Metal complex incorporated low-dimensional perovskite crystalline composition

Abstract

The invention relates to a new crystalline composition comprising low-dimensional perovskite structures incorporating metal complexes. Each crystalline unit cell is characterized by a defined empirical formula, and the metal complexes act as linkers between inorganic layers, contributing to the formation of low-dimensional perovskite arrays. The composition enables the creation of various low-dimensional perovskite structures, including 0D, 1D, and 2D configurations. The metal complexes exhibit various physicochemical properties, offering applications in catalysis, electronics, optics, quantum computing, drug delivery, and more. The fabrication methods include a variety of technological processes, making it adaptable to different formats and applications.

Description

[0001] Metal Complex Incorporated Low-Dimensional Perovskite Crystalline Composition

[0002] DESCRIPTION:

[0003] The invention pertains to a novel crystalline composition comprising low-dimensional perovskite structures incorporating metal complexes. Each crystal unit cell is characterized by a defined empirical formula, and the metal complexes act as linkers between inorganic layers, contributing to the formation of low-dimensional perovskite arrays. The composition allows the creation of various low-dimensional perovskite structures, including OD, 1D, and 2D configurations. The metal complexes exhibit diverse physicochemical properties, offering applications in catalysis, electronics, optics, quantum computing, drug delivery, and more. The fabrication methods encompass a variety of technological processes, making it adaptable for different formats and applications.

[0004] Background:

[0005] Low-dimensional perovskites are a class of materials that have gained significant attention in the field of materials science and condensed matter physics due to their unique electronic, optical, and structural properties [Z. Chu, et al. Small Struct 2021, 2, 2000133]. The term "perovskite” originally refers to a specific crystal structure found in certain minerals, named after a mineral called perovskite (CaTiOa) [N. Yaghoobi Nia, et al. Elsevier 2020, ISBN 9780081027622, 163-228]. The perovskite structure is characterized by a three-dimensional arrangement of metal cations (typically A-site), oxygen anions, and a larger cation (typically B- site) situated between oxygen octahedra. The general formula for a perovskite compound is ABX3. Low-dimensional materials are those that have reduced dimensions in one or more directions compared to their bulk counterparts. In the case of low-dimensional perovskites, the term refers to structures where the 3D perovskite lattice is confined in zero or one or two dimensions, leading to unique properties arising from quantum confinement effects. OD Perovskites: also known as perovskite quantum dots (QDs) or nanocrystals, are nanoscale structures that have been derived from the perovskite crystal structure but exhibit zerodimensional characteristics due to their extremely small size and quantum confinement effects. 0D perovskites have all their dimensions confined to the nanometer scale, resulting in unique electronic and optical properties. 0D perovskites are typically nanometer-sized particles with dimensions on the order of a few nanometers. Instead, they are discrete nanocrystals with confined electronic states. Due to their small size, 0D perovskites exhibit quantum confinement effects, which arise from the confinement of charge carriers and excitons within a nanoscale volume. These effects lead to quantized energy levels, where the electronic and optical properties of the nanocrystals are strongly influenced by their size. One of the most notable characteristics of 0D perovskites is their tunable optical properties [J. Yin, et al. Sci. Adv. 2017, 3, e1701793]. The size-dependent bandgap of these nanocrystals allows to control the wavelength of light they absorb and emit. This tunability makes OD perovskites attractive for various applications, including displays, lighting, and optical sensing. OD perovskites often exhibit high photoluminescence quantum yields (PLQYs), which means they efficiently emit light upon absorption of photons [P. Han, et al. Angew. Chem. 2020, 132, 12809]. This property is crucial for applications in optoelectronics and photonics. The properties of these nanocrystals are highly dependent on their size, shape, and composition, leading to tunable electronic and optical behavior. Specifically, OD perovskites consist of individual metal halide octahedral anions or metal halide clusters. These entities are isolated from each other by encircling inorganic or organic cations, and as a result, they do not give rise to the formation of electronic bands. Furthermore, OD perovskites contains a significant exciton binding energy, which enhances radiative recombination within optoelectronic devices. Notably, OD organic metal halide perovskites demonstrate exceptional stability in ambient conditions due to their structure as ideal host-guest systems, wherein metal halide octahedron units / clusters are safeguarded by organic shells [Y.-Y. Ma, et al. Adv. Opt. Mater. 2022, 10, 2200386]. All the conventional reported 0D perovskites have been formed by interaction of the bulky organic molecules (especially organic cations) with inorganic metal halide or metal oxide structures to form 0D perovskite crystals (inorganic metal halide or metal oxide units are surrounded by the organic cations) and there is not any report for formation of the 0D perovskite structures by incorporating of the transition metal complexes with inorganic metal halide and metal oxide units. Some examples of the conventional 0D perovskite structures can be listed as following patents: B. Ma,et al. (US11466040B2) made 0D perovskite structures by contacting an organic ligand halide salt with a metal halide in a liquid to form a precursor liquid and mixing the precursor liquid with an organic liquid to form micro crystals of the 0D metal halide perovskites. T. Krishnamoorthy, et al. (WO / 2019 / 013709) have used different organic cations with various alkyl chains as linker for formation of low-dimensional perovskite structures. M. Kuno, et al. (WO / 2022 / 006515) have reported a low-dimensional layer of formula (A)x(A')yA”(i-x~y)BX3 while it comprising a perovskite and a non-perovskite units while still organic cations have been used as linker in the mix-layered structure. 1D Perovskites: Unlike their 3D counterparts, 1D perovskites are characterized by elongated structures, forming chains, nano-rods or nanotubes. This departure from the typical cubic or tetragonal lattice arrangements imparts distinct electronic, optical, and mechanical properties to these materials. The constrained dimensionality of these structures provides several advantages. The quasi-1D nature of these structures often leads to improved stability, crucial for applications in optoelectronics, photovoltaics, and catalysis [T. Qiu, et al. Nanoscale, 2018,10, 20963; J. Li, et al. Nano Energy, 2024, 122, 109329; Y.Pi, Nano Energy, 2021, 88, 106251]. The reduced dimensionality minimizes defects and phase transitions, contributing to long-term material integrity. The confinement of charge carriers along one dimension allows for the engineering of unique electronic properties. This tunability is particularly advantageous in designing materials for specific electronic applications, such as transistors and sensors [N. Kaur, et al. Langmuir, 2020, 36, 6326; C. Wang, et al. Phys. Chem. Chem. Phys., 2022, 24, 18401]. Furthermore, quantum confinement effects become pronounced in 1D perovskites due to the restricted movement of charge carriers along one axis. This phenomenon leads to discrete energy levels, influencing the optical and electronic characteristics of the material. The anisotropic nature of 1D perovskites facilitates improved charge transport along the chains or columns. This property is instrumental in enhancing the efficiency of devices like solar cells and light-emitting diodes. All the reported inventions related to formation of 1D perovskite structures and their applications are based on using organic cations to surrounding the inorganic metal halide or metal oxide chains (e.g., B. Ma, et al. US20180037813; R. Gautier, et al. EP3581568) and there is not any report about incorporation or using of transition metal complexes as alternative of organic cations for this concept. 2D Perovskites: These are layered structures where the perovskite sheets are separated by organic or inorganic spacer molecules. These spacer molecules play a critical role in tuning the properties of the material. The most common 2D perovskites have the formula where R is an organic cation, A is the smaller cation, B is the larger cation, and X is the anion. Indeed, the perovskite layers are separated by the organic or inorganic spacers, leading to dimensional confinement along two axes. The thickness and composition of the perovskite layers can be controlled, allowing for tunable bandgaps and absorption properties ]M. Zendehdel, et al. Solar RRL, 2022, 6, 2100637], This is particularly useful for designing materials for specific optical and electronic applications. In addition, the reduced dimensionality of the layers can lead to weaker exciton binding energy compared to their 3D counterparts, which can improve charge carrier transport and device efficiency [K. Zheng, etal. J. Phys. Chem. Lett. 2019, 10, 19, 5881]. 2D perovskites often exhibit improved environmental stability compared to their 3D counterparts, making them suitable for applications like photovoltaics [M. Zendehdel, et al. Solar RRL, 2022, 6, 2100637]. Organic linkers or spacer molecules play a crucial role in defining the properties of 2D perovskites. These molecules separate the perovskite layers and determine the overall structure and properties of the material. Common organic linkers which have been used in the reported 2D perovskite structures include: i) Long Aliphatic Chains: Organic molecules with long aliphatic chains, such as n-butylamine or n-octylamine, are often used to provide sufficient spacing between the perovskite layers, ii) Aromatic Compounds: Aromatic molecules like phenethylammonium or phenylpropylammonium are also be used as linkers. These molecules can introduce π-conjugation, affecting the electronic properties of the material, iii) Diammonium Ions: Organic cations with two ammonium groups like ethylenediammonium and Butylenedlammonium can serve as linkers, iv) Other Organic Cations: Additional organic cations such as ammonium, formamidinium and Guanidinium also used as linkers. The choice of linker can significantly impact the electronic structure, crystalline packing, and overall performance of 2D perovskites [Z.-Y. Lin, et al. Angew. Chem. 2023, 62, e202305298]. The nature of the linker can affect the energy levels within the perovskite layers, including the valence and conduction bands. Different linkers can modify the bandgap and electronic structure, influencing the absorption and emission properties of the material. The size and shape of the organic linker influence the arrangement of perovskite layers. The linker affects the packing efficiency of the perovskite layers, which in turn influences the carrier mobility. Efficient packing and reduced structural disorder can lead to higher carrier mobility, resulting in better charge transport properties. The nature of the linker can impact the overall stability of the 2D perovskite structure. Certain linkers may enhance the material's resistance to environmental factors, such as moisture and oxygen [X. Li, et al. Chem. Rev.2021 , 121 , 2230]. However, selecting an appropriate linker requires a balance between factors such as stability, electronic properties, and the ability to form well-ordered layered structures. The linker should not only provide spacing but also contribute to the desired electronic properties of the material. Achieving high-quality crystallinity and minimizing defects is crucial for optimizing charge transport. The choice of linker and synthesis conditions can affect the crystal growth and structural integrity of the material. In addition, introducing organic linkers might lead to structural heterogeneity within the material, which can negatively impact carrier transport and overall device performance [Y. Zou, et al. Mater. Chem. Front., 2024, 8, 82]. While the linker can tune electronic properties, achieving a precise control over bandgap, energy levels, and charge carrier dynamics can be challenging due to complex interactions between the organic linker and the inorganic perovskite layers. In particular, incorporating 2D perovskites into functional devices, such as solar cells and photodetectors, requires careful consideration of how the linker choice affects the overall device performance. All the reported inventions related to formation of 2D perovskite structures and their applications are based on using various organic cations as linker or spacer between inorganic metal halide or metal oxide chains (e.g., J.-H. He and B. Cheng, US10756282B2; W. Peixi, et al. WO / 2022 / 047590) and there is not any report about incorporation or using of transition metal complexes as linker or spacer in the 2D perovskite structures.

[0006] The present invention relates to formation of a crystalline composition with substantially low dimensional including zero-dimensional, one-dimensional and two-dimensional array of the crystal unit cells of the perovskite structure in which each crystal unit cell having an empirical formula of such that each X Is positioned within an octahedral configuration of B and create a framework within which (A) is incorporated while [MmLn] coordination complexes placed in the crystal unit cell, in which it serves as linker between inorganic layers formed by A, B and X to generate a low-dimensional perovskite structure. Indeed, M comprise different group IIIB, IVA, VA and transition metals with different valence electrons and ionic charges, L consist of different ligands with different valence electrons, A and B comprise various organic and inorganic cations and X include diverse Group VA, VIA and VIIA anions, or a combination thereof. In the general formula p, q and r representing the formal charges wherein ~-4 +4 and l < q,r and wherein l < m, n, x, z and 0 < y representing the molar numbers of the components. In this crystalline composition the [MmLn] complexes are sandwiched between the inorganic layers formed by A, B and X structures to generate a low-dimensional perovskite array of the crystal unit cell. Different low-dimensional perovskite structures including OD, 1 D and 2D forms individually or a combination of two or more thereof by using [MmLn] complexes as linker depending to the size of [MmLn], A, B and X. In particular, 2D perovskite structure of this invention forms with different thickness of the inorganic layer that are stacked between the [MmLn] layers. The general formula for these 2D perovskite structures is , where "b" represents the number of inorganic layers between the [MmLrl] layers wherein 1 < a. Various types of [MmLn] metal complexes including but not limited to, transition metal complexes with different organic and inorganic ligands such as Schiff bases, porphyrins, salens, salophenes, phthalocyanines, amines, amides, water, carbonyls, cyanides, thionyls, amino acids, proteins and any other Lewies bases, organometallic compounds like metallocenes or a combination of two or more thereof use as linker. When [MmLn] complexes bounded in the unit cell of low-dimensional perovskite structure promotes novel physicochemical properties due to intracrystalline carrier transport and wavefunction couplings of the metal complexes with inorganic chains which can extend the lowdimensional properties of the lattice to supports stronger electron-phonon and spin-orbit coupling. The low-dimensional composition forms as single crystals, polycrystal, quasicrystals, thin films, thick films, nanoparticles, quantum dots, nanotubes, nanorods, nanopins, nanofibers, nanoflowers, and any other nanostructure as individual or composite with other compounds and materials. It fabricates via different technological processes including but not limited to slow evaporation, cooling crystallization, solvent evaporation, solvothermal synthesis, hydrothermal synthesis, vapor diffusion, layer-by-layer deposition, chemical vapor deposition, physical vapor deposition, flux crystal growth, zone melting, solution growth, template-assisted growth, self-assembly, electrochemical deposition, floating zone method, melt growth, dip-coating, spin coating, blade coating, slot die, meniscus coating, screen printing, roll-to-roll printing, spray coating, electrostatic coating, epitaxial growth, chemical bath deposition, ink-jet printing and electrospinning. It utilizes as precursor or additive of different chemical reactions or different deposition methods in the formats of solid, liquid, paste, powder, ink, sol, gel, core-shell, decorated structures, encapsulated and deposited and embedded on / in a substrate or a combination of two or more thereof. In particular, it uses for temporary incorporating of a metal complex and release / exchange it during a chemical reaction or a physicochemical interaction. Owing to extended physicochemical characteristics it utilizes in different applications including but not limited to catalyst of the chemical reactions, electrocatalysts, photoelectrocatalyst, semiconductor, capacitor, supercapacitor, superconductor, detectors, photovoltaics, magnetic, quantum computing, LASER, transistors, scintillators, radiation shielding, LEDs, sensors, luminescence, phosphorescence, drug delivery, pharmacy, microchips, piezo-electronics, triboelectricity, membranes, electrodes, alloying, organic synthesize, inorganic synthesize, biochemistry, building and construction materials, minerals and mining, optic and photonic, electronics, nuclear energy, batteries, electrolytes, lubricants, solid fuels, space technologies, dyes and pigments, food additives and nanotechnology. Incorporating a metal complex within the crystal unit cell of a low-dimensional perovskite led to a range of interesting and potentially useful properties and functionalities. The interaction between the metal complex and the perovskite matrix results in modifications to the electronic, optical, magnetic, and catalytic properties of the material. The presence of the metal complex introduces additional energy levels within the perovskite's band structure, leading to tunable electronic and optical properties. This is advantageous for applications in optoelectronic devices such as LEDs and solar cells, where precise control over the bandgap and energy levels is crucial. Metal complexes are often utilized as catalysts in various chemical reactions. Incorporating a catalytically active metal complex within a low-dimensional perovskite matrix led to enhanced catalytic activity, due to synergistic effects between the metal complex and the perovskite's inherent properties. Certain metal complexes exhibit magnetic properties due to unpaired electrons in their d- and f- orbitals. Incorporating of such complexes within a perovskite structure result in intriguing spin and magnetic interactions, potentially leading to novel magnetic properties that can be exploited in magnetic storage or spintronics applications. Metal complexes often exhibit luminescence properties, including phosphorescence and fluorescence. Incorporating luminescent metal complexes into lowdimensional perovskites enhances their photoluminescence properties, making them useful for applications in lighting, scintillators, displays, and sensors. Incorporation of a carefully chosen metal complex into the low-dimensional perovskite structure introduces a range of beneficial properties, including increased surface area, improved conductivity, facilitated charge transfer, tunable electrochemical characteristics, enhanced stability, and synergistic effects which can improve the performance of supercapacitors, making them more efficient and reliable for energy storage applications. Furthermore, the interaction between the metal complex and the low-dimensional perovskite conducts to new quantum states or coherent phenomena. These have implications for quantum computing and spintronics, where the control and manipulation of quantum states are critical. Incorporating a metal complex within a perovskite matrix improves the stability and protection of the metal complex against environmental factors such as oxidation or degradation. This is particularly relevant for applications in harsh conditions such as aerospace environments and high-energy radiation applications or for long-term device stability. It uses for protection and releasing of the metal complex depending on the environment which can provide a suitable choice for application in the chemical synthesis and drug delivery concepts. The combination of the metal complex's properties with those of the low-dimensional perovskite matrix led to synergistic effects, where the overall properties of the material are more than just the sum of its individual components. The invention will be described with reference to the attached Figures where:

[0007] Figure 1 represents a schematic of the metal complex incorporated low-dimensional perovskite crystalline composition of the present invention when it makes a 2D perovskite crystalline unit cell similar to Ruddlesden-Popper 2D perovskites unit cells where the [MmLn] metal complex linkers or spacer layer (3) is sandwiched between the Ab.iBbX3b-i inorganic layers of (1 ) and (2). Indeed, the inorganic layers are composited of the BbXsb+i inorganic units of (4) and the A small cation (5) is located in the octahedral spaces which are created by linking of the inorganic units (4). In this configuration the [MmLn] metal complexes (6) are linked together and each one to one of the adjacent inorganic layers via intermoiecular bonds such as hydrogen bonding, π- π and CH- π stackings.

[0008] Figure 2 represents a schematic of the metal complex incorporated low-dimensional perovskite crystalline composition of the present invention when it makes a 2D perovskite crystalline unit cell similar to Dion-Jacobson 2D perovskites unit cells where the [MmLn] metal complex linkers or spacer layer (9) is sandwiched between the Ab-iBbXsb+i inorganic layers of (7) and (8). The inorganic layers are composited of the BbXab+i inorganic units of (10) and the A small cation (11) is located in the octahedral spaces which are created by linking of the inorganic units. In this configuration the [MmLn] metal complexes (12) are linked together and each one to two of the adjacent inorganic layers via intermoiecular bonds such as hydrogen bonding, π- π and CH- π stackings.

[0009] Figure 3 shows a schematic configuration of the crystalline unit cell of the metal complex incorporated low-dimensional perovskite crystalline composition of the present invention when it makes a 0D perovskite structure (13). The A small cation (14) is located in the octahedral space which is created from linking of the BbXab+i inorganic units (15) and the [MmLn] metal complexes (16) are linked together and surrounding of inorganic unit via intermoiecular bonds such as hydrogen bonding, π- π and CH- π stackings.

[0010] Figure 4 shows a schematic configuration of the crystalline unit cell of the metal complex incorporated low-dimensional perovskite crystalline composition of the present invention when it makes a 1D perovskite structure (17). Accordingly, the A small cation (18) is located in the octahedral space which is created from linking of the BbXsb+i inorganic units (19) and the [MmLn] metal complexes (20) are linked together and surrounding of the inorganic unit via intermoiecular bonds such as hydrogen bonding, π- π and CH- π stackings leading to extension of the unit cell in one axis to form various 1D perovskite structures e.g., nanorods, nanopins, nanofibers and nanotubes.

[0011] Figure 5 shows a schematic configuration of the crystalline unit cell of the metal complex incorporated low-dimensional perovskite crystalline composition of the present invention when it makes a 2D perovskite structure (21). The A small cation (22) is located in the octahedral space which is created from linking of the inorganic units (23) and the [MmLn] metal complexes (24) are linked together and to two adjacent sheets of the inorganic unit via intermolecular bonds such as hydrogen bonding, π- π and CH- π stackings leading to extension of the unit cell in two axis to form various 2D perovskite structures e.g., nanoribons, nanoflakes, nanosheets, nanoflowers and nanoplates.

[0012] Figure 6 represents an example of the crystal unit cell of a Schiff base metal complex incorporated 2D perovskite crystalline composition of the present invention where a methylammonium small cation (26) is located in the octahedral space which is created from linking of the Pble inorganic units (25) and a chromium Schiff base complex consists of [CrL.2]* cation, in which L is a tridentate Schiff base ligand with full name of N-(2-(2- hydroxyethylamino)ethyl)5-methoxysalicylideneimine, and a chloride anion, in the asymmetric unit, served as metal complexes (27) which are linked together and to two adjacent sheets of the MAPbh inorganic unit via intermolecular bonds such as hydrogen bonding, n-n and CH-π stackings.

[0013] Figure 7 represents an example of the crystal unit cell of a metallocene organometallic complex incorporated 2D perovskite crystalline composition of the present invention where a methylammonium small cation (29) is located in the octahedral space which is created from linking of the Pble inorganic units (28) and a ferrocene served as metal complexes (30) which are linked together and to two adjacent sheets of the MAPbfo inorganic unit via intermolecular bonds such as hydrogen bonding, π- π and CH- π stackings.

[0014] Example 1: Different 2D perovskite thin film crystalline structure of a metallocene organometallic complex incorporated 2D perovskite crystalline composition of the present invention with general formula of has been fabricated and characterized by various techniques including X-ray diffraction, UV-Vis absorbance I reflectance, Photoluminescence (PL), Time-Resolved Photoluminescence (TRPL), scanning electron microscopy (SEM) and grazing incident wide angle X-ray scattering (GIWAXS) and the results confirm the formation of Ruddlesden-Popper (RP) 2D perovskite structure with different thicknesses of the inorganic layer, indeed, such metallocene organometallic complex incorporated 2D perovskite crystalline composition has been used as absorber and passivation layer of perovskite photovoltaics (solar cells, modules and panels) with both n-i-p and p-i-n stack configurations and the results show markedly enhancement of the photovoltaic performances and stability of the devices against various stressors. The fabricated perovskite photovoltaics showed long stability beyond standard protocols of ISOS and IEC61215 via performing various accelerated and outdoor tests including continuous light soaking (maximum power point tracking) at 1-sun solar irradiation, damp / heat test at 85=C and 85% relative humidity, continuous light soaking under UVA / UVB irradiation and outdoor performance tracking. In particular, the fabricated perovskite photovoltaics showed outstanding stability against harsh space environments via passing various stability test including, UV / O3 stability, space-based thermal cycling, proton irradiation tests (both high energy and low energy protons with high irradiation flux) and stratospheric flight tests.

Claims

Claims1. A crystalline composition is formed, consisting of a minimum of one layer with both first and second surfaces, where each layer includes:A substantially low dimensional including zero-dimensional, one-dimensional and two- dimensional array of the crystal unit cells of the perovskite structure in which each crystal unit cell having an empirical formula of such that each X is positionedwithin an octahedral configuration of B and create a framework within which (A) are incorporated while [MmLn] complexes oriented as linker between inorganic layers formed by A, B and X; wherein M comprise different group IIIB, IVA, VA and transition metals with different valence electrons and ionic charges, L comprise different ligands with different valence electrons, A and B comprise different organic and inorganic cations and X comprise different Group VA, VIA and VI I A anions, or a combination thereof; and wherein p, q and r representing the formal charges wherein and whereinand wherein the complexes are sandwiched between the inorganic layers formed by A,B and X structures to generate a low-dimensional perovskite array of the crystal unit cell. This crystalline composition forms, wherein:. r = 1+ and 2+ and B including but not limited to Cu, Fe, Co, Ni, Mn, Ca, Sr, Ba, Mg, Pb, Cd, Sn, Ru, Rh, Ir, Pd, Pt, Os and Lanthanides such as Eu and Sm or a combination of two or more thereof;. r - 3+ and B including but not limited to, Fe, Co, Cr, Al, Ga, Sc, Y, Mn, Ru, Rh, In, Sb, V and Lanthanides such as La, Ce, Pr and Nd or a combination of two or more thereof;. r = 4+ and B including but not limited to, Ti, Zr, Hf, Sn, Pb or a combination of two or more thereof;. r ~ 5+ and B including but not limited to, V, Nb, Ta or a combination of two or more thereof;. different types of [MmLn] metal complexes including but not limited to, transition metal complexes with different organic and inorganic ligands such as Schiff bases, porphyrins, salens, salophenes, phthalocyanines, amines, amides, water, carbonyls, cyanides, thionyls, amino acids, proteins and any other Lewies bases, organometallic compounds like metallocenes or a combination of two or more thereof use as linker.

2. The crystalline composition of claim 1 , wherein different low-dimensional perovskite structures including OD, 1 D and 2D form individually or a combination of two or more thereof by using [MmLn] complexes as linker depending to the size of [MmLn], A, B and X.

3. The crystalline composition of claim 1, wherein [MmLn] complexes bounded in the unit cell of low-dimensional perovskite structure promote novel physicochemical properties due to intracrystalline carrier transport and wave-function couplings of the metal complexes withinorganic chains. The interaction between the metal complex and the perovskite matrix results in modifications to the electronic, optical, magnetic, and catalytic properties of the material.

4. The crystalline composition of claim 1 , wherein forms 2D perovskite structure with different thickness of the inorganic layer that are stacked between the [MmLn] layers. The general formula for these 2D perovskite structures of claim 1 is [MmLn]aAb-iBbX3b+i , where “b" represents the number of inorganic layers between the [MmLn] layers wherein 1 < a.

5. The crystalline composition of claim 1 forms:. as single crystal, polycrystal, quasi-crystals, thin films, thick films, nanoparticles, quantum dots, nanotubes, nanorods, nanopins, nanofibers, nanoflowers, and any other nanostructure as individual or composite with other compounds and materials;. via different processes including but not limited to slow evaporation, cooling crystallization, solvent evaporation, solvothermal synthesis, hydrothermal synthesis, vapor diffusion, layer-by-layer deposition, chemical vapor deposition, physical vapor deposition, flux crystal growth, zone melting, solution growth, template-assisted growth, self-assembly, electrochemical deposition, floating zone method, melt growth, dipcoating, spin coating, blade coating, slot die, meniscus coating, screen printing, roll-to- roll printing, spray coating, electrostatic coating, epitaxial growth, chemical bath deposition, ink-jet printing and electrospinning.

6. The crystalline composition of claim 1 uses:. for temporary incorporating of a metal complex and release / exchange it during a chemical reaction or a physicochemical interaction;. as precursor or additive of different chemical reactions or different deposition methods in the formats of solid, liquid, paste, powder, ink, sol, gel, core-shell, decorated structures, encapsulated and deposited and embedded on / in a substrate or a combination of two or more thereof;. in different applications including but not limited to catalyst of the chemical reactions, electrocatalysts, photoelectrocatalyst, semiconductor, capacitor, supercapacitor, superconductor, detectors, photovoltaics, magnetic, quantum computing, LASER, transistors, scintillators, radiation shielding, LED, sensors, luminescence, phosphorescence, drug delivery, pharmacy, microchips, piezo-electronics, triboelectricity, membranes, electrodes, alloying, organic synthesize, inorganic synthesize, biochemistry, building materials, minerals and mining, optic and photonic, electronics, nuclear energy, batteries, solid electrolytes, lubricants, solid fuels, aerospace technologies, dyes and pigments, food additives and nanotechnology.

7. The presence of the [MmLn] metal complex in the crystalline composition of claim 1 led to:. promoting a tunable electronic and optical properties via introducing additional energy levels of metal complex within the perovskite's band structure which is an important advantageous for applications in optoelectronic devices such as LEDs and solar cells, where precise control over the bandgap and energy levels is crucial;• enhancing the catalytic activity when incorporating a catalytically active [MmLn] metal complex within a low-dimensional perovskite matrix, possibly due to synergistic effects between the metal complex and the perovskite's inherent properties;• intriguing spin and magnetic interactions when incorporating of magnetic [MmLn] metal complexes, potentially leading to novel magnetic properties that can be exploited in magnetic storage or spintronics applications;. enhancing the photoluminescence properties when incorporating luminescent [MmLn] metal complexes, making them useful for applications in lighting, displays, and sensors;. forming new quantum states or coherent phenomena when the interaction between [MmLn] metal complex and the low-dimensional perovskite occurs. These could have implications for quantum computing and spintronics, where the control and manipulation of quantum states are critical .

8. Incorporating of [MmLn] metal complex within the perovskite matrix of the crystalline composition of claim 1 improves the stability and protection of the metal complex and perovskite structure against environmental factors such as oxidation or degradation. This can be particularly relevant for applications in harsh conditions or for long-term device stability.

9. The integration of [MmLn] metal complex properties with the low-dimensional perovskite matrix outlined in claim 1 resulted in the enhancement of synergistic effects. This means that the material’s overall properties exceed the mere sum of its individual components.

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