Inorganic Hybrid Materials Research Articles

Crystal structure, structural geometry, and molecular motion of organic–inorganic perovskite [N(CH3)4]2MnCl4 crystals at phases I, II, and III

Various aspects of the new development of organic-inorganic hybrid [N(CH3)4]2MnCl4 single crystals have been discussed. The phase transition temperatures were determined to be 268 K (TC2) and 291 K (TC1), and the thermodynamic stability was maintained at temperatures up to 669 K. The crystal structures at 250 K (phase III), 275 K (phase II), and 300 K (phase I) are monoclinic, orthorhombic, and orthorhombic, respectively. Notably, while the 1H and 13C chemical shifts gradually changed near TC1 and TC2, the 14N resonance frequency exhibited a split in the number of signals near TC1. Furthermore, the shorter spin-lattice relaxation time T1ρ of 1H than that of 13C suggests facile energy transfer for1H. Additionally, analysing the temperature dependencies of T1ρ for 13C revealed that the activation energy Ea in phase I is approximately five times greater than those in phases III and II. The high Ea observed in phase I primarily stems from the collective motion of the N(CH3)4 group, which contrasts with the considerable freedom observed for the CH3 group in phases III and II. These distinctive physical properties suggest potential applications for [N(CH3)4]2MnCl4 as an organic‒inorganic hybrid material.

Toward a green economy: Lignin-based hybrid materials as functional additives in flame-retardant polymer coatings

This study describes the combination of unique properties of lignin with TiO2 as an innovative and effective preparation method for high-performance flame-retardant additives that may be utilized as polymer coatings. The use of lignin resulted in numerous advantages including an increased number of functional groups, satisfactory biocompatibility, low toxicity, and high carbon content. The major benefit of lignin is associated with the reduced carbon footprint of the manufactured product. Lignin can be classified as a natural flame-retardant agent owing to the high amount of char formed during combustion. In turn, TiO2 exhibits high chemical stability and low operating costs and is considered a non-toxic and environmentally friendly material. During the experiments, commercial TiO2 in anatase crystallographic form, TiO2 synthesized from titanyl sulfate hydrate, and kraft lignin as well as organic–inorganic hybrid materials composed of these materials were evaluated as functional additives in epoxy-resin-based polymer coatings (Epidian 601) and their properties were investigated in detail. The cone colorimetry test confirmed that the obtained hybrids are effective flame-retardant additives for polymer coatings, with a notable fire hazard reduction observed for samples containing a synergistic system of titanium oxide and lignin. The coating with lignin was the most effective in fire suppression processes. The conducted thermal and mechanical investigations confirmed good performance properties of the coatings indicating thermal resistance up to 360 °C and Shore D hardness in a range of 80.36–86.28°Sh, accordingly. Optical profilometry investigations show that the lignin/TiO2 hybrids exhibit a stable topological surface shape as well as good dispersion and uniformity in the polymer matrix. All the conducted tests allowed confirmation that the presence of functional additives in polymer coatings in the form of lignin and TiO2 can be a promising alternative to non-biodegradable synthetic materials which improve flame-retardant properties.

Advanced Organic–Inorganic Hybrid Materials for Optoelectronic Applications

AbstractResearch on organic–inorganic hybrid materials (OIHMs) has experienced explosive growth in the past decades. The diversity of organic components allows for the introduction of various spatial scales, functional groups, and polarities, while inorganic components provide higher hardness, heat resistance, and stability, their flexible combination facilitates the formation of diverse structures. Furthermore, simple and cost‐effective synthesis methods, such as room temperature solution processes and mechanochemical techniques, enable precise control over the materials' properties at different scales, thus achieving adjustable structure–performance relationships. This review will discuss the recent research progress of OIHMs within the field of optoelectronics and related optoelectronic device applications. According to the dimension of inorganic components and the nature of organic–inorganic interface, this review divides OIHMs into four structural categories. The ongoing research has revealed diverse applications for OIHMs in the fields of solar cells, light‐emitting devices, detectors, and memristors. As an outlook, the potential of perovskite and 0D metal halide materials, which are currently the most studied, for enhancing optoelectronic performance and stability is discussed.

Fabrication of metal‐organic frameworks macro-structures for adsorption applications in water treatment: A review

Metal-organic frameworks (MOFs) are emerging porous organic–inorganic hybrid materials composed of metal centers/clusters and various organic ligands, which are widely used in water and wastewater treatment applications due to their large specific surface area, high porosity, tunable chemical properties and abundant active sites. However, pure MOFs powders have limitations such as poor recovery, blocked pipelines and secondary contamination in practical water treatment processes. Enabling the magnetization of MOFs or immobilizing MOFs as macroscopic MOFs materials offers new opportunities to improve solid–liquid separation performances of powdered MOFs. Besides, macroscopic MOFs materials with outstanding adsorption performance and mechanical properties by the combining of 3D particles and 2D nanosheets MOFs with other substrates are widely used for water treatment. This paper provides a comprehensive review of recent advancements in MOFs macro-structures. We firstly summarized the synthesis strategies of magnetic MOFs composites and various MOFs macro-structures such as hydrogels/aerogels, membranes, beads/spheres, others composites, etc. which can be constructed by various methods, including in-situ growth, solvothermal method, direct mixing, self-assembly, layer-by-layer growth, etc. Innovative preparation strategies to improve the mechanical properties of MOFs macro-structures were highlighted. Next the article discusses its application for adsorptive removal of various pollutants (i.e., dyes, heavy metal ions, oils and organic pollutants) from water. Finally, the challenges of macroscopic MOFs materials and their practical applications are presented, while future research directions to overcome these existing limitations are also pointed out.

Control over phase structures’ evolution within the novel organic–inorganic hybrid system for achieving a comprehensive thermal, mechanical, and dielectric properties

Significant challenges persist in developing high-performance, wave-transparent capable of operating above 500 ℃ using organic–inorganic hybrid materials. This study introduced a novel, highly reactive terminal carborane monomer, 4-(3-carborylphenyl) phthalonitrile (CB-Ph), to create a cross-linked network structure and inorganic phase. By integrating this with the conventional high-performance poly (phthalazine ether nitrate ketone) (PPENK), a novel organic–inorganic hybrid system was successfully constructed. Simultaneously, the modifications in the inorganic layer and phase structure of the material with increasing CB-Ph content were examined through nanoindentation and SEM analysis systems, establishing a structural foundation for optimizing the balance between thermal resistance, mechanical strength, and dielectric properties (balance of T-M−D). The thermal performance testing results indicates that the hybrid materials achieved high glass transition temperatures (Tg exceeding 500 ℃). This enhancement is attributable to the synergistic effects of cyanide side group micro-crosslinking and the phthalonitrile crosslinking network, which collectively restricted the movement of chain segments. The P-CB50 resin (PPENK+50 wt% CB-Ph), with its distinctive transition phase structure, boasts the most outstanding comprehensive performance. In terms of thermal stability, it not only features a Tg surpassing 500 ℃ In terms of thermal stability, it not only has a Tg exceeding 500 °C, but also loses only 5 % weight at 599.3° C in a nitrogen atmosphere (Td5%–N2 = 599.3 °C). Mechanical testing reveals that the flexural strength of the P-CB50 composite reaches an impressive 384.3 MPa, while the impact strength attains a significant 109.4 KJ/m2. Even at temperatures as high as 500 ℃, the dielectric constant of the P-CB50 composite material remains below 4, underscoring its superior high temperature wave-transparent properties. These results have firmly established a correlation between the phase structure of the hybrid system and the comprehensive performance of T-M−D, thereby laying a solid foundation for the development of high-temperature resistant and wave-transparent materials with enhanced overall performance.

Metal Oxocluster-Based Organic–Inorganic Hybrid Materials: From Design Principles to Applications

Metal Oxocluster-Based Organic–Inorganic Hybrid Materials: From Design Principles to Applications

Light Emissive Nanocomposites Containing a Blue Fluorescent Dicationic Tetraphenylethene and a Red Phosphorescent [Mo6I8(OCOC2F5)6]2− Octahedral Cluster for Optical Writing

AbstractAn emissive organic–inorganic hybrid material is obtained by a cationic metathesis between a blue fluorescent tetraphenylethylene‐based salt: [TPEIm2]I2, and a red‐NIR phosphorescent octahedral molybdenum cluster compound: Cs2[Mo6I8(OCOC2F5)6]. As demonstrated by Single Crystal X‐Ray Diffraction, the hybrid [TPEIm2][Mo6I8(OCOC2F5)6] crystallizes as a 2:2 dimer and emits in the red‐NIR area. Its emission properties are studied in the solid state and once embedded in poly(methylmethacrylate) by steady state and time dependent photoluminescence spectroscopy. They are further compared to the case in which the two starting salts are directly integrated in the polymer matrix. Obtained nanocomposites show evanescent UV‐2A optical writing and reading behavior, with color contrasts depending on how emitters have been introduced.

Designing Organic–Inorganic Hybrid Materials to Construct a Complementary Interface with Versatility for Li–S Batteries

Designing Organic–Inorganic Hybrid Materials to Construct a Complementary Interface with Versatility for Li–S Batteries

[Cs14Cl][Tm71Se110]: An unusual salt-inclusion chalcogenide containing different valent Tm centers and ultralow thermal conductivity

As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs14Cl][Tm71Se110] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm71Se110]13− framework and the guest [Cs14Cl]13+ polycation. Notably, this structure reveals the presence of mixed-valent Tm2+/Tm3+ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/m⋅K within the temperature range of 323–673 K, which is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.

Bright insights: Examining fluorescence behavior using 5,7‐dibromo‐8‐hydroxyquinoline in organic–inorganic hybrid materials

Expanding on prior research with 8‐hydroxyquinoline (8hq) derivatives, this study investigates 5,7‐dibromo‐8‐hydroxyquinoline (8hqBr2) as a ligand in organic–inorganic hybrid materials (OIHMs). A series of 19 compounds and two of its salts were synthesized, employing d‐ and p‐block metal halides to explore the effect of solid‐state supramolecular structures on emission properties. Through the use of density functional theory (DFT), this work emphasizes the critical role of the bromine position within the ligand, contrasting with its effect when located exclusively in halogenometallate anions. The findings reveal that emission is profoundly influenced by π–π stacking, anion‐π interactions, and the configuration of metal cations and bromine substituents. This study not only provides insights into the specific impact of bromine positioning in 8hqBr2 on fluorescence but also contributes to the development of advanced emitters for optoelectronics and sensing, enhancing the understanding of fluorescence modulation in 8‐hydroxyquinoline‐based OIHMs.

Metal-organic framework and MXene (ZIF-8:Ti3C2Tx) based organic and inorganic nanocomposite for bio-synaptic applications

Organic and inorganic hybrid materials have drawn more interest in the field of electronic devices. The metal-organic frameworks (MOFs) have emerged as one of the promising hybrid materials for electronic devices. However, their limited electrical conductivity hinders their electronic applications. To overcome these shortcomings, we synthesized MOF:MXene nanocomposite to enhance the stability and electrical conductivity of MOF. In particular, we synthesized and characterized zeolitic imidazolate framework-8 (ZIF-8):MXene (Ti3C2Tx) hybrid nanocomposite. From the application point of view, we demonstrated the analog memory effect and mimicked various synaptic learning functionalities using Ag/ZIF-8:Ti3C2Tx/FTO resistive switching (RS) device. The fabricated device exhibits a good analog-type bipolar RS effect. The device mimics various bio-synaptic properties such as potentiation, depression, excitatory-post synaptic current, and paired-pulse facilitation (PPF) index (%). The inherent non-ideal memristor property was dominated in the device, owing to the double-valued charge-flux relation. The conduction and possible RS mechanisms of the Ag/ZIF-8:Ti3C2Tx/FTO device were reported. These results suggested that the ZIF-8:Ti3C2Tx nanocomposite is a potential nanomaterial for brain-inspired computing applications.

Synthesis and characterization of ligand-introduced [P2W12O44(C6H5PO3)2]10−

Abstract Lacunary polyoxometalates represent a distinctive category of inorganic multidentate ligands that serve as precursors for building organic–inorganic hybrid materials and multinuclear metal oxo clusters. In this study, we successfully synthesized and characterized the organic–inorganic hybrid, [P2W12O44(C6H5PO3)2]10−. Two phenylphosphonato ligands were introduced at both ends of the vacant site to form the unique organic–inorganic–organic structure.

Ligand Meta‐Anchoring Strategy in Metal–Organic Frameworks for Remarkable Promotion of Quantum Yields

AbstractAggregation is a conventional method to enhance the quantum yields (QYs) of pure organic luminophores due to the restriction of intramolecular motions (RIM). However, how to realize RIM in metal–organic frameworks (MOFs) is still unclear and challenging. In this work, the ligand meta‐anchoring strategy is first proposed and proved to be an effective and systematic approach to restrict the intramolecular motions of MOFs for the QY improvement. By simply shifting the substituent position in the ligand from para to meta, the QY of the resulting MOF is significantly enhanced by eleven‐fold. The value is even higher than that of ligand aggregates, demonstrating the strong RIM effect of this ligand meta‐anchoring strategy. The introduction of co‐ligand induces the appearance of visible yellow room temperature phosphorescence with a lifetime of 222 ms due to the QY enhancement and the charge transfer between the donor and accepter units. The present work thus broadens the understanding of the RIM mechanism from a new perspective, develops a novel method to realize RIM and expands the applicable objects from pure organic materials to organic–inorganic hybrid materials.

Formation process of organic–inorganic layered hybrid materials from vacuum-deposited bilayer thin films of CH3(CH2)11NH3I and SnI2 by post-annealing

Abstract We investigated the formation process of Sn-based 2D organic–inorganic layered hybrid materials from sequentially vacuum-deposited bilayer thin films of CH3(CH2)11NH3I (DDAI) and SnI2 by post-annealing. DDA2SnI4 or DDASnI3 was selectively formed depending on the DDAI/ SnI2 molar ratio and the annealing temperature. It was revealed that DDASnI3 is formed via the phase transformation of DDA2SnI4 that has been formed at a low temperature from a SnI2-rich bilayer thin film by a temperature increase.

Organismal Function Enhancement through Biomaterial Intervention.

Living organisms in nature, such as magnetotactic bacteria and eggs, generate various organic-inorganic hybrid materials, providing unique functionalities. Inspired by such natural hybrid materials, researchers can reasonably integrate biomaterials with living organisms either internally or externally to enhance their inherent capabilities and generate new functionalities. Currently, the approaches to enhancing organismal function through biomaterial intervention have undergone rapid development, progressing from the cellular level to the subcellular or multicellular level. In this review, we will concentrate on three key strategies related to biomaterial-guided bioenhancement, including biointerface engineering, artificial organelles, and 3D multicellular immune niches. For biointerface engineering, excess of amino acid residues on the surfaces of cells or viruses enables the assembly of materials to form versatile artificial shells, facilitating vaccine engineering and biological camouflage. Artificial organelles refer to artificial subcellular reactors made of biomaterials that persist in the cytoplasm, which imparts cells with on-demand regulatory ability. Moreover, macroscale biomaterials with spatiotemporal regulation characters enable the local recruitment and aggregation of cells, denoting multicellular niche to enhance crosstalk between cells and antigens. Collectively, harnessing the programmable chemical and biological attributes of biomaterials for organismal function enhancement shows significant potential in forthcoming biomedical applications.

High anhydrous proton conductivity and a smart proton transportation approach of a sulfate coordination polymer.

We successfully synthesized a one-dimensional cobalt sulfate coordinating polymer, whose simple hydrogen bond web structure facilitated the analysis of the proton transfer process. At 175 °C, without humidity, the conductivity is 0.0311 S cm-1, which exceeds those of most of the organic inorganic hybrid materials under anhydrous conditions (world record rank 8). Based on its crystal structure and theoretical calculations, the subversive proton conduction pathway was inferred clearly. We, for the first time, found that the proton smartly chose the path with a lower energy barrier but not the one with short distance to transport avoiding short circuit.

Design of a novel green bio-based organic–inorganic hybrid material for cost-effective and sustainable monitoring of antibiotic residues

An economical bio-based adsorbent was prepared by loading HA on silicon substrate using abandoned PVA as a physical crosslinking material. The adsorbent can achieve sustainable and simultaneous detection of multiple trace MACs in complex matrices.

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.

Lightning Up the Structural Complexity: Challenging Bromine’s ‘Heavy’ Reputation in Fluorescence Properties of Organic–Inorganic Hybrid Materials with 5,7-Dichloro-8-Hydroxyquinolinium

Lightning Up the Structural Complexity: Challenging Bromine’s ‘Heavy’ Reputation in Fluorescence Properties of Organic–Inorganic Hybrid Materials with 5,7-Dichloro-8-Hydroxyquinolinium

Improving the capacitive performance of phosphomolybdic acid using methylene blue or natural red for solid-state suprcapacitors

The main way to improve the specific energy of a supercapacitor is to implement rational design and engineering of electrode materials. In this work, methylene blue (MB, C16H19N3SCl) and neutral red (NR, C15H18N4Cl) have been chosen as cation to react with H3PMo12 to form organic–inorganic hybrid materials of (C16H18N3S)3PMo12O40 and (C15H17N4)3PMo12O40 (abbreviated as MB3PMo12 and NR3PMo12). [PMo12O40]3− and organic cation are connected by electrostatic interaction and hydrogen bond. When applied as electrode materials, MB3PMo12/NR3PMo12 electrode shows a high specific capacitance (354/241 F g−1) in 0.5 M H2SO4. The MB3PMo12 electrode, moreover, supply an amazing specific capacitance of 583 F g−1 when NH4VO3 is used as a redox additive for 0.5 M H2SO4. The solid-state supercapacitor of MB3PMo12//MB3PMo12 can operate at a voltage of 1.0 and provide a moderate specific energy. We believe that this work provides inspiration for the design and preparation of excellent supercapacitors electrodes based on polyoxometalates.