Valence Shell Research Articles

Exploring Interatomic Electron Transfer and Metal-Ligand Binding Mechanism in Trimethylenemethane Iron Tricarbonyl: Insights from Potentials per Electron and Corresponding Force Density Fields.

This study employs an analysis of the per-electron potentials and the superposition of the electrostatic and kinetic force fields, Fes(r) and Fk(r), and the gradients of the potential energy and one-electron densities to investigate the binding mechanism in trimethylenemethane iron tricarbonyl complex (TMM)Fe(CO)3. Our approach permits the delineation of the "ligand-binding" force field generated by the metal nucleus but partially operating within the ligand atoms. A mechanical rationale for metal-ligand interactions is thus presented: In the corresponding area, the attractive force Fes(r) provides the backdrop against which the homotropic static force (r) and the heterotropic kinetic force Fk(r) exert attractive and repulsive influences, respectively, toward the metal nucleus on a portion of the electrons belonging to the ligand atoms. This area thus represents electron sharing, which emerges as a quantum chemical response against the metal-to-ligand electron transfer. It has been demonstrated that the response is facilitated by the decreased potential energy density in the vicinity of the interatomic surface. Our findings indicate that the polar coordination bonds in (TMM)Fe(CO)3 exhibit notable quantum chemical responses. However, the previously described nonbonded contact also features an unexpectedly pronounced response, despite the absence of a bond path. It can be proposed that the unforeseen response is a consequence of the formation of the 18-electron, closed valence shell, rather than an indication of the establishment of an organometallic chemical bond.

Unraveling latent affinity of strategically designed histidine-rich biosurfactant via tannery waste bio-upcycling in environmentally-relevant lignin removal from pulp and paper industry effluent

Bioremediation of pulp and paper industry (PPI) effluent is hindered due to biorefractory lignin. Herein, we demonstrate a lignin-specific designer biosurfactant with synergistic binding sites for enhanced lignin removal from PPI effluent. The histidine rich-cationic lipoprotein biosurfactant (HR-CLB) was synthesized by Bacillus tropicus using tanning industry solid waste, animal fleshing by de novo substrate-dependent synthesis pathway. Interestingly, the HR-CLB anchored functionalized carbon (HR-CLBAFC) demonstrated a high lignin sequestration capacity of 93.2 mg/g HR-CLBAFC at optimized time, 60 min; pH, 5; temperature, 45 °C; and mass of HR-CLBAFC, 1.0 g. The sequestration was confirmed by HR-SEM, UV–Vis., FT-IR, and WCA analyses. The isotherm studies revealed the involvement of Freundlich isotherm (regression coefficient, R2: 0.988) in regulating lignin sequestration onto HR-CLBAFC with a Freundlich constant (Kf) of 16.46 ((mg/g)(L/mg)1/n). Moreover, the kinetics studies divulged the contribution of the pseudo-second-order kinetic model (R2: 0.992) in regulating the dynamic mechanism of lignin sequestration onto HR-CLBAFC with a rate constant (k2) of 0.00022 g/mg min. Additionally, the thermodynamics studies discovered a positive Gibbs free energy (ΔG: +170 kJ/mol) and entropy (ΔS°: +130 kJ/mol), indicating the involvement of chemical interaction during the sequestration. Furthermore, the mechanistic study confirmed the role of an incomplete valence shell of nitrogen in histidine centers of HR-CLB in regulating electrostatic interaction with lignin molecules during the sequestration process. Subsequently, the HR-CLBAFC applied for lignin sequestration from the real-time PPI effluent demonstrated an outstanding sequestration efficiency (>99.4%), confirming the unequivocal potential of the HR-CLBAFC matrix in lignin sequestration from real-time PPI effluent.

An investigation of the electrochemical characteristics of NiO-Co3O4/graphite/PVDF composites for the development of a supercapacitor with ultrahigh stability

Abstract Supercapacitor is a groundbreaking electrical energy storage technology that falls between batteries and dielectric capacitors which has undergone significant progress in recent years. Among the several elements influencing a supercapacitor's capacitance, the choice of electrode materials plays a crucial role. Nanomaterials formed from transition metal oxides with incorporated 3-D graphite are said to possess high capacitance, conductivity, increased area of active site, distinct redox properties, and several valence shells, making them an appropriate material for electrode synthesis. Therefore, in this study, three composites of NiO and Co3O4 are prepared in the ratio 2:8, 3:7 and 4:6 using facile sol-gel method. To the prepared composites, graphite and PVDF are added in equal quantities. The resultant samples are characterized using XRD, SEM, FTIR and UV-Vis spectroscopy. The samples are further integrated on an FTO electrode and subjected to CV, GCD and EIS for electrochemical study. The highest specific capacitance is obtained for NiO and Co3O4 composite in the ratio 3:7 and is equal to 156.66F/g at a sweep rate of 10 mV/s. This material is further used for a two-electrode study to check the feasibility of a symmetric solid-state device, which demonstrated a specific capacitance of 36F/g with 100% capacitive retention.

Sr2B8: A new member to the [formula omitted] and π double aromaticity

In this paper, we have employed the CALYPSO method to perform structure search on the Sr2Bn0/− (n = 1–12) clusters, resulting in the determination of the global energy minimum structures. Moreover, we have conducted PES simulations on each of the obtained structures with the aim of comparing them to experimental data. Upon comparison, we have identified a relatively more stable inverse sandwich structure Sr2B8, and have conducted an analysis of its internal atomic bonding characteristics. The results indicate that there is a significant transfer of valence electrons from the Sr atoms to the B atoms, leading to the occupied orbitals being predominantly contributed by the valence shell of the B atoms. The B atoms are interconnected by covalent single bonds to form a ring structure, with the two Sr atoms positioned on either side of the B ring, binding to the ring through ionic bonds. The entire Sr2B8 exhibits double aromaticity by the delocalized σ occupied orbitals and the delocalized π occupied orbitals.

Determining the binding mechanism of B12N12(Zn) with CH4, CO, CO2, H2O, N2, NH3, NO, NO2, O2, and SO2 gases

In this study, an exploration of molecular interactions between CH4, CO, CO2, H2O, N2, NH3, NO, NO2, O2, SO2 gas molecules and B12N12(Zn) nanocage is conducted using advanced computational techniques, ωB97XD/Def2tzvp, unraveling fundamental behaviors. Employing global optimization methods and sophisticated tools like the bee colony algorithm in ABCluster software, the research offers insights into energy adsorption processes, confirming molecular stability through DFT calculations. The determination of electrophilicity index values through conceptual DFT analysis sheds light on relative reactivity levels and charge transfer phenomena, emphasizing that in some cases the nanocage's role as a potential electron acceptor. Natural bond analysis of charge transfer direction and valence shell orbital interactions enriches understanding, supported by comprehensive parameter compilation and critical point visualization. Further confirmation of interaction types and strengths through G(r)/V(r) ratios and ELF values enhances comprehension through quantum theory of atoms in molecule analysis. Ultimately, this study contributes significantly to computational chemistry, laying foundations for molecular design and engineering advancements. It sets the stage for future progress in materials science and catalysis, promising innovation in sustainable energy solutions and technological development.

An aqueous symmetric supercapacitor with wide window and high energy density using redox electrode of Cu-Al-layered double hydroxides and λ-manganese dioxide.

Manganese oxide is a potential agent in the field of energy storage owing to its changeable redox characteristics, high theoretical specific capacitance and valence shells for charge transfer. On the other hand, due to huge surface area, affordability, customisable composition, layered structure and high theoretical specific capacitance, layered double hydroxides, or LDHs, have drawn a lot of interest. This study employs a three-electrode setup to investigate the supercapacitive performance of λ-manganese dioxide/Cu-Al LDH composite at different compositional ratios. To enhance the adhesive and conductivity capabilities, 10% of CNT additive and PVDF binder are added for the composites. Out of all the composites, the one with the greatest weight percentage of λ-manganese dioxide shows the best electrode performance with a superior specific capacitance of 164 F/g at a scan rate of 10mV/s. Additionally, using a symmetrical two-electrode setup, the best-performing electrode is examined. The result shows an exceptional potential window of 2.7V in a basic electrolyte, a power density of 4.04kW/kg at 3 A/g, an energy density of 20.32 Wh/kg at 1 A/g, and a specific capacitance of 37 F/g.

Synergism of carbonaceous additives in engineering of the supercapacitive performance of α-and λ-phases of manganese oxide

Owing to the presence of valence shells for charge transfer, a high theoretical specific capacitance, and variable redox properties, MnO2 appears as a promising agent in the realm of energy storage. Crystallographic structures of manganese oxide (MnO2), a transition metal oxide, play a crucial role in determining its capacitive behavior by controlling the ion intercalation and double-layer formation. In this work, two different phases of MnO2 were synthesized using the facile chemical reduction method and biological method, say α-MnO2 and λ-MnO2. The phases were incorporated with different carbonaceous additives including GO and CNT while maintaining a constant weight ratio of 8:1:1 between active materials (MnO2), additive, and PVDF binder. Among different composites formed, the best electrode performance is demonstrated by λ-MnO2/CNT/PVDF composite with an excellent specific capacitance of 356 F/g at a scan rate of 1 A/g. Moreover, the best-performing electrodes are investigated with a symmetrical two-electrode system yielding a wide potential window of 1.8V with an outstanding power density of 13.5 KW/Kg at 5 A/g and an energy density of 53.78 Wh/Kg at 1A/g having a specific capacitance of 190 F/g.

Microscopic derivation of the octupole magic numbers from symmetry considerations

The valence shells of medium mass and heavy nuclei consist of the normal and the intruder parity orbitals; therefore the Shell Model SU(3) symmetry of Elliott cannot have a straightforward application on them. The proxy-SU(3) can be applied instead, since it uses a unitary transformation, meant to act on the intruder orbitals to alter their parity and transform them to their proxy orbitals. The inverse unitary operator transforms the proxy orbitals back to the intruder ones. The highest weight proxy-SU(3) irreducible representations (irreps) allows one to determine the corresponding number of occupied intruder orbitals. In this way we obtain the so-called ‘octupole magic numbers’ 32, 56, 90, 134 and 194 without any parameter. Moreover, the proxy (unitary) mapping and its inverse transformation make the proxy space eligible for the calculation of observables associated with octupole deformation and the relevant treatment of mixed parity states. The implemented study validates the proxy-SU(3) approach with respect to the octupole deformation and suggests its full applicability in the corresponding mass regions.

A theoretical model considering the photochemical and photothermal behavior of arc radiation-induced gassing materials ablation

In this study, we introduce a theoretical model designed to explore both the photochemical and photothermal behavior of arc plasma radiation-induced ablation in gassing materials. We employ time-dependent density functional theory to analyze the photochemical behavior, while reactive force field molecular dynamics are used to explore the photothermal behavior. The phenomena, behavior and consequences of valence shell electronic excitation are analyzed in terms of ultraviolet (UV) absorption, electron-hole distribution, and Mayer bond order. Based on the photochemical findings, we apply a periodic electric field that corresponds to the vibration frequency of the permanent dipole moment to simulate infrared radiation, and convert UV photon energy into atomic kinetic energy to analyze UV radiation. This atomic-scale insight into photothermal behavior enables us to identify the final composition of ablation gases, including H2, CO, H2O, NH3, as well as specific cyanides, amines, and hydrocarbons. The results of the theoretical model and physical properties indicate that the concentration of hydrogen-containing gases in the ablation gas significantly affects the arc extinguishing capabilities of different polymers. Finally, we propose modification schemes suitable for polymers in power circuit breakers, considering UV absorption and smoke black production. Additionally, we present the potential application of theoretical models for calculating the ablation rate, necessitating further in-depth re-search.

Valence shell electronically excited states of 1-phenylimidazole and 1-benzylimidazole

The valence shell electronically excited states of 1-phenylimidazole and 1-benzylimidazole have been studied by employing synchrotron radiation to measure the absolute photoabsorption cross-section of each molecule, from threshold up to an energy of 10.8 eV. Assignments have been proposed for some of the broad absorption bands using calculated transition energies and oscillator strengths. Natural transition orbital plots have allowed the Rydberg and/or valence character of the electronically excited states to be assessed. Some of the calculated transitions in 1-benzylimidazole and 1-phenylimidazole have initial and final orbitals that are analogous to those of transitions in the isolated constituent rings of imidazole and benzene. Other mixed Rydberg/valence transitions, especially those leading to some of the low energy electronically excited states in 1-phenylimidazole, have an initial orbital located on the imidazole ring while valence character in the final orbital is localised on the phenyl ring. Thus, photoexcitation results in charge transfer from the donor site (imidazole) to the acceptor (the phenyl ring) in the nascent ion core of the Rydberg state. In both 1-benzylimidazole and 1-phenylimidazole the lowest energy excited state arises from a transition analogous to the 1e1g → 1e2u 1B2u electric dipole-forbidden transition in benzene.

PENGEMBANGAN MEDIA BERBASIS KOMPUTER UNTUK PEMBELAJARAN KIMIA KELAS XI PADA SEKOLAH MENENGAH ATAS

Difficulty learning abstract consepts in material forms of the molecule based on the theory of electron domain and molecular hybridization in the formation of simple covalent coumpounds involving electron is verry small in size. With conventional learning to use the media shaped balloons and images/charta make their experience misconceptions. Make use of computer assisted animations media adobeflash program. The program is able to help students discover and explore the concepts of learning materials to animate the process of formation of the molecules of the compound geometry. The program is easy to obtain and can be used on all computers. Material forms of molecules according to VSEPR theory (valence shell electron pair repulsion) and Hybridization theory contained in the computer based media is aimed at helping students learn to achieve mastery of core competencies which are already contained in the syllabus set by time. Products are developed in accordance with the educational technology area abstract include students in determining the geometry of the steps forming the molecules of the compound. The stages are carried out in the development of media, namely: design learning, create computer based animation media, validate products with product testing. Advice of expert material/content, media expert, design expert, and data from trials of the target group to be enter performance improvement products. Based on the results of the expert validation and testing of the target group can be concluded that the computer –based instructional media products on the molecular forms of material at Senior High School chemistry in particular at ninth grade IPA (Natural Sciences). With regard to these results the school, especially Senior High School 8 Batanghari media products in order to incorporate this learning into the school website that can be accessed by the wider media users for further development. Keyword: Development, Computer based Media, Molecular Forms.

Influence of the use of 3D printing technology for teaching chemistry in STEM disciplines

AbstractTeachers can create engaging learning environments in engineering courses through pedagogical innovation using Information and Communication Technologies (ICT). Introductory chemistry courses in Science, Technology, Engineering and Mathematics (STEM) disciplines typically include the study of molecular models and periodic properties, which are inherently visual concepts. Unfortunately, these concepts are often taught using two‐dimensional drawings, although three‐dimensional (3D) printing offers an engaging approach to learning chemistry in these disciplines. Undergraduate engineering students are provided with modelling software and a 3D printer, allowing them to construct 3D models of basic Valence Shell Electron Pair Repulsion theory shapes using polylactic acid. The results of this research showed that the average score of the students in the control group was lower than that of the students in the 3D technology group. This research has found that the learning curve for modelling and the time required for printing are high, limiting the practical application of this exercise in student laboratory classes. However, in an appropriate environment, 3D printing technology has the potential to be a valuable tool for teaching and learning molecular models and periodic properties of chemistry courses in STEM disciplines.

Systematic study of cluster radioactivity within the generalized liquid drop model* *Supported by the National Natural Science Foundation of China (12175170), Hubei Provincial Natural Science Foundation of China (2023AFB035), Hunan Outstanding Youth Science Foundation (2022JJ10031), and Natural Science Research Project of Yichang City (A23-2-028)

Cluster radioactivity is studied within the generalized liquid drop model (GLDM), in which the shell correction energy, pairing energy, and cluster preformation factor are considered. The calculations show significant improvements and can reproduce the experimental data within a factor of 8.04 after considering these physical effects. In addition, the systematic trend of the cluster preformation factors is discussed in terms of the scheme to study the influence of the valence proton-neutron interaction and shell effect on cluster radioactivity. It is found that is linearly related to . This is in agreement with a recent study [L. Qi et al., Phys. Rev. C 108, 014325 (2023)], in which , obtained using different theoretical models and treatment methods than those used in this study, also had a linear relationship with . Combined with the work by Qi et al., this study suggests that the linear relationship between and is model-independent and both the shell effect and valence proton-neutron interaction play essential roles in cluster radioactivity. An analytical formula is proposed to calculate the cluster preformation factor based on the scheme. In addition, the cluster preformation factors and the cluster radioactivity half-lives of some heavy nuclei are predicted, which can provide a reference for future experiments.

Valence shell electronically excited states of norbornadiene and quadricyclane.

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1-11A1 (3sa1 ← 5b1) band and that predicted by Franck-Condon and Herzberg-Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0eV.

Two-Electron Scenario of High-Order Harmonics Generation by Atom in an Intense Infrared Field and Attosecond Pulse

The two-electron scenario is proposed for the high-order harmonic generation (HHG) by an atom interacting with an intense infrared field and attosecond pulse. The two-electron dynamics involved in the proposed scenario is realized for the specific attosecond pulse, which can excite the resonance between the valence and deeper shells. Within the numerical solution of the time-dependent Kohn–Sham equations, we analyze the contribution of the single [Phys. Rev. A 98, 063433 (2018)] and two-electron scenarios of HHG by decreasing the duration of attosecond pulse having carrier frequency detuned from the atomic resonance. Favorable conditions are formulated for the realization of a two-electron scenario, which causes the enhancement of the harmonic yield in the spectral range exceeding the cutoff energy of the HHG spectrum in the infrared field.

High energy laser & systems to neutralise stellar coronal mass ejections (CME) plasma

With CME plasma and shockwave travelling at 600+ km/sec, active methods such as high energy electron lasers (HEL) and mirrors are effective at making contact with ionised atoms in CME. Electrons pulsed from kW to MW laser(s) could polarise ionised atoms such as Fe16+, O7/8+, Mg, He2+,etc to fill valence pairs. As high-FIP atoms are electromagnetically trapped with a higher susceptibility from lower e- density and temperatures, CME plasma clouds can be neutralised, separated, and reduced in velocity trajectory around planet. Study outlines interactions between Electron Laser and CME plasma cloud, orbital geometry, build of high energy lasers, subsystems, as well as recoils, and cloud charge dynamics with e- interactions to neutralise CME particles. Additional space-based systems are designed such as mirrors in closer orbit to align lower velocity light beams. In approaching higher electron recombination and FIP ionisation of laser-plasma ion cluster density, max absorption of e- to CME could be approached with similar beam, CME, mirror angles and alignment, where e- couple and fill valence shells. Models evaluate efficacy of coherent laser beams of charged electrons, X-rays, infrared (IR), and/or electron/radio Hz to polarize CME column charge densities, with optimal CME scatter geometry and time window. Low cost ground experiments are discussed. Models suggest every ~1 km gap laser creates when CME t=8.255min creates a 10,067 km gap for Earth to orbit through. Such a HEL laser, reflecting mirrors, and space systems could neutralize plasma CME Cloud within 92.818M mi (Sun-Earth distance) and mitigate effects and trillion dollar costs from Carrington-type CME flares, and supernovae.

Reconstructing perspectives: investigating how molecular geometry cards (MGCards) and molecular model building (MMB) disrupt students' alternative notions of molecular structure – a qualitative study

The range of abstract concepts encountered when learning chemistry and the inability of students to make connections between the macroscopic, sub-microscopic, and symbolic representations, used in chemistry teaching, are believed to be the main reasons for students’ difficulty when learning chemistry. Prediction and determination of molecular geometry using the theory of valence shell electron pair repulsion (VSEPR) is a sample of the abstract concept that is hard to understand by students who learn chemistry. Students may comprehend these ideas better if the learning process is supplemented with cutting-edge, interactive learning aids. To address the conceptual difficulties that students encounter when learning how to predict the shapes of molecules, a card game (MGCards) has been developed which is supported by simple molecular model building (MMB). The card game allows students to work through the steps required to predict the shape of a molecule in an engaging format. The student learning process is supported by feedback at all stages (if students make a mistake, they receive hints that will help them in the next step of the game). Action research with qualitative methods has been used to design, develop, and evaluate the MGCards. The MGCards and MMB were piloted at the University of Leicester with year one Natural Sciences students and modified based on the feedback received. Both MGCards and MMB were then used as part of the first-year chemistry education programme at Tanjungpura University in Indonesia. The findings of students’ answer analysis (pre- and post-test) in both cycles showed that students had a better understanding after learning with MGCards and MMB. The positive feedback for MGCards and MMB confirmed that these resources were effective in delivering an engaging learning experience. The results suggest that MGCards and MMB play a significant role in enhancing students’ understanding while also keeping them engaged.

Study of electronic structure and optical transition properties of low-lying excited states of AuB molecules based on configuration interaction method

High-level configuration interaction method including the spin-orbit coupling is used to investigate the low-lying excited electronic states of AuB that is not reported experimentally. The electronic structure in our work is preformed through the three steps stated below. First of all, Hartree-Fock method is performed to compute the singlet-configuration wavefunction as the initial guess. Next, we generate a multi-reference wavefunction by using the state-averaged complete active space self-consistent field (SACASSCF). Finally, the wavefunctions from CASSCF are utilized as reference, the exact energy point values are calculated by the explicitly correlated dynamic multi-reference configuration interaction method (MRCI). The Davidson correction (+Q) is put forward to solve the size-consistence problem caused by the MRCI method. To ensure the accuracy, the spin-orbit effect and correlation for inner shell electrons and valence shell electrons are considered in our calculation. The potential energy curves of 12 Λ-S electronic states are obtained. According to the explicit potential energy curves, we calculate the spectroscopic constants through solving radial Schrödinger equation numerically. We analyze the influence of electronic state configuration on the dipole moment by using the variation of dipole moment with nuclear distance. The spin-orbit matrix elements for parts of low-lying exciting states are computed, and the relation between spin-orbit coupling and predissociation is discussed. The predissociation is analyzed by using the obtained spin-orbit matrix elements of the 4 Λ-S states which spilt into 12 Ω states. It indicates that due to the absence of the intersections between the curves of spin-orbit matrix elements related with the 4 low-lying Λ-S states, the predissociation for these low-lying exciting states will not occur. Finally, the properties of optical transition between the ground Ω state <inline-formula><tex-math id="M3">\begin{document}$ {\rm A}^{1}{{{\Pi}}}_{1} $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231347_M3.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231347_M3.png"/></alternatives></inline-formula> and first excited Ω state <inline-formula><tex-math id="M4">\begin{document}$ {{\mathrm{X}}}^{1}{{{\Sigma }}}_{{0}^{+}} $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231347_M4.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231347_M4.png"/></alternatives></inline-formula> are discussed in laser-cooling filed by analyzing the Franck-Condon factors and radiative lifetime. And the transition dipole moment is also calculated. But our results reveal that the AuB is not an ideal candidate for laser-cooling. In conclusion, this work is helpful in deepening the understanding of AuB, especially the structures of electronic states, interaction between excited states, and optical transition properties. All the data presented in this paper are openly available at <ext-link ext-link-type="uri" xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="https://www.doi.org/10.57760/sciencedb.j00213.00009">https://www.doi.org/10.57760/sciencedb.j00213.00009</ext-link>.

Ligand-enforced geometric constraints and associated reactivity in p-block compounds.

The geometry at an element centre can generally be predicted based on the number of electron pairs around it using valence shell electron pair repulsion (VSEPR) theory. Strategies to distort p-block compounds away from these predicted geometries have gained considerable interest due to the unique structural outcomes, spectroscopic properties or reactivity patterns engendered by such distortion. This review presents an up-to-date group-wise summary of this exciting and rapidly growing field with a focus on understanding how the ligand employed unlocks structural features, which in turn influences the associated reactivity. Relevant geometrically constrained compounds from groups 13-16 are discussed, along with selected stoichiometric and catalytic reactions. Several areas for advancement in this field are also discussed. Collectively, this review advances the notion of geometric tuning as an important lever, alongside electronic and steric tuning, in controlling bonding and reactivity at p-block centres.

Molecular Fe(II)-Ln(III) dyads for luminescence reading of spin-state equilibria at the molecular level.

Due to the primogenic effect, the valence shells of divalent iron Fe(II) ([Ar]3d6) and trivalent lanthanides Ln(III) ([Xe]4fn) are compact enough to induce spin-state equilibrium for the 3d-block metal and atom-like luminescence for the 4f-block partner in Fe(II)-Ln(III) dyads. In the specific case of homoleptic pseudo-octahedral [Fe(II)N6] units, programming spin crossover (SCO) around room temperature at normal pressure requires the design of unsymmetrical didentate five-membered ring chelating N∩N' ligands, in which a five-membered (benz)imidazole heterocycle (N) is connected to a six-membered pyrimidine heterocycle (N'). Benefiting from the trans influence, the facial isomer fac-[Fe(II)(N∩N')3]2+ is suitable for inducing SCO properties at room temperature in solution. Its connection to luminescent [LnN6O3] chromophores working as non-covalent podates in the triple-stranded [Fe(II)Ln(L10)3]5+ helicates (Ln = Nd, Eu) controls the facial arrangement around Fe(II). The iron-based SCO behaviour of the 3d-4f complex mirrors that programmed in the mononuclear scaffold. Because of the different electronic structures of high-spin and low-spin [Fe(II)N6] units, their associated absorption spectra are different and modulate the luminescence of the appended lanthanide luminophore via intramolecular intermetallic energy transfers. It thus becomes possible to detect the spin state of the Fe(II) center, encoded by an external perturbation (i.e. writing), by lanthanide light emission (i.e. reading) in a single molecule and without disturbance. Shifting from visible emission (Ln = Eu) to the near-infrared domain (Ln = Nd) further transforms a wavy emitted signal intensity into a linear one, a protocol highly desirable for future applications in data storage and thermometry.