Hybrid Halide Research Articles

A new halide hybrid compound based on Zn (II) and 3,3′-diaminodiphenylsulfone: A combined experimental and theoretical study

• Slowly evaporation method was used to synthesize a new tetrachlorozincate hybrid compound. • Hirshfeld surfaces and their associated two-dimensional fingerprint plots provides information about the intermolecular interactions. • Vibrational study was realized based on the calculated frequencies. • HOMO-LUMO band gap energy of the crystal is 4.96 eV. • The optical properties were performed. A new organic-inorganic hybrid compound of formula (C 12 H 14 N 2 O 2 S)(ZnCl 4 ) . 1.33H 2 O was obtained by slow evaporation of a H 2 O/EtOH solution at room temperature. The solid-state structure, determined by single X-ray crystal diffraction, indicates that the synthesized compound crystallizes in the triclinic system with P-1 space group. The title compound was further characterized by spectroscopies analysis (Infrared, Raman and UV-Visible) and its thermal behavior was investigated by using TGA and DSC. In the crystal packing ZnCl 4 2- anions, (C 12 H 14 N 2 O 2 S) 2+ cations and water molecules are present. The stability of the three-dimensional framework is assured via intermolecular hydrogen bonds, which were analyzed by using Hirshfeld Surface analysis. Vibrational and UV-vis spectra of the investigated compound were recorded and discussed. Theoretical calculations were carried out by using the PM6 semiempirical model. Moreover, Molecular Electrostatic Potential (MEP) map and the frontier molecular orbitals (HOMO-LUMO) of the compound were calculated and discussed using the optimized structure.

Achieving Large Second Harmonic Generation Effects via Optimal Planar Alignment of Triangular Units

AbstractTrigonal planar units with large polarizability anisotropy and high physicochemical stability are ideal structural units for exploring nonlinear optical (NLO) materials. Integrating the merits of two types of triangular‐like moieties, a family of second‐order NLO‐active hybrid halides, MATX (X = Cl (1), Br (2), and I (3)), are achieved. MATX crystallizes in a nonpolar space group of 2c but exhibits the optimal spatial arrangement and superior NLO performance. The low coordination planar trigonal AgX3 units enable segregation in layers of the three‐winged propeller‐like Me3TPA units. All of the layers are packed in a perfect parallel fashion, making the functional materials exhibit superior NLO performances, including the phase matchable behavior with strong SHG responses (6.2/1, 6.5/2, and 7.6/3 times that of potassium dihydrogen phosphate), large birefringence (0.232/1, 0.252/2 and 0.260/3 at 1064 nm), high laser damage threshold, wide transparent window, and easiness of crystal growth. The first‐principles calculations reveal that the coexistence of strong linear and nonlinear optical properties are ascribed to the synergistic effect of the trigonal moieties. This study points out a useful path for the rational design of excellent NLO materials.

Two Zero‐Dimensional In3+‐Based Hybrid Halides: Single‐Component Materials Showing Bluish‐White‐Light Emission

AbstractLow‐dimensional organic‐inorganic hybrid halides (OIHs) with wide emission band have drawn in plenty of consideration in recent years, due to their good luminescence potential, low cost and stable chemical properties. In this work, we reported two new zero‐dimensional (0D) OIH single‐crystals, (N‐AEP)InCl6 ⋅ H2O (N‐AEP=N‐Aminoethylpiperazine, 1) and (N‐AEP)InBr6 ⋅ H2O (2), both belong to the orthorhombic space group of C2221. Systematic characterizations of the compounds including crystal structure, thermal, and photophysical properties were carried out. Luminescence properties studies indicated their dual‐emission characteristics, which was attributed to the synergy of organic and inorganic groups. Significantly, complex 1 showed blue‐light (color coordinates: (0.18, 0.16)) emission upon UV excitation, while a rare bluish‐white light (color coordinates: (0.24, 0.24)) was observed in 2, depending on the assembly of high‐energy emission in (N‐AEP)3+ and low‐energy emission in [InBr6]3− octahedron. This paper offered a particular example on the research for In3+‐based single‐component materials with wide emission bands.

Intrinsic Ion Migration Dynamics in a One-Dimensional Organic Metal Halide Hybrid

Metal halide perovskites possess many physical properties amenable to optoelectronic applications, whereas the realization of these potentials has been hampered by their environmental and electronic instabilities. The morphological and molecular low dimensional perovskites and perovskite related materials have shown much promise in enhancing the chemical stability due to their unique molecular structures. Here we report on robust and reproducible four-terminal (4T) electrical measurements in a one-dimensional (1D) organic metal halide hybrid, (R)-{\alpha}-methylbenzylammonium lead triiodide ((R-{\alpha}-MBA)PbI3) made possible by its chemical stability. The results reveal a distinct intrinsic ion migration dynamic of single exponential, which underlies the unique 4T I-V characteristics. The dynamic is directly verified by real-time measurements of the transient ionic current. Our observations are consistent with photo-activation and field-assisted ion migration. The elucidated intrinsic ion dynamics may provide the physical basis for understanding and modelling the ubiquitous hysteresis in metal halides based electronic devices and new insights into the dynamics of ion migration in metal halide perovskites and hybrids in general.

Enhanced oxidization and corrosion resistance of silver nanowire based transparent conductor by nickel electroplating to obtain power conversion efficiency > 18 % in perovskite solar cells

Silver nanowire based transparent conductor is expected to be widely used in optoelectronic devices. However, when used in perovskite solar cells, it suffers from heavy corrosion caused by the lead halide hybrid perovskite. To solve the problem, nickel electroplating is used to modify the transparent conductor in this study. It is observed that nickel electroplating not only improves the conductance, but also upgrades the corrosion resistance and the oxidization resistance of the transparent conductor. In addition, SnO2 quantum dots are applied to flatten the conductor surface, while ITO sputtering is used to further improve the film conductance. After that, perovskite solar cells are fabricated on the modified transparent conductors. Current-voltage curves scanning under simulated irradiation shows that, power conversion efficiency of 18.37 % is achieved. Transient photocurrent / photovoltage decay curves and impedance spectroscopy tests show that, nickel treated transparent conductors could ensure efficient charge-extraction process, while retard charge recombination. Storage-stability of the devices is monitored, 80 % of initial performance is reserved after storage in dark for 432 h. The study paves the way for the application of silver nanowire basing transparent conductor in devices when heavy corrosion is involved.

3D printed optical sensor for highly sensitive detection of picric acid using perovskite nanocrystals and mechanism of photo-electron transfer

Hand-held, compact and portable sensors for on-site detection of environmental contaminants are in high demand for industry 4.0. Here, we have developed a sensor based on luminescent organic–inorganic metal halide hybrid perovskites nanocrystals (CH3NH3PbBr3) with p-xylylenediamine as an additional capping agent for highly sensitive and selective detection of picric acid (PA), with a good linear range of 1.8 μM–14.3 μM achieving detection of limit (LOD) of 0.3 μM. The electrostatic interaction between PA and the capping ligand of perovskite nanocrystals resulted in significant fluorescence quenching, as revealed by the steady-state and time-resolved spectroscopy. The applicability of the developed sensor for PA detection was validated with a 3D printed device integrating surface mounting device (SMD) and paper microfluidics. This prototype device was successfully applied as a fluorescence turn-off sensor to detect PA, showing great potential for on-site detection. This 3D-printed paper-based microfluidic optical sensor proved very efficient for naked-eye detection of PA with an inbuilt excitation source, avoiding the requirement of expensive and complex instrumentation.

(C4H10NO)PbX3 (X = Cl, Br): Design of Two Lead Halide Perovskite Crystals with Moderate Nonlinear Optical Properties.

Introducing electronegative species into organic constituents was considered to be one effective strategy for adjusting crystal symmetry and designing new nonlinear optical (NLO) materials. By substitution of C4 in piperidine (C5H11N) with electronegative oxygen, organic morpholine (C4H9NO) was easily obtained. Therefore, to design NLO crystals, we focused on combinations of stereochemically active lone-pair (SCALP) cation (Pb2+)-based chloride and bromide with morpholine molecules. In this work, two lead halide hybrid perovskite (C4H10NO)PbX3 (X = Cl, Br, abbreviated as MPbCl3 and MPbBr3, respectively) single crystals with moderate nonlinear optical properties were synthesized by a slow evaporation method. The two title crystals belong to orthorhombic space group P212121 with one-dimensional (1D) chainlike perovskite structures. Theoretical calculations revealed that the second harmonic generation (SHG) responses mainly originate from distorted {PbX6} octahedrons of the inorganic framework. Remarkably, moderate phase-matching SHG effects of about 0.70 and 0.81 times KH2PO4, large birefringences of 0.098 and 0.111 at 1064 nm, and large laser damage thresholds (LDTs) of 19.94 and 46.82 MW/cm2 were estimated for MPbCl3 and MPbBr3, respectively. This work provides a novel strategy for new purpose-designed hybrid NLO crystals by adjustment and modulation of chemical modification.

Polaron mobility modulation by bandgap engineering in black phase α-FAPbI3

Lead halide hybrid perovskites (LHP) have emerged as one of the most promising photovoltaic materials for their remarkable solar energy conversion ability. The transportation of the photoinduced carriers in LHP could screen the defect recombination with the help of the large polaron formation. However, the physical insight of the relationship between the superior optical-electronic performance of perovskite and its polaron dynamics related to the electron-lattice strong coupling induced by the substitution engineering is still lack of investigation. Here, the bandgap modulated thin films of α-FAPbI3 with different element substitution is investigated by the time resolved Terahertz spectroscopy. We find the polaron recombination dynamics could be prolonged in LHP with a relatively smaller bandgap, even though the formation of polaron will not be affected apparently. Intuitively, the large polaron mobility in (FAPbI3)0.95(MAPbI3)0.05 thin film is ∼30% larger than that in (FAPbI3)0.85(MAPbBr3)0.15. The larger mobility in (FAPbI3)0.95(MAPbI3)0.05 could be assigned to the slowing down of the carrier scattering time. Therefore, the physical origin of the higher carrier mobility in the (FAPbI3)0.95(MAPbI3)0.05 should be related with the lattice distortion and enhanced electron–phonon coupling induced by the substitution. In addition, (FAPbI3)0.95(MAPbI3)0.05 will lose fewer active carriers during the polaron cooling process than that in (FAPbI3)0.85(MAPbBr3)0.15, indicating lower thermal dissipation in (FAPbI3)0.95(MAPbI3)0.05. Our results suggest that besides the smaller bandgap, the higher polaron mobility improved by the substitution engineering in α-FAPbI3 can also be an important factor for the high PCE of the black phase α-FAPbI3 based solar cell devices.

Coupling Intracompound Charge Transfer and Cluster‐Centered Excited States in Cu(I) Halide Hybrids for Efficient White Light Emission

Abstract0D hybrid organic–inorganic metal halides have attracted significant interest due to their unique optoelectronic properties, but attainment of efficient and stable white light emission (WLE) in such compounds remains a challenge. Here, efficient WLE via a molecular design that couples intracompound charge transfer and cluster‐centered excited states in 0D halide hybrids is demonstrated. Two Cu(I) halide hybrids, K(18‐crown‐6)Cu2Br3 and Na4(18‐crown‐6)5In2Cu4Br14·8H2O, are synthesized wherein luminescent [Cu4Br6]2− clusters are isolated from each other and surrounded by 18‐crown‐6 coordinated alkali metal cations. In the case of K(18‐crown‐6)Cu2Br3, [Cu4Br6]2− clusters are only partially isolated, leading to strong orange emission with a photoluminescence quantum yield (PLQY) of 53% under UV excitation. Strikingly, to a larger extent of isolation as that, in Na4(18‐crown‐6)5In2Cu4Br14·8H2O as a result of the incorporation of nonemissive [InBr4]− clusters, intense white light emission with a PLQY of 97% is achieved. The dual cluster‐centered states, coupled with a mixed metal‐to‐ligand and halide‐to‐ligand charge transfer state, are responsible for this bright white luminescence. This work provides new design principles for expanding the materials library for single‐component, solid‐state WLE.

Bromo- and iodo-bridged building units in metal-organic frameworks for enhanced carrier transport and CO2 photoreduction by water vapor

Organolead halide hybrids have many promising attributes for photocatalysis, e.g. tunable bandgaps and excellent carrier transport, but their instability constraints render them vulnerable to polar molecules and limit their photocatalysis in moisture. Herein, we report the construction of metal–organic frameworks based on [Pb2X]3+ (X = Br–/I–) chains as secondary building units and 2-amino-terephthalate as organic linkers, and extend their applications in photocatalytic CO2 reduction with water vapor as the reductant. Hall effect measurement and ultrafast transient absorption spectroscopy demonstrate the bromo/iodo-bridged frameworks have substantially enhanced photocarrier transport, which results in photocatalytic performances superior to conventional metal-oxo metal-organic frameworks. Moreover, in contrast to lead perovskites, the [Pb2X]3+-based frameworks have accessible porosity and high moisture stability for gas-phase photocatalytic reaction between CO2 and H2O. This work significantly advances the excellent carrier transport of lead perovskites into the field of metal-organic frameworks.

Inorganic Chain Mediated Excitonic Properties in One-Dimensional Lead Halide Hybrid Perovskites.

Semiconductors that emit intrinsic white light are considered next-generation lighting sources. Herein, the broadband emission of one-dimensional (1D) lead halide perovskites, TMAPbBr3-xIx (x = 0, 1, 1.5, 2, 3; TMA+ = tetramethylammonium), is systematically investigated. Lattice distortion causes the conversion of dark excitons to bright self-trapped excitons. Owing to its strongly localized exciton recombination and high absorption probability, TMAPbBr3 is the most viable in this family. A delocalized hole increases the nonradiative recombination rate of excitons in TMAPbBr3-xIx alloys. In 1D TMAPbBr3-xIx perovskites, the vibration mode of the Pb-X bond stretching of the PbX6 octahedra contributes more to the effect on exciton-phonon coupling than the mode of the X-Pb-X angle bending. Pb-X bond stretching and spontaneous polarization can tune exciton binding energy. This systematic study of excitonic behavior in 1D compounds relates the nature of ground states to the unknown excited states and provides the rational design of materials with stable and efficient broadband emission.

Enhanced Stokes Shift and Phase Stability by Cosynthesizing Perovskite Nanoparticles (MAPbI3/MAPbBr3) in a Single Solution

Herein, diblock copolymer reverse micelle templating (RMD) is used to control the reaction kinetics of metal halide hybrid perovskites formation to fabricate systems showing dual‐phase emission. Through micelle templating, desired compositions can be engineered which show high phase stability of mixtures of perovskite nanoparticles (NPs) through micellar shielding and stabilizing of the cage structure. In addition, Stokes shift of around 150 nm, one of the largest reported for perovskite systems, can be obtained with careful control over synthesis kinetics. Using an unconventional approach, that is, mixing methylammonium iodide (MAI) and lead bromide PbBr2, systems consisting of both green‐ and red‐emitting NPs are fabricated by a two‐step reaction process using RMD. By obtaining two stable phases in a single solution, the NP system can absorb in the ultraviolet region and emit in the red region, making them excellent candidates for downconversion to improve solar cells efficiency, as shown for two polymer active layers in organic bulk heretojunction solar cells (OPVs). Exploiting the phase stabilizing effect of the micelles, the reaction kinetics of perovskite formation can be tuned for various halide substitutions, opening up new avenues for coexisting perovskite phases for photovoltaic and light‐emitting applications.

Amino-Acid-Induced Circular Polarized Luminescence in One-Dimensional Manganese(II) Halide Hybrid.

Circular polarized luminescence (CPL)-active materials attract great attentions owing to their widely applications in 3D optical displays and encrypted transmission. Inspired by the strategies adopted in perovskite based CPL materials, herein, CPL-active hybrids (D)- and (L)-(tert-butyl prolinate)MnCl3 were successfully prepared by assembling chiral D/L tert-butyl prolinate with manganese (II) chloride. Single crystal structures show the as-formed hybrids possess one-dimensional (1D) structure containing linear chains of face-sharing MnCl6 octahedral surrounded by prolinate cations. The 1D Mn(II) hybrids display strong red emission peaked at 646 nm with PLQY of 67.1 % and 57.2 % for d-type and l-type, respectively, representing the highest PLQY for 1D MnII hybrids. Interestingly, the 1D Mn(II) hybrids exhibit prominent circular dichroism (CD) signals and remarkable CPL activity with the dissymmetry factor g of 6.1*10-3 and -6.3*10-3 from 550 to 800 nm for (D)- and (L)-(tert-butyl prolinate)MnCl3 , respectively, owing to the existence of chiral cations. It is worthy noted the obtained g represents the highest value for non-lead organic-inorganic hybrids.

Two [Co(bipy)3]3+-Templated Silver Halobismuthate Hybrids: Syntheses, Structures, Photocurrent Responses, and Theoretical Studies.

Employing in situ-generated metal complexes as structural decorating agents, we, for the first time, isolated two [Co(bipy)3]3+-templated silver halobismuthate hybrids, namely [Co(bipy)3]2Ag4Bi2X16 (X = Br (1), I (2); bipy = 2,2'-bipyridine). Compounds 1 and 2 belong to the isomorphic phrases and exhibit the nonperovskite structures characteristic of the discrete [Ag4Bi2X16]6- anions. UV-vis absorption spectra analyses showed that the optical band gaps of compounds 1 and 2 are 2.40 and 1.95 eV, respectively, implying the visible light responding semiconductor properties. Moreover, under the alternate light illumination, the title compounds exhibited "on/off" photocurrent behaviors, with high photocurrent densities comparable to many metal halide hybrids. Presented in this work also involved the Hirshfeld surface analyses and X-ray photoelectron spectroscopy studies together with the theoretical band structures, density of states, and electron wave functions.

Circularly Polarized Luminescence based on 0D Lead‐Free Antimony (III) Halide Hybrids

AbstractChiral materials with circularly polarized luminescence (CPL) are currently attracting great attention for their wide applications in bioresponsive imaging, 3D displays, and storage of information. Herein, CPL‐active enantiomorphic hybrids (R)‐ and (S)‐C6H15Cl2NO⋅SbCl5are obtained by self‐assembling chiral R/S‐(3‐chloro‐2‐hydroxypropyl)trimethylammonium chloride with antimony(III) chloride, giving a 0D structure with SbCl5pyramids isolated by (3‐chloro‐2‐hydroxypropyl)trimethylammonium chloride cations. The formed enantiomers exhibit brilliant orange emission peaked at 604 nm with photoluminescence quantum yield as high as 71.2%, originating from the self‐trapped exciton emission demonstrated by photophysical characterization. Due to the existence of chiral organic cations, the enantiomers exhibit strong chiral‐optical properties with mirror‐image circular dichroism signals in ground state and obvious CPL activity with the dissymmetry factorglumof 2.5 × 10−4and −1.6 × 10−4for R‐type and S‐type, respectively. It should be mentioned that these are the first reported 0D hybrids with CPL‐activity. This work paves an avenue for developing eco‐friendly CPL materials with highly ‐efficient luminescence.

Halogen substitution assisted modification on phase transition point and band gap of (DBU) PbX3 (X = Cl, Br, I)

Lead halide hybrid perovskite with typical formula ABX3 has great application prospects in the field of optoelectronic devices due to their excellent characteristics, including easy processing, adjustable structure, tunable band gaps. In this work, we report three halogen-substituted lead halide hybrid perovskites, namely, (DBU) PbX3 (DBU ​= ​1,8-diazabicyclo [5.4.0] undec-7-ene, X ​= ​Cl, Br, I). These hybrid compounds have similar one-dimensional chain perovskite structures and undergo above-room temperature solid to solid phase transition. The variation of the heavy halogen atoms from Cl, Br to I on the X site causes a gradually larger octahedral space, which contributes to the decrease in phase transition temperature, because of the confinement effect. Meanwhile, a reduction in the band gap occurs for (DBU) PbX3 was obtained. This work highlights the halogen substitution on the lead halide hybrid perovskite towards excellent performance, which will benefit the field of optoelectronics.

Regulated room temperature phosphorescence from zero-dimensional organometallic halide hybrids for anti-counterfeiting and encryption

Organometallic materials with room temperature phosphorescence (RTP) emission are of bright development prospects in optoelectronic application. Herein, we prepared two types of isostructural zero-dimensional metal-organic single crystals with RTP effect named as bis(tetraphenylphosphonium) titanium hexafluoride (Ph4P)2TiF6·2H2O and bis(tetraphenylphosphonium) zirconium hexafluoride (Ph4P)2ZrF6·2H2O. The as-prepared fluoride crystals can simultaneously emit ultraviolet (UV) fluorescence and green phosphorescent emission under 290 nm excitation at room temperature. The RTP could be observed by naked eyes for more than 6 s after removing the excited UV source. By introducing bromide ions into the crystal framework to enhance the heavy-atom effect, the photoluminescence quantum yield of the compounds dramatically boosted to 19.47%. These results provide a facile design strategy for the adjustment of efficient transient and long-lasting RTP. Furthermore, the as-prepared materials were blended in the resins and printed as the anti-counterfeiting signal labels. Therefore, this work does not only reveal the efficient RTP phenomenon in the zero-dimensional metal-organic ionic compounds, but also provide potential candidates for the realization of anti-counterfeiting technology.

Organic–Inorganic Hybrid Tin Halide Single Crystals with Sulfhydryl and Hydroxyl Groups: Formation, Optical Properties, and Stability

Lead (Pb)-free halide hybrid materials have received a great deal of attention because of their potential in optoelectronic applications. However, heteroatom-based amine lead-free tin halide hybrid single crystals have not been well investigated yet. Detailed synthetic processes, growth, crystal structures, and stability of (ACH2CH2NH3)2SnBr6 (A = OH or SH) and (BCH2CH2NH3)2SnI4 (B = I or SH) single crystals were investigated. Interestingly, (IH3NCH2CH2SSCH2CH2NH3)2HPO3 exhibited orange-red photoluminescence (PL) at about 620 nm with an average PL lifetime of about 912 ns. (HSCH2CH2NH3)2SnI4 single crystals exhibited a PL peak at 620 nm with an average PL lifetime of about 0.607 ns. More importantly, (HSCH2CH2NH3)2SnI4 single crystals exhibited reversible red-black color transformations when exposed to a H3PO2 solution and an ambient atmosphere, which was attributed to oxidation from Sn2+ to Sn4+, rather than from I- to I3- (I2). The intriguing characteristics should provide guidance for further optoelectronic applications of these Pb-free halide hybrid materials.

Multi-Mode and Dynamic Persistent Luminescence from Metal Cytosine Halides through Balancing Excited-State Proton Transfer.

Persistent luminescence has attracted great attention due to the unique applications in molecular imaging, photodynamic therapy, and information storage, among many others. However, tuning the dynamic persistent luminescence through molecular design and materials engineering remains a challenge. In this work, the first example of excitation‐dependent persistent luminescence in a reverse mode for smart optical materials through tailoring the excited‐state proton transfer process of metal cytosine halide hybrids is reported. This approach enables ultralong phosphorescence and thermally activated delayed fluorescence emission colors highly tuned by modulation of excitation wavelength, time evolution, and temperature, which realize multi‐mode dynamic color adjustment from green to blue or cyan to yellow‐green. At the single crystal level, the 2D excitation/space/time‐resolved optical waveguides with triple color conversion have been constructed on the organic‐metal halide microsheets, which represent a new strategy for multi‐dimensional information encryption and optical logic gate applications.

Controlled Modulation of the Structure and Luminescence Properties of Zero-Dimensional Manganese Halide Hybrids through Structure-Directing Metal-Ion (Cd2+ and Zn2+) Centers.

Zero-dimensional (0D) metal halide hybrids with high exciton binding energy are excellent materials for lighting applications. Controlling/modulating the structure of the constituent metal halide units allows tunability of their photoluminescence properties. 0D manganese halide hybrids are currently attracting research efforts in lighting applications due to their eco-friendly and strong emission. However, structural transformation-induced tunability of their photophysical properties has rarely been reported. Herein, we demonstrate a rational synthetic strategy to modulate the structure and luminescence properties of 0D Mn(II) halide hybrids utilizing the structure-directing d10 metal ions (Cd2+/Zn2+). 0D metal halide hybrids of Cd2+/Zn2+, which act as hosts with tunable structures, accept Mn2+ ions as substitutional dopants. This structural flexibility of the host d10 metal ions is realized by optimizing the metal-to-ligand ratio (Cd/AEPip). This reaction parameter allows structural transformation from an octahedral (AEPipCdMnBrOh) to a tetrahedral (AEPipCdMnBrTd) 0D Mn halide hybrid with tunable luminescence (orange → green) with high photoluminescence quantum yield. Interestingly, when Zn2+ is utilized, a tetrahedral AEPipZnMnBr structure forms exclusively with strong green emission. Optical and single-crystal X-ray diffraction structural analysis of the host and the doped system supports our experimental data and confirms the structure-directing role played by Cd2+/Zn2+ centers. This work demonstrates a rational strategy to modulate the structure/luminescence properties of 0D Mn(II) halide hybrids, which can further be implemented for other 0D metal halide hybrids.