are one of the most prevalent functional groups in chemistry. Perhaps even more importantly, amines represent one of the most ubiquitous moieties within the realm of bioactive natural products and life-saving pharmaceuticals. The archetypal geometrical property of amines is their sp3 hybridization with the lone pair of nitrogen occupying the apex of the pyramid. Herein, we present a blueprint for quantifying the properties of extremely sterically hindered alkylamines. These amines reach planarity around the nitrogen atom due to the excessive steric hindrance, which results in a conformational re-modeling of the amine moiety. Crucially, the steric properties of amines are characterized by the %V Bur index, which we show is a general predictive parameter for evaluating the properties of sterically hindered amines. Computational studies on the acidic nature and the reactivity of organometallic Au and Pd complexes are outlined. Density functional theory calculations permit for predictive catalysis, ordering the mapping of extremely hindered tertiary amines by employing artificial intelligence via machine learning. Overall, the study outlines the correlation between the unusual geometry and the key thermodynamic and kinetic properties of extremely hindered alkylamines. The steric hindrance, as quantified by %V Bur, is the crucial factor influencing the observed trends and the space required to accommodate sterically hindered tertiary amines.

Free-Base Corrole Anion.

Free-base corroles have long been known to be acidic, readily undergoing deprotonation by mild bases and in polar solvents. The conjugate base, however, has not been structurally characterized until now. Presented here is a first crystal structure of a free-base corrole anion, derived from tris(p-cyanophenyl)corrole, as the tetrabuylammonium salt. The low-temperature (100 K) structure reveals localized hydrogens on a pair of opposite pyrrole nitrogens. DFT calculations identify such a structure as the global minimum but also point to two cis tautomers only 4-7 kcal/mol above the ground state. In terms of free energy, however, the cis tautomers are above or essentially flush with the trans-to-cis barrier so the cis tautomers are unlikely to exist or be observed as true intermediates. Thus, the hydrogen bond within each dipyrrin unit on either side of the molecular pseudo-C2 axis through C10 (i.e., between pyrrole rings A and B or between C and D) qualifies as or closely approaches a low-barrier hydrogen bond. Proton migration across the pseudo-C2 axis entails much higher activation energies >20 kcal/mol, reflecting the relative rigidity of the molecule along the C1-C19 pyrrole-pyrrole linkage.

Effect of pendent alkyl group of ancillary ligand on molecular structures of new metal(II)-2, 4-dinitro benzoate complexes- spectral, structural and photoluminescence studies

A series of new metal(II) complexes having general formulae, [M (2, 4-dnb)2(L)2] (where 2, 4-dnbH = 2,4-dinitro benzoic acid; M = Co(1), Ni(2), Zn(3) and Cd(4), L = methyl hydrazine carboxylate (mc); M = Co(5), Ni(6), Zn(7) and Cd(8), L = ethyl hydrazine carboxylate (ec)) were prepared and characterized using elemental analysis, UV-Visible, FT-IR, emission spectroscopic and powder XRD techniques. Single crystal X-ray study for 3 and 7 shows that metal ion, in both complexes, adopts distorted MN2O4 geometry arising from a pair of N,O-chelating methyl/ethyl hydrazine carboxylate ligands at equatorial sites and monodendate 2, 4-dnb ions at the axial sites. The pair of nitrogen (or) oxygen atoms of chelating ligands (L) are trans positioned in 3 whereas they are cis positioned in 7. All the complexes exhibit photoluminescence property. On heating all the complexes show explosive nature of decomposition.

Synthesis and Computational Studies of pyrazole-chromeno[2,3-d]pyrimidines: As a novel Hg2+ fluorescent sensor

The synthesis of pyrazole-chromeno[2,3-d]pyrimidines through the three-component condensation reaction of salicylaldehyde, pyrazolone derivatives, and barbituric acid has been reported in the presence of Fe3O4@SiO2@Pr-SO3H under reflux conditions. Fe3O4@SiO2@Pr-SO3H as a heterogeneous magnetic catalyst is a green, effective and reusable magnetic nanoparticle, which can readily separate by an external magnet. The sensing ability of 4b was tested by adding various cations by fluorescence emission spectroscopy. It was shown outstanding Hg2+ fluorescence activity among various competing cations with a detection limit of 8.5 × 10−7 M. DFT results indicated two intramolecular O–H⋯O and C–H⋯O hydrogen bonds in the most stable configuration of the pyrazol-chromeno[2,3-d]pyrimidine. Natural bonding orbital analysis, Bader Atom in Molecule theory, and frequency analysis were employed to confirm the proposed intramolecular hydrogen bonds. The pyrazol-chromeno[2,3-d]pyrimidine complex with Hg2+ ion has two different Hg2+ coordination. The strongest interaction between ligand and metal is due to the delocalization of electrons from lone donor pairs of nitrogen and oxygen atoms to the empty LP* of transition metals as an acceptor.

Multiple resonance type thermally activated delayed fluorescence by dibenzo [1,4] azaborine derivatives.

We studied the photophysical and electroluminescent (EL) characteristics of a series of azaborine derivatives having a pair of boron and nitrogen aimed at the multi-resonance (MR) effect. The computational study with the STEOM-DLPNO-CCSD method clarified that the combination of a BN ring-fusion and a terminal carbazole enhanced the MR effect and spin-orbit coupling matrix element (SOCME), simultaneously. Also, we clarified that the second triplet excited state (T2) plays an important role in efficient MR-based thermally activated delayed fluorescence (TADF). Furthermore, we obtained a blue–violet OLED with an external EL quantum efficiency (EQE) of 9.1%, implying the presence of a pronounced nonradiative decay path from the lowest triplet excited state (T1).

Engineering the electronic structure of Ni3FeS with polyaniline for enhanced electrocatalytic performance of overall water splitting

Developing highly efficient and stable electrocatalysts for oxygen evolution reaction is of significant importance for applications in energy conversion and storage. Modulation of electronic structure of catalysts is critical for improving the performance of the resulting electrodes. Here, we report a facile way to engineer the electronic structure of Ni3FeS by coating a thin polyaniline (PANI) layer for improving electrocatalytic activity for overall water splitting. Experimental investigations unveil that the strong electronic interactions between the lone electron pairs of nitrogen in PANI and d orbitals of iron, nickel in Ni3FeS result in an electron-rich structure of Ni and Fe, and consequently optimize the adsorption and desorption processes to promote the OER activity. Remarkably, the resulting PANI/Ni3FeS electrode exhibited much enhanced OER performance with a low overpotential of 143 mV at a current density of 10 mA·cm−2 and good stability. Promisingly, coupled with the reported MoNi4/MoO2 electrode, the two-electrode electrolyzer achieved a current density of 10 mA·cm−2 with a relatively low potential of 1.55 V, and can generate oxygen and hydrogen bubbles steadily driven by a commercial dry battery, endowed the composite electrocatalyst with high potential for practical applications.

Ultrasensitive detection of Cr(VI) using a novel SERS optical fiber probe modified by dual-functional methimazole

Ultrasensitive detection of highly toxic Cr(VI) is of paramount importance as trace amount of Cr(VI) will result in inevitable deterioration to human health and the environment. In this work, a novel methimazole-functionalized SERS optical fiber probe was used for the first time for Cr(VI) determination with ultrahigh sensitivity. A special functionalization process of methimazole was designed after successful fabrication of silver coated fiber probe via a SnCl 2 -sensitized solvothermal method. Dual functional methimazole guaranteed ultrahigh sensitivity and good stability of the SERS fiber probe for Cr(VI) detection. On one hand, methimazole functions as a Raman reporter which exhibits SERS peak intensity decline in the presence of Cr(VI). On the other hand, methimazole acts as an oxidation inhibitor via coordinating with silver atoms through the lone pair of nitrogen and sulfur atoms. The optimized SERS fiber probe not only presents good stability and excellent reproducibility, but also exhibits ultrahigh sensitivity (10 −11 M) which exceeds SERS or other techniques for Cr(VI) determination reported so far. • Methimazole-functionalized SERS fiber probe was synthesized for the first time. • Methimazole acts as Raman reporter with ultrahigh sensitivity of 10 −11 M for Cr(VI). • Methimazole also functions as oxidation inhibitor of silver with good stability.

Architecting the AuPt alloys for hydrazine oxidation as an anolyte in fuel cell: Comparative analysis of hydrazine splitting and water splitting for energy-saving H2 generation

Replacing the kinetically sluggish anodic oxygen evolution reaction (OER) with hydrazine (N2H4) oxidation reaction (HzOR) could be the effective approach for achieving energy-saving hydrogen (H2) fuel production in a water electrolyzer system. Thus, developing the efficient HzOR electrocatalysts, combined with the cathodic H2 evolution reaction (HER) is of vital importance for the high-rate H2 fuel generation as well as for the advancement of a N2H4 fuel cell. Herein, we utilized a facile integrated process of pulsed laser irradiation and sonochemical process to synthesize AuPt alloys by the irradiation of laser to a mixture of Au/Pt solution in methanol/DI water in varied proportions. The AuPt alloy plays a key role in the chemisorption of N2H4 on its surface, forming a dative bond involving electrons of the lone pair of nitrogen in N2H4 and empty orbitals of Pt in the alloy, indicating its high intrinsic activity against HzOR. The optimal composition of Au1Pt8 electrode demonstrates outstanding characteristics of HER with an ultralow overpotential of 26 mV at 10 mA cm−2 in alkaline medium while requiring 502 mV to attain 10 mA cm−2 for HzOR in 0.5 M N2H4/1.0 M KOH electrolyte. In addition, the assembled overall N2H4 splitting electrolyzer cell using Au1Pt8 alloys as both anode and cathode requires cell voltage of only ~0.172 V at 10 mA cm−2 with tremendous stability over 10 h, which is much lower than the voltage of 1.773 V required for the overall water splitting electrolyzer. The present study validates the feasibility of AuPt alloys for stimulating N2H4 fuel cells in the future to achieve both electrical energy generation and high-rate H2 fuel production.

O:H[sbnd]N bond cooperativity in the energetic TATB under mechanical and thermal perturbation

Incorporating the mechanical and thermal perturbations to the Raman spectroscopy has enabled resolution to the response of the individually segmented CN2H:2ONC interactions for the 1,3,5-triamona, 2,4,6-trinitorbenzene (TATB, C6H6N6O6) assembly with “:” representing the electron lone pair of nitrogen or oxygen at the molecular interfaces. It is uncovered that: (i) the NH bond possesses the negative compressibility and negative thermal expansivity; (ii) the C(N2H) bond undergoes both compressive and thermal contraction; (iii) the (O,N):H and rest interactions follow the regular compressibility and thermal expansivity. The unusual response of the HN bond in TATB to perturbation is the same to the HO segment of the O:HO bond of water ice and the N:HO bond of the cyclo-N5−:4H3O+ complexes, which proves that the O:⇔:N repulsion couples the inter-(O:H) and the intramolecular (HN) interactions and drives the O:HN to relax cooperatively in the segmental length, energy, and vibration frequency when subjecting to perturbation. Discoveries demonstrate not only the significance of molecular coupling interactions but also the power of mechanical and thermal perturbations that enable detailed information of individual bond relaxation, advancing the engineering in chemistry and devising of functional molecular materials.

Fe-Co controlled super-hygroscopic hydrogels toward efficient atmospheric water harvesting.

Extracting atmospheric moisture for freshwater production is an appealing way to mitigate the global water crisis. However, the low moisture sorption capacity and high desorption temperature are the major bottlenecks for efficient atmospheric water harvesting. Herein, we develop a transition metal super-hygroscopic hydrogel by an economical strategy, which is constructed through a facile coordination between metal salts and ethanolamine. When the empty electron orbital of the metal ion is coordinated with the lone electron pair of nitrogen or oxygen atom, the water active sorption site is formed. A single water layer is bonded on the sites by a coordination effect, followed by physical interaction with water to form multi-layer structures. The Fe and Co ions in the hydrogel function as dual sorption sites to capture moisture, which can harvest additional water by the synergistic effect of bimetals. As a result, the bimetal hydrogel contributes to a high water uptake of 5.22 g g-1 at 95% RH, triggering the desorption process by one solar intensity due to its low desorption temperature (≤50 °C).

Synthesis of Open‐Cage Fullerenes with Pyrrole, Pyrrolone, Pyridinone, Iminofuran, and Pyranone Fragments Embedded on the Rim of the Orifice

AbstractAn open‐cage fullerene derivative with a pyranone and a diiminopentanone moiety was prepared. Further reaction with aniline could convert the pyranone moiety into a pyrrole moiety through the pyridinone moiety as an intermediate. During the process, decarboxylation and dehydroxylation aromatization reactions also took place on the diiminopentanone moiety and the two adjacent hydroxyl groups, thus forming iminofuran or pyrrolone moiety on the rim of the open‐cage fullerene. Protonation experiment showed that the imino nitrogen atom on the rim of the orifice is more basic than the pyrrole nitrogen atom. The lone pair of the pyrrole nitrogen is partially conjugated with the π system of the fullerene cage as shown by single crystal X‐ray structures.

Directed Gas-Phase Formation of Aminosilylene (HSiNH2; X1A'): The Simplest Silicon Analogue of an Aminocarbene, under Single-Collision Conditions.

The aminosilylene molecule (HSiNH2, X1A')-the simplest representative of an unsaturated nitrogen-silylene-has been formed under single collision conditions via the gas phase elementary reaction involving the silylidyne radical (SiH) and ammonia (NH3). The reaction is initiated by the barrierless addition of the silylidyne radical to the nonbonding electron pair of nitrogen forming an HSiNH3 collision complex, which then undergoes unimolecular decomposition to aminosilylene (HSiNH2) via atomic hydrogen loss from the nitrogen atom. Compared to the isovalent aminomethylene carbene (HCNH2, X1A'), by replacing a single carbon atom with silicon, a profound effect on the stability and chemical bonding of the isovalent methanimine (H2CNH)-aminomethylene (HNCH2) and aminosilylene (HSiNH2)-silanimine (H2SiNH) isomer pairs is shown; i.e., thermodynamical stabilities of the carbene versus silylene are reversed by 220 kJ mol-1. Hence, the isovalency of the main group XIV element silicon was found to exhibit little similarities with the atomic carbon revealing a remarkable effect not only on the reactivity but also on the thermochemistry and chemical bonding.

Enhanced sensitivity of caterpillar-like ZnO nanostructure towards amine vapor sensing

Owing to the uprising health issues due to amine exposure, this work has been taken up to design a novel caterpillar-like ZnO nanoarchitecture using a combined hydrothermal and Forcespinning® technology for sensing amine vapor. This study presents two different approaches to investigate the sensing behavior of the caterpillar-like ZnO nanostructure compared to both commercially available ZnO nanoparticles and laboratory synthesized carbon/ZnO composite fibers. It is found that ZnO caterpillar-like nanostructure shows the best performance owing to its highest surface to volume ratio. Electrochemical investigations suggest maximum enhancement in current density from the caterpillar-like ZnO nanostructure on amine exposure due to the increased involvement of electron pair of nitrogen owing to its high hydroxyl concentration. Photoluminescence spectroscopy depicts defect induced blue emission owing to defect in native ZnO nanoparticles which quenches on amine exposure. The quenching has been found to be monotonic over the entire range of exposed n-propyl amine (NPA, 0–500 ppm) and attributed to defect annihilation upon exposing to amine vapor. Optical detection of NPA by the caterpillar-like ZnO nanostructure based on emission quenching shows a linear response in the studied NPA concentration range with a detection limit (LOD) of 12.54 ppm. Our results demonstrate the importance of structure, morphology and architecture of ZnO for gas sensing activity.

On the mechanism underlying the elimination of nitrogen-oxygen shallow thermal donors in nitrogen-doped Czochralski silicon at elevated temperatures

Nitrogen-doped Czochralski (NCZ) silicon has been a base material for integrated circuits. The interaction between nitrogen (N) and interstitial oxygen (Oi) atoms in the low temperature regime (300–650 °C), which leads to N–O complexes in the form of NOx (x = 1, 2, or 3), forms a series of shallow thermal donors (denoted as N–O STDs). Such N–O STDs are detrimental to the stability of electrical resistivity of NCZ silicon. In this work, we have experimentally investigated the elimination of N–O STDs in NCZ silicon by means of conventional furnace anneal (CFA) and rapid thermal anneal at elevated temperatures ranging from 900 to 1250 °C, aiming to explore the underlying mechanism. It is found that most of the N–O STDs formed in NCZ silicon can be eliminated by a very short period of anneal at the aforementioned temperatures, providing solid evidence for the viewpoint that the elimination of N–O STDs is ascribed to the decomposition of NOx complexes. Somewhat unexpectedly, the residual N–O STDs are much more after the 1250 °C/2 h CFA than after the 900 °C/2 h or 1000 °C/2 h counterpart, which is found to be due to the fact that more nitrogen pairs [(N2)s] are remaining after the 1250 °C/2 h CFA. It is proposed that most of the (N2) atoms are involved in the growth of grown-in oxide precipitates during the 900 or 1000 °C/2 h CFA. The first-principles calculations and molecular dynamics simulation indicate that the elimination of N–O STDs is essentially ascribed to the destruction of “NO ring” that is the core of NOx complexes. Furthermore, based on the experimental and theoretical results, we have made a thorough thermodynamic analysis to account for the details of elimination of N–O STDs as revealed in this work. It is believed that our experimental and theoretical studies have gained more insight into the N–O STDs in NCZ silicon.

Single, double and triple cobalt atoms confined in 2D regular framework for oxygen electrocatalysis

Many natural metalloenzymes consist of multi-nuclear metal sites. The multiple metal centers trigger a cooperative catalytic effect that decreases the reaction energy barrier. However, it remains a grand challenge in mimicking the metalloenzymes in heterogeneous catalysts. C2N is an emerging 2D material with a predictive regular holey framework. Its large hole with a diameter of ~8.35 Å contains three pairs of pyridinic nitrogen, allowing the capture of transition metals from single to triple atoms. Based on quantum chemistry calculations, we find that the introduction of double (Co2@C2N) and triple cobalt (Co3@C2N) atom clusters turns C2N nanosheet from semiconducting into a nearly metallic state. The confined double or triple atoms can work cooperatively toward oxygen reduction and evolution reaction (ORR and OER). Impressively, with the activation barrier of 0.57 eV, Co3@C2N is a competitive novel candidature that can substitute bulk Pt catalyst (~0.80 eV). In-depth analysis indicates that the formation of an oxo-doped field environment is the key to realize efficient oxygen electrocatalysis.

Atomistic Understanding of the Ferroelectric Properties of a Wurtzite‐Structure (AlN)n/(ScN)m Superlattice

For ferroelectric applications, wurtzite (WZ)‐phase (Al,Sc)N is investigated using ab initio calculations. The key ferroelectric properties, such as the ferroelectric switching barrier and spontaneous polarization, are examined in (AlN)n/(ScN)m superlattice (SL) structures by varying the ScN fraction, and compared with an (Al,Sc)N solid solution (SS). The reduction of the switching barrier is dominated by the local structural instability rather than the flattening of the buckled monolayer composed of metal–nitrogen pairs in WZ‐stacking. This argument is supported by the doping effects of other metal elements as well as the reduction of the switching barrier in the SL, which does not accompany the flattening of the buckled monolayer. The decrease in the spontaneous polarization along the ScN fraction is explained by structural parameters (the in‐plane area and the buckling parameter) and the Born effective charge (BEC). The slight decrease in the spontaneous polarization in the SL is attributed to the larger increase in the in‐plane area rather than the BEC. In contrast, the decrease in the buckling parameter in the SS is suggested to more significantly reduce the spontaneous polarization along the ScN fraction.