Unpaired Electron Research Articles

Dynamic Nuclear Polarization with Conductive Polymers.

The low sensitivity of liquid-state nuclear magnetic resonance (NMR) can be overcome by hyperpolarizing nuclear spins by dissolution dynamic nuclear polarization (dDNP). It consists of transferring the near-unity polarization of unpaired electron spins of stable radicals to the nuclear spins of interest at liquid helium temperatures, below 2 K, before melting the sample in view of hyperpolarized liquid-state magnetic resonance experiments. Reaching such a temperature is challenging and requires complex instrumentation, which impedes the deployment of dDNP. Here, we propose organic conductive polymers such as polyaniline (PANI) as a new class of polarizing matrices and report1H polarizations of up to 5%. We also show that13C spins of a host solution impregnated in porous conductive polymers can be hyperpolarized by relayed DNP. Such conductive polymers can be synthesized as chiral and display current induced spin selectivity leading to electron spins hyperpolarization close to unity without the need for low temperatures nor high magnetic fields. Our results show the feasibility of solid-state DNP in conductive polymers that are known to exhibit chirality-induced spin selectivity.

La-exacerbated lattice distortion of high entropy alloys for enhanced electrocatalytic water splitting

The complex active site configurations of high entropy alloys (HEAs) limit their performance optimization and wide applications. Herein, we report a FeCoNiMnRuLa/CNT catalyst for efficient electrocatalytic water splitting by introducing La to break the lattice ordering of FeCoNiMnRu. The introduction of La reduces the number of unpaired electrons in FeCoNiMnRu, which in turn accelerates the transition of singlet state oxygen-containing intermediate to triplet state oxygen. The DFT results verify that the lattice distortion exacerbated by La alters the d-orbital electronic configuration of FeCoNiMnRu, so that Fe and Ni play an important role in the critical adsorption of *OH in the OER as well as *H2O in the HER, and Ru, Co, and Mn provide a strong safeguard for the desorption of oxygen-containing intermediates, thereby retaining excellent activity and stability during water decomposition. Our work showcases that the incorporation of rare earth elements opens new opportunities to improve the performance of HEAs.

Synthesis and reactivity of the di(9-anthryl)methyl radical.

The di(9-anthryl)methyl (DAntM) radical was synthesized and investigated to elucidate its optical, electrical properties, and reactivity. The generation of the DAntM radical was confirmed by its ESR spectrum, which showed two broad signals. The unpaired electron is primarily localized on the central sp2 carbon and slightly delocalized over the two anthryl moieties. Although the DAntM radical undergoes dimerization in solution, the radical still remains even at 190 K due to the bulky nature of the two anthryl groups. Interestingly, upon exposure to air, the purple color of the radical solution quickly fades to orange, resulting in decomposition to give 9-anthryl aldehyde and anthroxyl radical derivatives.

CaY@C2n: Exploring Molecular Qubits with Ca-Y Metal-Metal Bonds.

Metal-metal bonding is crucial in chemistry for advancing our understanding of the fundamental aspects of chemical bonds. Metal-metal bonds based on alkaline-earth (Ae) elements, especially the heavier Ae elements (Ca, Sr, and Ba), are rarely reported due to their high electropositivity. Herein, we report two heteronuclear di-EMFs CaY@Cs(6)-C82 and CaY@C2v(5)-C80, which contain unprecedented single-electron Ca-Y metal-metal bonds. These compounds were characterized by single-crystal X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, and DFT calculations. The crystallographic study of CaY@Cs(6)-C82 shows that Ca and Y are successfully encapsulated into the carbon cage with a Ca-Y distance of 3.691 Å. The CW-EPR study of both CaY@Cs(6)-C82 and CaY@C2v(5)-C80 exhibits a doublet, suggesting the presence of an unpaired electron located between Ca and Y. The combined experimental and theoretical results confirm the presence of a Ca-Y single-electron metal-metal bond with substantial covalent interaction, attributed to significant overlap between the 4s4p orbitals of Ca and the 5s5p4d orbitals of Y. Furthermore, pulse EPR spectroscopy was used to investigate the quantum coherence of the electron spin within this bond. The unpaired electron, characterized by its s orbital nature, is effectively protected by the carbon cage, resulting in efficient suppression of both spin-lattice relaxation and decoherence. CaY@Cs(6)-C82 behaves as an electron spin qubit, displaying a maximum decoherence time of 7.74 μs at 40 K. This study reveals an unprecedented Ae-rare-earth metal-metal bond stabilized by the fullerene cages and elucidates the molecular qubit properties stemming from their unique bonding character, highlighting their potential in quantum information processing applications.

Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott-Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction.

Regulating the adsorption of an intermediate on an electrocatalyst by manipulating the electron spin state of the transition metal is of great significance for promoting the activation of inert nitrogen molecules (N2) during the electrocatalytic nitrogen reduction reaction (eNRR). However, achieving this remains challenging. Herein, a novel 2D/2D Mott-Schottky heterojunction, Co9S8/Nb2CTx-P, is developed as an eNRR catalyst. This is achieved through the in situ growth of cobalt sulfide (Co9S8) nanosheets over a Nb2CTx MXene using a solution plasma modification method. Transformation of the Co spin state from low (t2g 6eg 1) to high (t2g 5eg 2) is achieved by adjusting the interface electronic structure and sulfur vacancy of Co9S8/Nb2CTx-P. The adsorption ability of N2 is optimized through high spin Co(II) with more unpaired electrons, significantly accelerating the *N2→*NNH kinetic process. The Co9S8/Nb2CTx-P exhibits a high NH3 yield of 62.62µg h-1 mgcat. -1 and a Faradaic efficiency (FE) of 30.33% at -0.40V versus the reversible hydrogen electrode (RHE) in 0.1m HCl. Additionally, it achieves an NH3 yield of 41.47µg h-1 mgcat. -1 and FE of 23.19% at -0.60V versus RHE in 0.1m Na2SO4. This work demonstrates a promising strategy for constructing heterojunction electrocatalysts for efficient eNRR.

Ekstraksi dan uji aktivitas antioksidan ekstrak etanol batang bintangur (calophyllum soulattri)

Background: Cigarette smoke, fried and grilled foods, excessive exposure to sunlight, motor vehicle fumes, certain drugs, toxins and air pollution are some sources of free radical compounds. As a result of homolytic breakdown, a molecule will break down into free radicals that have unpaired electrons. Electrons need a partner to balance their spin value, so that radical molecules become unstable and easily react with other molecules, forming new radicals. Findings: To prevent or reduce chronic diseases due to free radicals, antioxidants are needed. Antioxidants can slow down or inhibit the oxidation of substances that are easily oxidized even in low concentrations. Antioxidants can neutralize free radicals by donating one proton atom, making free radicals stable and non-reactive. Methods: Extraction is carried out by the maceration method, which is to soak the simplicia with ethanol solvent. This maceration process is carried out for 24 hours, then the solution containing the extract is filtered using filter paper. This maceration process is carried out three times. Conclusion: Ethanol extract of bintangur stem has quite high antioxidant activity, this can be proven by the IC50 value obtained of 3.05 ppm, this value is almost close to the IC50 value of vitamin C, which is 2.9 ppm, and by the appearance of spots in the Thin Layer Chromatography test.

Bridge vs Terminal Cyano-coordination in Binuclear Cobalt Porphyrin Dimers: Interplay of Electrons between Metal and Ligand and Spin-Coupling via Bridge.

Three cyano-coordinated cobalt porphyrin dimers were synthesized and thoroughly characterized. The X-ray structure of the complexes reveals that cyanide binds in a terminal fashion in both the anti and trans isomers of ethane- and ethylene-bridged cobalt porphyrin dimers, while in the cis ethylene-bridged dimer, cyanides bind in both terminal and bridging modes. The nonconjugated ethane-bridged complex stabilizes exclusively a diamagnetic metal-centered oxidation of type CoIII(por)(CN)2 both in the solid and in solution. In contrast, the complexes with the conjugated ethylene-bridge contain signatures of both paramagnetic ligand-centered oxidation of the type CoII(por•+)(CN)2 and diamagnetic metal-centered oxidation of type CoIII(por)(CN)2 with the metal-centered oxidized species being the major component in the solid state as observed in XPS, while the ligand-centered oxidized species are present in a significant amount in solution. 1H NMR spectrum in solution displays two set of signals corresponding to the simultaneous presence of both the diamagnetic and paramagnetic species. EPR and magnetic investigation reveal that there is a moderate ferromagnetic coupling between the unpaired electrons of the low-spin CoII center and the porphyrin π-cation radical in CoII(por•+)(CN)2 species as well as an antiferromagnetic coupling between the two CoII(por•+) units through the ethylene and CN bridges.

Harnessing Radicals: Advances in Self-Assembly and Molecular Machinery.

Radicals, with their unpaired electrons, exhibit unique chemical and physical properties that have long intrigued chemists. Despite early skepticism about their stability, the discovery of persistent radicals has opened new possibilities for molecular interactions. This review examines the mechanisms and applications of radically driven self-assembly, focusing on key motifs such as naphthalene diimides, tetrathiafulvalenes, and viologens, which serve as models for radical assembly. The potential of radical interactions in the development of artificial molecular machines (AMMs) are also discussed. These AMMs, powered by radical-radical interactions, represent significant advancements in non-equilibrium chemistry, mimicking the functionalities of biological systems. From molecular switches to ratchets and pumps, the versatility and unique properties of radically powered AMMs are highlighted. Additionally, the applications of radical assembly in materials science are explored, particularly in creating smart materials with redox-responsive properties. The review concludes by comparing AMMs to biological molecular machines, offering insights into future directions. This overview underscores the impact of radical chemistry on molecular assembly and its promising applications in both synthetic and biological systems.

Creating high, portable proton polarization with photo-excited triplet DNP

Dynamic nuclear polarization (DNP) is a powerful tool to polarize nuclear spins and enhance the intensity of their magnetic resonance signal. For DNP a sample is doped with an agent providing unpaired electron spins. Then the sample is cooled in a strong magnetic field to polarize these electron spins and a microwave field is applied to transfer this polarization to the nuclear spins. While DNP is very efficient, it has two inherent issues: the electron spins needed to polarize the nuclear spins are also the main source of polarization decay. Furthermore, polarizing the electron spins requires strong magnets and powerful cryogenics, that may obstruct further use of the polarized nuclear spins.These issues can be addressed by using the electron spin of photo-excited triplet states for DNP. After DNP the light creating the electron spins can be shut off, thus eliminating the main source of decay of the nuclear polarization. Moreover, for some well-chosen molecules the photo-excitation process creates the triplet state in a highly polarized state, so magnets and cryogenics can be significantly simplified.The present article presents the state of the art of producing a high proton polarization – up to 0.80 – with a long lifetime – typically 50 h at liquid nitrogen temperature and in a field of 0.75 T – using the photo-excited triplet state of pentacene in a naphthalene host. It describes sample preparation, experimental equipment and procedures required to obtain this result, as well the theoretical background required to maximize the polarization transfer from the triplet spins to the proton spins and to optimize the photo-excitation process. It finishes with methods for long-distance transport and final application of polarized samples.

Dual structure cobalt sites on surface hydroxyl and oxygen vacancy of BiOCl for cooperative CO2 reduction and tetracycline oxidation

Metal ion cocatalysts have huge prospect for photocatalytic CO2 reduction coupled with organic decomposition because of their cost effectiveness and abundant active sites. Herein, we exploit a defect−group oriented tactic to induce dual−structured Co sites on BiOCl with rich surface hydroxyls (OHs) and oxygen vacancies (OVs) (labeled as BiO1−xCl−OH), in which the surface OHs and OVs acted as anchoring points to anchor Co2+ ions. Density functional theory calculations manifested that surface OHs anchored Co2+ ions via hydrogen bonding to produce tight OH−Co sites, meanwhile, surface OVs with unsaturated metal sites and unpaired electrons captured Co2+ ions through chemical bonding to form close−knit OV−Co site. The as−generated OV−Co and OH−Co site served as reductive and oxidative cocatalyst for CO2 reduction and tetracycline oxidation, respectively, thereby achieving high−efficiency redox activity. This work provided a novel strategy to devise progressive dual functional metal ions cocatalysts for high−efficiency CO2 reduction and organic pollutants oxidation.

Antioxidant Activity of MgSO4 Ion Pairs by Spin-Electron Stabilization of Hydroxyl Radicals through DFT Calculations: Biological Relevance.

Magnesium sulfate has been of great interest as an antioxidant for its ability to decrease the oxidizing capacity of the hydroxyl radical. Previously, it was shown that the contact ion pair of this salt could stabilize •OH by coordinating with Mg and delocalizing the unpaired electron over sulfate. The present study explores in detail the MgSO4 antioxidant properties, considering all its ion pairs with •OH in different conformations. The analyses were based on structural, spin, and energetic properties using the DFT approach. As a result, the high antioxidant potential of MgSO4 is related to the spin-electron transfer from SO4 -2 to •OH causing electron spin delocalization and electrostatic stabilization. This transfer occurs for all ion pairs when •OH approaches the Mg first solvation shell, without being coordinated to Mg. The direct Mg-•OH interaction further stabilizes the radical system. These results show that spin-electron transfers are feasible in all hydrated ion pairs MgSO4-•OH, even at a •OH-sulfate distance greater than 10 Å.

The Role of Rare-Earth Atoms in the Anisotropy and Antiferromagnetic Exchange Coupling at a Hybrid Metal-Organic Interface.

Magnetic anisotropy and magnetic exchange interactions are crucial parameters that characterize the hybrid metal-organic interface, a key component of an organic spintronic device. It is shown that the incorporation of 4f RE atoms to hybrid metal-organic interfaces of CuPc/REAu2 type (RE = Gd, Ho) constitutes a feasible approach toward on-demand magnetic properties and functionalities. The GdAu2 and HoAu2 substrates differ in their magnetic anisotropy behavior. Remarkably, the HoAu2 surface promotes the inherent out-of-plane anisotropy of CuPc, owing to the match between the anisotropy axis of substrate and molecule. Furthermore, the presence of RE atoms leads to a spontaneous antiferromagnetic exchange coupling at the interface, induced by the 3d-4f superexchange interaction between the unpaired 3d electron of CuPc and the 4f electrons of the RE atoms. It is shown that 4f RE atoms with unquenched quantum orbital momentum ( ), as it is the case of Ho, induce an anisotropic interfacial exchangecoupling.

Electrodeposition of Ni/Cu Bimetallic Conductive Metal-Organic Frameworks Electrocatalysts with Boosted Oxygen Reduction Activity for Zinc-Air Batteries.

Zinc-air batteries employing non-Pt cathodes hold significant promise for advancing cathodic oxygen reduction reaction (ORR). However, poor intrinsic electrical conductivity and aggregation tendency hinder the application of metal-organic frameworks (MOFs) as active ORR cathodes. Conductive MOFs possess various atomically dispersed metal centers and well-aligned inherent topologies, eliminating the additional carbonization processes for achieving high conductivity. Here, a novel room-temperature electrochemical cathodic electrodeposition method is introduced for fabricating uniform and continuous layered 2D bimetallic conductive MOF films cathodes without polymeric binders, employing the organic ligand 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and varying the Ni/Cu ratio. The influence of metal centers on modulating the ORR performance is investigated by density functional theory (DFT), demonstrating the performance of bimetallic conductive MOFs can be effectively tuned by the unpaired 3d electrons and the Jahn-Teller effect in the doped Cu. The resulting bimetallic Ni2.1Cu0.9(HITP)2 exhibits superior ORR performance, boasting a high onset potential of 0.93V. Moreover, the assembled aqueous zinc-air battery demonstrates high specific capacity of 706.2mA h g-1, and exceptional long-term charge/discharge stability exceeding 1250 cycles.

Structural and Electronic Properties of the Magnetic and Nonmagnetic X0.125Mg0.875B2 (X = Nb, Ni, Fe) Materials: A DFT/HSE06 Approach to Investigate Superconductor Behavior.

MgB2 material has a simple composition and structure that is well-reported and characterized. This material has been widely studied and applied in the last 20 years as a superconductor in wire devices and storage material for H in the hydride form. MgB2 doped with transition metals improves the superconductor behavior, such as the critical temperature (T cs) or critical current (J sc) for the superconducting state. The results obtained in this manuscript indicate that Nb-, Fe-, and Ni-doping in the Mg site leads to a contraction of the unit cell through the spin polarization on the electronic resonance of the boron layer. Fe and Ni transition metals doping perturb the electronic resonance because of stronger dopant-boron bonds. The unpaired electrons are transferred from 3d orbitals to the empty 2p z orbitals of the boron atoms, locating α electrons in the σ bonds and β electrons in the π orbitals. The observed influence of magnetic dopants on MgB2 enables the proposal of an electronic mechanism to explain the spin polarization of boron hexagonal rings.

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms.

A series of minimally sized regular dodecahedron-embedded metallofullerene REC20 clusters (RE = Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd) as basic units of nanoassembled materials with tunable magnetism and UV sensitivity have been explored using density functional theory (DFT). The contribution of the 4f orbital of the rare earth atom at the center of the C20 cage to the frontier molecular orbital of REC20 gives the REC20 cluster additional stability. The AdNDP orbitals of the four REC20 superatoms that conform to the spherical jellium model indicate that through natural population analysis and spin density diagrams, we observe a monotonic increase in the magnetic moment from Ce to Gd. This is attributed to the increased number of unpaired electrons in the 4f orbitals of lanthanide rare earth atoms. The UV-visible spectrum of REC20 clusters shows strong absorption in the mid-UV and near-UV bands. REC20 clusters encapsulating lanthanide rare earth atoms stand out for their tunable magnetism, UV sensitivity, and stability, making them potential new self-assembly materials.

Synthesis of MeBICAAC Supported Si(III) Radicals and a Silylone via Reduction Route From MeBICAAC-Si(IV) Precursors.

Past one decade has witnessed a tremendous growth in the field of carbene stabilized low-valent silicon compounds unravelling very exciting properties of these molecules. Herein, we have employed a bicyclic (alkyl)(amino)carbene, (MeBICAAC) to explore the low-valent chemistry of silicon. The reduction of bicyclic (alkyl)(amino)carbene-SiCl4 complex, [(MeBICAAC)SiCl4] (1) with KC8 afforded low-valent Si complexes, including Si(III) radical [(MeBICAAC)SiCl3] (2) and a complex with silicon center in a formal zero-valent state, [(MeBICAAC)2Si] (3). Similarly, the reduction of in-situ generated MeBICAAC adduct of Me2SiCl2 with one equivalent of KC8 led to the formation of [(MeBICAAC)SiMe2Cl] (4) complex having an unpaired electron. These complexes have been characterized by IR, UV-Vis., NMR, HRMS, EPR and their solid-state structures were also elucidated by single crystal X-ray crystallography. Further, DFT calculations revealed the lower energy singlet state for complexes 1, 3 and doublet state for complexes 2, 4.

The striking influence of solubility on the nuclearity of cobalt NCN pincer complexes

The synthesis and characterization of two Co(II) complexes stabilized by NCN pincer ligands are described. The paramagnetic Co(II) complex [Co(κ3NCN-NCNCH2-iPr)Br] is obtained via a transmetalation protocol from CoBr2 and NC(C–Br)NCH2-iPr in THF. Surprisingly, the dinuclear complex [Co2(κ3NCN-μ2-NCNCH2-iPr)(μ-Cl)(Cl)2] was synthesized following the same synthetic protocol but using an ultrasonicated CoCl2 suspension instead of CoBr2 in the same solvent. Both complexes are paramagnetic species exhibiting solution magnetic moments of 1.9(1) and 5.8(3) μB, respectively. This corresponds to low-spin and high-spin d7 configurations featuring one and three unpaired electrons at the metal centers. X-ray structures of both complexes are presented.Graphical abstract

Refining Mn(III) Active Sites in MnO2-Based Self-Assembled Electrodes Via Oxygen Vacancy Induction to Enhance Oxygen Reaction Performance in Zinc-Air Batteries

Rechargeable zinc-air batteries are considered as a promising candidate for next-generation electrochemical energy conversion devices due to their safety, low cost, and high theoretical capacity/ energy density. Over the past few decades, α-MnO2-based electrodes have demonstrated their excellent performance and competitiveness in oxygen catalytic reactions. (1) According to eg filling theory, Mn(III) (t2g3eg1) sites in [MnO6] octahedral unit deliver superior bifunctional activity compared to Mn(II) (t2g3eg2) and Mn(IV) (t2g3eg0) sites.(2) However, the presence of unpaired single electrons of the Mn(III) site leads to low thermodynamic stability. Introducing oxygen vacancies to promote the electron rearrangement of the [MnO6] unit is a promising approach for enhancing the durability of Mn(III) active sites. Herein, we construct an oxygen-vacancy-enhanced MnO2-based electrode via a self-assembly process (NiCo2O4-MnO2@Ni foam). The intrinsic oxygen catalytic activity of NiCo2O4-MnO2@Ni foam is significantly improved by forming abundant highly stable Mn(III) active sites, which accelerate the mass transfer ability. As expected, the NiCo2O4-MnO2@Ni foam shows good bifunctional activity with a low overpotential of 0.69 V. The zinc-air battery assembled by NiCo2O4-MnO2@Ni foam exhibits a high peak power density of 576 mW cm-2, surpassing that of the Pt/C-Ir/C electrode. Additionally, benefiting from its stable flower-shaped hierarchical structure, the self-assembled electrode demonstrates long-term charge-discharge cycling stability, which lasts over 800 hours. This work provides innovative insights into enhancing MnO2-based electrodes by oxygen vacancy introduction.References N. Xu, Q. Nie, L. Luo, C. Z. Yao, Q. Gong, Y. Liu, X. Zhou, and J. Qiao, ACS applied materials & interfaces (2018).Z. Yin, R. He, H. Xue, J.-M. Chen, Y. Wang, X. Ye, N. Xu, J. Qiao and H. Huang, Energy Materials (2022).

On-Surface Synthesis of Graphene Nanoribbons and Spin Chains

Recent advances in on-surface synthesis has allowed the selective fabrication of a number of prototypical types of graphene nanoribbons. The thereby achieved properties include width-dependent electronic band gaps in armchair graphene nanoribbons, edge-localized states in zigzag graphene nanoribbons and topological band engineering in width-modulated topological graphene nanoribbons. More recently, on-surface synthesis of magnetic nanographenes has been reported. Here, the spin originates from unpaired electrons present in nanographenes with controlled sublattice imbalance or topological frustration. The corresponding magnetic moments live in p-orbitals and are hence largely delocalized, which allows for chemical control over their exchange interaction when covalently linking several molecular building blocks. Here, I will present synthesis of various prototypical magnetic nanographenes and the possibility to covalently link them to form coupled spin systems where exchange coupling can exceed 100 meV. Using halogen-substituted precursors, we achieve the on-surface synthesis-based deterministic bottom-up fabrication of various spin chains including a triangulene spin-1 chain revealing the predicted Haldane gap and fractional excitations at the chain termini or a strictly alternating spin-½ chain with chemically engineered coupling strengths J1 and J2 . Scanning tunneling microscopy and spectroscopy is used to explore length- and site-dependent magnetic excitations. Furthermore, we apply hydrogenation to achieve spin site passivation and controlled tip-based local reactivation to fabricate and characterize specific spin patterns in one-dimensional spin chains and spin clusters.

A systematic DFT study of the structural, electronic and magnetic properties of 3d transition metal based double perovskites Rb2MCl6 (M = V, Cr, Mn)

Transition-metal-based halide double perovskites constitute a new fascinating playground for investigating the deep relationship between the crystal structure, unique physical properties and their promising applications. Among these halides, Rb2MCl6 are attractive compounds since they show ferromagnetic, half-metallic (HM) and semiconductor natures due to the M-site substitution effect. In this work, we have studied the structural, thermodynamic, magnetic and electronic properties of perovskites Rb2MCl6 (M = V, Cr, Mn). Theoretically, the current investigations have relied heavily on Wien2k computational code, which exploits the density functional theory (DFT) based on generalized gradient approximation (GGA). Herein, we analyzed the effect of M-3d on the core physical properties of Rb2MCl6. We found that all Rb2MCl6 compounds are stable and crystallize in the face-centered cubic (fcc; Fm-3 m) structure. The electronic band structures and density of states indicate that Rb2MCl6 compounds exhibit HM nature for (M = V and Cr), and semiconductor behavior for (M = Mn). The direct band-gap for HM cases is found to be in the spin-down with 2.128 eV (M = V) and 2.111 eV (M = Cr), whereas (M = Mn)-based semiconductor compound shows a band-gap of 1.264 eV in spin-up and 1.701 eV in spin-down. The magnetic properties confirm that perovskites Rb2MCl6 are ferromagnetic (FM) materials with an integer total magnetic moment of 1.0 µB, 2.0 µB and 3.0 µB, respectively, in good agreement with the expected high-spin state of unpaired electrons on the M-3d ions. The above results reveal that the Rb2MCl6 perovskites are reliable inorganic materials and candidates for spintronics and optoelectronics applications.