Single Mn2 Research Articles

A nascent riboswitch helix orchestrates robust transcriptional regulation through signal integration

Widespread manganese-sensing transcriptional riboswitches effect the dependable gene regulation needed for bacterial manganese homeostasis in changing environments. Riboswitches – like most structured RNAs – are believed to fold co-transcriptionally, subject to both ligand binding and transcription events; yet how these processes are orchestrated for robust regulation is poorly understood. Through a combination of single-molecule and bulk approaches, we discover how a single Mn2+ ion and the transcribing RNA polymerase (RNAP), paused immediately downstream by a DNA template sequence, are coordinated by the bridging switch helix P1.1 in the representative Lactococcus lactis riboswitch. This coordination achieves a heretofore-overlooked semi-docked global conformation of the nascent RNA, P1.1 base pair stabilization, transcription factor NusA ejection, and RNAP pause extension, thereby enforcing transcription readthrough. Our work demonstrates how a central, adaptable RNA helix functions analogous to a molecular fulcrum of a first-class lever system to integrate disparate signals for finely balanced gene expression control.

Mineralization of Ni2+-Bearing Mn Oxide through Simultaneous Sequestration of Ni2+ and Mn2+ by Enzymatically Active Fungal Mn Oxides

A fungus, Acremonium strictum KR21-2, produces biogenic manganese oxides (BMOs) that can oxidize exogenous Mn2+ ions to form different BMO phases. When other guest ions are present during the BMO formation, it can strongly affect the mineralogical characteristics of the resultant BMO phase. The impact of coexisting Ni2+ ions on the mineralogy of BMO phases formed through enzymatic Mn(II) oxidation and its sequestration ability is not yet fully understood. To better understand it, repeated sequestration experiments were conducted using BMOs in Ni2+/Mn2+ binary, single Ni2, and single Mn2+ solution systems with a pH range of 6.0 to 7.5. It was observed that simultaneous sequestration of Ni2+ and Mn2+ was efficient, with irreversible Ni2+ incorporation at pH values above 7.0. The resultant BMO phases showed that Ni2+-bearing Mn oxides resembling feitknechitite (β-MnOOH) were developed through enzymatic Mn(II) oxidation. At pH values below 6.5, the turbostratic birnessite structure was maintained even in Ni2+/Mn2+ binary solutions, and subsequently, the Ni2+ sequestration efficiency was low. The pseudo-first-order rate constants of enzymatically inactivated BMOs for Mn2+ sequestration were two orders of magnitude lower than those of active BMOs, indicating the crucial role of the enzymes in precipitating Ni2+-bearing Mn oxide phases. These findings provide new insights into the mechanism of Ni2+ interaction with Mn oxide through microbial activity under circumneutral pH conditions.

Spectroscopic properties and photoluminescence of the Li2B4O7:Mn,Sm glass

The Li2B4O7:Mn,Sm glass containing 1.0 mol.% MnO2 and Sm2O3 were researched by X-ray diffraction (XRD), electron paramagnetic resonance (EPR), and optical spectroscopy methods. The studied glass of high optical quality was obtained by high temperature melting technique. Parameters of the local structure (interatomic distances and coordination numbers) of Li2B4O7:Mn,Sm glass were derived from XRD data analysis. The EPR and optical spectroscopy (absorption, luminescence excitation, emission, decay kinetics) show the presence of Mn2+(3d5) and Mn3+(3d4) impurity ions in the Li2B4O7:Mn,Sm glass. By EPR spectroscopy in the studied glass were identified three types of Mn2+ centres: single Mn2+ (1) centres in the strongly distorted sites (ratio of rhombic and axial constants, |E/D| ≤ 1/3), single Mn2+ (2) centres in the sites with almost cubic symmetry (D ≅ 0, E ≅ 0) as well as Mn2+ pairs and small clusters coupled by magnetic dipolar and exchange interaction, respectively. The Mn2+ EPR spectra parameters in the Li2B4O7:Mn,Sm glass have been determined at T = 295 K. Optical absorption spectrum of the Li2B4O7:Mn,Sm glass contains a very broad intense band peaked at 467 nm belonging to the 5Eg(D) → 5T2g(D) transition of Mn3+ ions and several weak narrow lines corresponding to the 6H5/2 → 6P3/2, 6H5/2 → 6F9/2, 6F7/2, 6F5/2 transitions of Sm3+ (4f5, 6H5/2) ions. Emission spectrum of the Li2B4O7:Mn,Sm glass exhibits a broad band corresponding to the 4T1g(G) → 6A1g(S) transition of Mn2+ ions and three characteristic bands in the yellow-orange-red range belonging to the 4G5/2 → 6H5/2, 6H7/2, 6H9/2 transitions of Sm3+ ions. Photoluminescence spectra (excitation and emission) and decay kinetics of the Mn2+ and Sm3+ ions in the Li2B4O7:Mn,Sm glass are interpreted in comparison with corresponding results for Li2B4O7:Mn and Li2B4O7:Sm glasses. Energy transfer processes Sm3+→Mn2+, Mn3+, and Mn2+→Mn3+ in the studied glass are considered.

Achieving Multicolor Anti‐Counterfeiting via Simultaneous X‐Ray and UV/Blue Excitation in Ca2YMgScSi3O12: Mn2+

AbstractOptical materials have attracted much attention in anti‐counterfeiting applications due to their visualization and multi‐emission modes. However, the unit occupancy predestines the material to only monochromatic emission, inhibiting the application of optical materials in advanced information encryption. Here, a green to yellow to deep‐red phosphor is reported in a Mn2+‐activated garnet compound Ca2YMgScSi3O12: Mn2+ (CYMSS: Mn2+), originating from the abundant lattice sites occupying within the crystal structure by Mn2+ ions. Three different photoluminescence (PL) emission bands peaked at 517, 576, and 720 nm from 4T1 (G) → 6A1 (S) are observed, which are attributed to the substitution of [Sc/MgO6] octahedron and [Ca/YO8] dodecahedron sites by Mn2+ ions, respectively. Hence, tunable emissions from green to deep‐red are realized in single Mn2+ doping by switching the excitation source of ultraviolet (UV)/blue and X‐ray, which can be further regulated by varying the Mn2+ concentration. Multi‐position occupying, color‐tunable light‐emitting materials offer the possibility of more advanced optical information encryption.

Dual-emissive luminescence in OIHMH single crystals: tunable red-green emissions via Mn2+ doping and theoretical insights.

The burgeoning demand for materials with tunable photoluminescence properties for applications has necessitated the exploration of novel luminescent materials. This study presents the synthesis and characterization of a novel 0D organic-inorganic hybrid metal halide (OIHMH) single crystal, C6H14N2CdBr4, which exhibits intriguing luminescent properties upon Mn2+ doping. The introduction of single Mn2+ ions results in a dual-emission, with the unexpected emergence of a red emission peak at 627 nm, in addition to the conventional tetrahedral green emission at 525 nm. This dual-emission is attributed to the distinct inter-tetrahedral distances within the crystal structure of C6H14N2CdBr4 with varying distances between [CdBr4]2- tetrahedra, influencing the spatial distribution and interaction of the [MnBr4]2- tetrahedra. Electron paramagnetic resonance (EPR) spectroscopy and theoretical calculations reveal the 627 nm and 525 nm emissions are attributed to the d-d transition of magnetic coupled Mn2+-Mn2+ pairs and isolated Mn2+ ions, respectively. This study not only advances the understanding of the luminescence mechanisms of Mn2+ but also paves the way for the development of tunable luminescent materials.

Lead-Free Organic Manganese (II) Bromide Hybrid with Highly Efficient and Stable Green Emission for UV Photodetection

Lead halide perovskites have been widely used in optoelectronic devices due to their excellent properties; however, the toxicity of lead and the poor stability of these perovskites hinder their further application. Herein, we report a zero-dimensional (0D) lead-free organic manganese (II) bromide hybrid compound of (TBA)2MnBr4 (TBA+ = tetrabutylammonium cation) single crystals (SCs) with great environmental stability. The (TBA)2MnBr4 SCs show a strong green emission peak at 518 nm with a high photoluminescence quantum yield (PLQY) of 84.98% at room temperature, which is attributed to the d-d transition of single Mn2+ ions, as also confirmed through density functional calculation. A green light-emitting diode was produced based on (TBA)2MnBr4 SCs, which exhibited CIE coordinates (0.17, 0.69) close to those of standard green. A photodetector fabricated by the (TBA)2MnBr4 SCs shows an obvious photo response with a rapid millisecond rise/decay response time (at 365 nm). Our findings promote the research of Mn(II)-based organic–inorganic hybrid materials and pave the way by using these materials for future high-performance optoelectronic devices.

Evidence of ferromagnetic coupling for manganese pairs in a layered van der Waals GaS semiconductor

Using high-frequency electron paramagnetic resonance (EPR), we have observed the ferromagnetic coupling of manganese Mn2+ pairs in a layered van der Waals GaS semiconductor. The EPR spectra of Mn2+ pairs (Mn24+) [replacing covalently bonded Ga24+ pairs oriented along the chain axis (c axis) of two gallium ions and being situated in the center of the layer] were recorded at 94 and 130 GHz. The fine structure parameters for the lower multiplets with spin S = 5 and S = 4 were determined equal to D = −0.040 cm−1 and D ≅ −0.035 cm−1, respectively. Based on the observation of additional EPR lines in the region of intersection of the levels in the magnetic field of the multiplet with S = 5 and S = 4, the energy of the isotropic exchange interaction J was estimated to be ∼−0.5 cm−1. For all transitions, a well-resolved hyperfine structure was observed, due to the interaction with two equivalent 55Mn nuclei, leading to the appearance of 11 lines with a hyperfine interaction constant A = 30(1) × 10−4 cm−1, which is approximately half the hyperfine interaction constant for single Mn2+ ions. In addition, a signal from single manganese ions Mn2+ with spin S = 5/2 and a hyperfine interaction constant A = 60(1) × 10−4 cm−1 was observed, which are characterized by extremely large fine structure splitting of D = −0.15 cm−1. Simultaneously with EPR studies, the crystals were monitored by photoluminescence and micro-Raman scattering measurements using a microscope with confocal optics.

Stress‐Induced Multi‐Stimulus‐Responsive Mechanoluminescence in Mn2+ Doped Double Perovskite Compound

AbstractMulti‐mode mechanoluminescence (ML) materials are have applications such as anti‐counterfeiting, stress sensing, and information security. There is limited general consensuses on the luminescent mechanisms, even though exploring ML mechanism based on defects has shown significance in further studies exploring both ML materials design and application. Here, a deep‐red to near‐infrared (NIR) ML material is reported in a Mn2+‐activated double perovskite‐type compound (CaZnGe2O6: Mn2+). The abundant lattice sites within the crystal structure have enabled Mn2+ doping and defects. Two different photoluminescence (PL) emission bands peaked at 536 and 676 nm from 4T1(4G)→6A1(6S) are observed, which are attributed to the substitution of Zn2+ and Ca2+ sites by Mn2+, respectively. Hence, tunable emissions from green to red are realized in single Mn2+ doping, which can be further regulated by varying the Mn2+ concentration. Electrons and holes are captured by cation and anion defects ( and , , vacancy of Zn, Ca and O ions), followed by the combination of such carriers to transfer energy to the Mn2+ 3d states to produce ML/persistent luminescence (PersL) under mechanical/thermal stimuli. Proof‐of‐concept applications in multi‐mode anti‐counterfeiting, temperature sensing, and X‐ray imaging fields are demonstrated. These results will deepen the understanding of single Mn2+‐doped multi‐stimulus‐responsive ML materials, inspiring the development of more high‐performance ML phosphors for practical applications.

Spectral fingerprints of individual Mn2+ impurities and Mn2+ pairs in magic-sized nanoclusters.

The chemical synthesis of (CdSe)13 magic-sized clusters (MSCs) allows the replacement of host atoms by individual transition metals such as Mn. By analyzing the spectral fingerprints of the Mn2+ photoluminescence (PL) in MSCs with different dopant concentrations, we are able to distinguish between single Mn2+ ions and coupled Mn2+ pairs. In case of Mn2+ pair emission, temperature-dependent studies show a pronounced red shift, followed by a distinct blue shift of the PL energy upon heating. This is related to a spin ladder formation of the ground and excited states due to Mn2+-Mn2+ exchange interaction at cryogenic temperatures, which is assumed to vanish at higher temperatures. In contrast, single Mn2+ ion PL exhibits a unique redshift with increasing temperature, which can be attributed to a particularly strong coupling to vibronic modes due to the ultimate small size of the MSCs.

Achieving large thermal hysteresis in an anthracene-based manganese(II) complex via photo-induced electron transfer

Achieving magnetic bistability with large thermal hysteresis is still a formidable challenge in material science. Here we synthesize a series of isostructural chain complexes using 9,10-anthracene dicarboxylic acid as a photoactive component. The electron transfer photochromic Mn2+ and Zn2+ compounds with photogenerated diradicals are confirmed by structures, optical spectra, magnetic analyses, and density functional theory calculations. For the Mn2+ analog, light irradiation changes the spin topology from a single Mn2+ ion to a radical-Mn2+ single chain, further inducing magnetic bistability with a remarkably wide thermal hysteresis of 177 K. Structural analysis of light irradiated crystals at 300 and 50 K reveals that the rotation of the anthracene rings changes the Mn1–O2–C8 angle and coordination geometries of the Mn2+ center, resulting in magnetic bistability with this wide thermal hysteresis. This work provides a strategy for constructing molecular magnets with large thermal hysteresis via electron transfer photochromism.

Enhanced afterglow performance of Zn2SiO4:Mn2+ by Pr3+ doping and mechanism

High luminescence intensity and long persistent duration is desired for practical application of long persistent materials. But it still remains challenging due to insufficient phosphors to meet the commercial request and a general lack of understanding of luminescence mechanism. In this work, green persistent luminescent phosphor Zn2SiO4:Mn2+,Pr3+ was first synthesized by traditional solid-state reaction method with self-made SiO2 submicrospheres as silicon source. The morphology, crystal structure, photoluminescence and the long afterglow performance have been investigated systematically. Interestingly, the longest persistent luminescence is observed for 0.025 Mn2+, 0.001 Pr3+ co-doped Zn2SiO4 with a persistent time of ∼2640 s at (0.32 mcd/m2), which is 20 times longer than those of Zn2SiO4 host or single Mn2+ doped Zn2SiO4 phosphors. The possible persistent mechanism has been discussed. The finding will be beneficial for developing persistent phosphors with superior functionalities.

Designing a Polyphosphate Polymorph of CsMg(PO3)3 as Host Lattice for Preparing Single Mn2+-Oxidation Doped Phosphor in the Open Environment.

Within Mn-activated phosphors, the oxidation state of Mn dopant strongly depends on the structural features of the host lattice. This paper reported a new polymorph of CsMg(PO3)3 (CMP) with a complicated three-dimensional (3D) framework of [Mg(PO3)3]∞ that is constructed by MgO6 octahedra and 1D infinite [PO3]∞ chains. Then we prepared a series of red phosphors CsMg1-x(PO3)3:xMn2+ (CMP:xMn2+) by high temperature solid state reactions in the open air. Powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) studies revealed the single Mn2+-oxidation. Under 404 nm light exciting, CMP:0.2Mn2+ can emit single-band emission at around 630 nm with full-width at half-maximum (fwhm) of 70 nm. Besides, CMP:0.2Mn2+ possesses excellent thermostability up to 450 K. These features indicate that CMP:0.2Mn2+ is suitable to be used for LED backlight display. Moreover, this work suggests that a host lattice with suitable structure feature can form single Mn2+-oxidation and is rigid enough to protect Mn2+ from being oxidized by O2 at high temperature.

Orientation of Individual Anisotropic Nanocrystals Identified by Polarization Fingerprint.

The polarization of photoluminescence emitted from anisotropic nanocrystals directly reflects the symmetry of the eigenstates involved in the recombination process and can thus be considered as a characteristic feature of a nanocrystal. We performed polarization resolved magneto-photoluminescence spectroscopy on single colloidal Mn2+:CdSe/CdS core-shell quantum dots of wurtzite crystal symmetry. At zero magnetic field, a distinct linear polarization pattern is observed, while applying a magnetic field enforces circularly polarized emission with a characteristic saturation value below 100%. These polarization features are shown to act as a specific fingerprint of each individual nanocrystal. A model considering the orientation of the crystal c⃗ axis with respect to the optical axis and the magnetic field and taking into account the impact of magnetic doping is introduced and quantitatively explains our findings. We demonstrate that a careful analysis of the polarization state of single nanocrystal emission using the full set of Stokes parameters allows for identification of the complete three-dimensional orientation of the crystal anisotropy axis of an individual nanoobject in lab coordinates.

Site preference and the optical thermometry strategy by different temperature response from two sites environment of Mn2+ in K7ZnSc2B15O30

A novel optical thermometry strategy based on different temperature response from two sites environment of Mn2+ in K7ZnSc2B15O30:Mn2+ had been reported. The color tunable Mn2+ doped K7ZnSc2B15O30 luminescence materials were successfully prepared, and the photoluminescence properties were studied. Using density functional theory, the electronic structure was estimated. The calculated result showed that K7ZnSc2B15O30 was a direct-band gap material with the energy gap of 4.22 eV. Upon the excitation of UV light, the photoluminescence spectra of K7ZnSc2B15O30:Mn2+ phosphors demonstrated two emission bands centered at 584 nm and 675 nm attributed to the substitution of Zn2+ and Sc3+ sites with Mn2+ respectively. Depending on the concentration of Mn2+, the emitting color can be tunable from yellow to red in the Mn2+ doped single-phase phosphors. The temperature-dependent luminescence properties of K7ZnSc2B15O30:Mn2+ was anlysized range from 300 K to 520 K. The results indicated that the thermal quenching properties of Mn2+ at the two kinds of lattice sites are different. When Mn2+ occupied the position of Sc3+, the luminescence intensity decreased significantly with the increasing of temperature, on the contrary, when Mn2+ occupied the position of Zn2+, the luminescence intensity decreased slightly with the rise of temperature. This situation caused a significant change in the fluorescence intensity ratio of the two emission bands. Further study showed that the typical phosphor had a high relative and absolute sensitivity respectively with maximum value of 1.84% K−1 and 0.0311 K−1 at 520 K, and the temperature resolution is about 0.8 K. These results indicated that the single Mn2+ doped K7ZnSc2B15O30 materials showed a potential application for optical thermometry.

Relaxation Dynamics of Excited States in Mn2+-Doped ZnCdS (Core)/ZnS (Shell) Quantum Dots Ions in Propylene Carbonate

It has been shown that luminescence in Mn@Zn0.49Cd0.51S/ZnS quantum dots (QDs) in propylene carbonate is due to a single Mn2+(4T1 → 6A1) band and has a quantum yield of ~24%. The Mn2+(4T1) level is excited through the light absorption in the exciton absorption bands of Zn0.49Cd0.51S/ZnS. The femtosecond dynamics of the difference spectra of Mn@Zn0.49Cd0.51S/ZnS QDs show fast relaxation of the exciton on the subpicosecond–picosecond timescale. At delay times in picosecond range, the band of stimulated luminescence has been detected in difference absorption spectra in the Mn2+(4T1 → 6A1) transition region. A qualitative hypothetical mechanism of nonradiative energy transfer from the exciton to Mn2+(4T1) involving the Auger transition in the trap states has been proposed. The assumption solves the problems of the energy excess of 0.98 eV in the energy transfer to the 3d5 level of Mn and of the conservation of the total spin of the system.

A single Mn2+ ions activated fluosilicate glass with continuously tunable broadband emission from 475 nm to 800 nm

Broadband phosphor-converted light-emitting diodes are replacing the conventional light sources in spectroscopy application owning to the high efficiency, long lifetime, and compactness. However, the broadband emission originated from multi-component phosphors exhibits low quantum efficiency (QE) and poor thermal stability. Herein, a single Mn2+ ions activated fluosilicate (SF) glass, with broadband emission from 475 nm to 800 nm and good thermal conductivity (2.3 W/m·K), was presented. Their optical properties, structural characteristics and thermal performances were investigated through UV/VIS/NIR spectrophotometer, fluorescence spectrometer, Raman system, as well as thermal analyzer. The results show that continuously tunable broadband emission from green to orange, enhanced QE from 27.9% to 43.8%, and improved thermal stability (increasing Tg from 546°C to 665°C and decreasing thermal quenching) were achieved by increasing the Y2O3 content of SF glass composition. All of those investigations provide a new approach for exploring a continuously tunable broadband emission based on single-component phosphor with one activator.

Directed Exciton Magnetic Polaron Formation in a Single Colloidal Mn2+:CdSe/CdS Quantum Dot.

One of the most prominent signatures of transition-metal doping in colloidal nanocrystals is the formation of charge carrier-induced magnetization of the dopant spin sublattice, called exciton magnetic polaron (EMP). Understanding the direction of EMP formation, however, is still a major obstacle. Here, we present a series of temperature-dependent photoluminescence studies on single colloidal Mn2+:CdSe/CdS core/shell quantum dots (QDs) performed in a vector magnetic field providing a unique insight into the interaction between individual excitons and numerous magnetic impurities. The energy of the QD emission and its full width at half-maximum are controlled by the interplay of EMP formation and statistical magnetic fluctuations, in excellent agreement with theory. Most important, we give the first direct demonstration that anisotropy effects-hypothesized for more than a decade-dominate the direction of EMP formation. Our findings reveal a pathway for directing the orientation of optically induced magnetization in colloidal nanocrystals.

A single-phase full-visible-spectrum phosphor for white light-emitting diodes with ultra-high color rendering.

Excellent luminous performance and high color rendering are the keys to white light-emitting diode (WLED) illumination. This work reports a single-phase full-visible-spectrum Y2Mg2Al2Si2O12(YMAS):Eu2+,Mn2+ phosphor for WLEDs with ultra-high color rendering. The luminescence of a single Mn2+ doped YMAS phosphor is very weak due to the spin-forbidden transition of Mn2+, while it can be dramatically enhanced in the YMAS:Eu2+,Mn2+ system through efficient energy transfer from the sensitizer Eu2+. Meanwhile, the luminescent color of this phosphor can be tuned from cyan to cold white, to warm white, and finally close to the yellow region by controlling the activator concentration and energy transfer process. Its good thermal and chromaticity stability meet the requirements of application in WLEDs. Its stable photochromic performance at different excitation wavelengths (365-395 nm) indicates that it can be used in different ultraviolet chips. The YMAS:0.03Eu2+,0.30Mn2+ phosphor-converted WLED achieves an ultra-high color rendering index (Ra = 93.3), near-standard chromaticity coordinates (CIE = (0.3343, 0.3388)) and a suitable correlated color temperature (CCT = 5417 K).

Electric field tuning of spin splitting in topological insulator quantum dots doped with a single magnetic ion

We investigate theoretically the electron spin states in a disk-shaped topological insulator quantum dot (TIQD) containing a single magnetic Mn2+ ion. We demonstrate that the energy spectra and the density distributions of the symmetry-protected edge states in a HgTe TIQD can be modulated effectively by a single magnetic impurity Mn2+. Additionally, when an in-plane external electric field is applied., it not only tunes the spin splittings of edge states via the s(p)-d exchange interaction between the electron (hole) and the magnetic Mn2+ ion respectively, but also gives rise to the bright-to-dark transitions in the optical transition spectrum. Such spin properties of TIQDs with single Mn2+ ion as illustrated in this work could offer a new platform for topological electro-optical devices.

8-Layer Shifted Hexagonal Perovskite Ba8MnNb6O24: Long-Range Ordering of High-Spin d5 Mn2+ Layers and Electronic Structure.

A new 8-layer shifted hexagonal perovskite Ba8MnNb6O24 has been synthesized in air, featuring unusual long-range B-cation ordering with single octahedral high-spin d5 Mn2+ layers separated by ∼1.9 nm within the corner-sharing octahedral d0 Nb5+ host, analogous to Ba8(Zn/Co)Nb6O24. The large size and charge differences between high-spin Mn2+ and Nb5+, as well as the out-of-center distortion of NbO6 octahedra associated with the bonding covalence and second-order Jahn-Teller effect of Nb5+, drive long-range cationic ordering, thus stabilizing Ba8MnNb6O24. The Ba8MnNb6O24 pellet exhibits a high dielectric permittivity, εr ∼ 38, and a large temperature coefficient of resonant frequency, τf ∼ 20 ppm/K, but a dielectric loss ( Qf ∼ 987 GHz) and conductivity (∼10-8-10-3 S/cm within 473-1173 K) much higher than those of Ba8ZnNb6O24. Electronic structures from density functional theory calculations reveal that Ba8MnNb6O24 is a Mott insulator in contrast with the charge-transfer insulator nature of Ba8ZnNb6O24, and they confirm that the off-center distortion of Nb5+ contributes to stabilization of the 8-layer ordered shifted structure. The contrast between conductivity and dielectric loss of Ba8MnNb6O24 and Ba8ZnNb6O24 is understood based on the electronic structure that depends on high-spin d5 Mn2+ and d10 Zn2+ cations. The hopping of 3d valence electrons in high-spin Mn2+ to Nb5+ 4d conduction bands over a small gap (∼2.0 eV) makes Ba8MnNb6O24 more conductive than Ba8ZnNb6O24, where the electrons are conducted via the hopping of a lattice O 2p valence electron to the Nb5+ 4d conduction bands over a larger gap (∼3.9 eV). The high microwave dielectric loss of BMN may be mainly ascribed to the half-filled Mn 3d orbits, which is understood based on the softened infrared modes that increase the lattice vibration anharmonicity as well as the resonant spin excitation of unpaired d electrons.