Elevating the energetic capabilities of metal coordination compounds by incorporating nitrate anions.

In the realm of energetic materials research, there has been notable interest in energetic coordination compounds (ECCs) owing to their remarkable thermal stability and resistance to mechanical stimuli. This study successfully demonstrated the synthesis of an azole-based C-C bonded ECC1 under ambient conditions. A comprehensive characterization study, employing techniques such as IR, TGA-DSC, NMR and single-crystal X-ray diffraction analysis, was conducted. The bulk compound was investigated by PXRD analysis. In-depth exploration of its physicochemical and energetic performance revealed good detonation properties such as a detonation velocity (VOD) of 8553 m s-1 and a detonation pressure (DP) of 36.2 GPa, which surpass those of heat resistant explosives HNS and TATB. Due to its remarkable high melting and onset decomposition temperature (278/379 °C), it also outperforms the benchmark explosive HMX (279 °C) and the heat-resistant explosive HNS (318 °C) and shows a high impact sensitivity (IS) of 20 J and friction sensitivity (FS) of 360 N. The study also employed Hirshfeld surface and 2D fingerprint analysis to elucidate the close contact of atoms within the molecules. The combination of high detonation properties, thermal stability, and low sensitivity makes the synthesized ECC1 intriguing for further investigations and suggests its potential applications as a safe and high-energy-dense material.

Highly Dense N-N-Bridged Dinitramino Bistriazole-Based 3D Metal-Organic Frameworks with Balanced Outstanding Energetic Performance.

Due to the inherent conflict between energy and safety, the construction of energetic materials or energetic metal-organic frameworks (E-MOFs) with balanced thermal stability, sensitivity, and high detonation performance is challenging for chemists worldwide. In this regard, in recent times self-assembly of energetic ligands (high nitrogen- and oxygen-containing small molecules) with alkali metals were probed as a promising strategy to build high-energy materials with excellent density, insensitivity, stability, and detonation performance. Herein, based on the nitrogen-rich N,N'-([4,4'-bi(1,2,4-triazole)]-3,3'-dial)dinitramide (H2BDNBT) energetic ligand, two new environmentally benign E-MOFs including potassium [K2BDNBT]n (K-MOF) and sodium [Na2BDNBT]n (Na-MOF) have been introduced and characterized by NMR, IR, TGA-DSC, ICP-MS, PXRD, elemental analyses, and SCXRD. Interestingly, Na-MOF and K-MOF demonstrate solvent-free 3D dense frameworks having crystal densities of 2.16 and 2.14 g cm-3, respectively. Both the E-MOFs show high detonation velocity (VOD) of 8557-9724 m/s, detonation pressure (DP) of 30.41-36.97 GPa, positive heat of formation of 122.52-242.25 kJ mol-1, and insensitivity to mechanical stimuli such as impact and friction (IS = 30-40 J, FS > 360 N). Among them, Na-MOF has a detonation velocity (9724 m/s) superior to that of conventional explosives. Additionally, both the E-MOFs are highly heat-resistant, having higher decomposition (319 °C for K-MOF and 293 °C for Na-MOF) than the traditional explosives RDX (210 °C), HMX (279 °C), and CL-20 (221 °C). This stability is ascribed to the extensive structure and strong covalent interactions between BDNBT2- and K(I)/Na(I) ions. To the best of our knowledge, for the first time, we report dinitramino-based E-MOFs as highly stable secondary explosives, and Na-MOF may serve as a promising next-generation high-energy-density material for the replacement of presently used secondary thermally stable energetic materials such as RDX, HNS, HMX, and CL-20.

Energetic coordination compounds: self-assembled from the nitrogen-rich energetic C-C bonded pyrazoles and triazoles.

In energetic materials research, energetic coordination compounds (ECCs) have received much attention due to their high thermal stability and insensitivity to mechanical stimuli. The energetic characteristics of ECCs can be modified by combining various metal cations, potent anions, and ligands. In this study, we have synthesized two energetic ligands, 5-(4-nitro-1H-pyrazol-3-yl)-1H-1,2,4-triazol-3-amine (NPTA) and (Z)-N-(5-(4-nitro-1H-pyrazol-3-yl)-2,4-dihydro-3H-1,2,4-triazol-3-ylidene)nitramide (NPTN), from a commercially viable starting material and reacted them with nitrate salts of various 3d metals (e.g., Ni, Co, Zn) to obtain six new ECCs, [Ni(NPTA)(H2O)3]2·2NO3 (1), [Co(NPTA)(H2O)3]2·2NO3 (2), [Zn(NPTA)(H2O)3]2·2NO3 (3), [Ni(NPTN)(H2O)3]2 (4), [Co(NPTN)(H2O)3]2 (5), and [Zn(NPTN)(H2O)3]2 (6) under ambient conditions. All the newly prepared ECCs were characterised through PXRD, IR, SEM, and TGA-DSC analysis. Furthermore, single crystal analysis proved that 1-6 are dimeric complexes. Moreover, 1-6 show excellent density ranges from 1.94 to 2.06 g cm-3 and remarkable thermal stability (216-352 °C), and are highly insensitive towards impact (>40 J) and friction (>360 N), describing their potential as high performing energetic materials. All the ECCs revealed good enthalpy of combustion (-6.3 to -9.94 kJ g-1). Additionally, the Hirshfeld surface and 2D fingerprint analysis were used to understand the close contact of atoms within the molecules. High crystal densities, thermal stabilities and low sensitivities make the synthesized ECCs interesting for further studies and potential applications as safe high-energy dense materials.

Poly Tetrazole Containing Thermally Stable and Insensitive Alkali Metal-Based 3D Energetic Metal-Organic Frameworks.

Poly tetrazole-containing thermally stable and insensitive alkali metal-based 3D energetic metal-organic frameworks (EMOFs) are promising high energy density materials to balance the sensitivity, stability, and detonation performance of explosives in defense, space, and civilian applications. Herein, the self-assembly of L3- ligand with alkali metals Na(I) and K(I) was prepared at ambient conditions, introducing two new EMOFs, [Na3(L)3(H2O)6]n (1) and [K3(L)3(H2O)3]n (2). Single crystal analysis reveals that Na-MOF (1) exhibited a 3D wave-like supramolecular structure with significant hydrogen bonding among the layers, while K-MOF (2) also featured a 3D framework. Both EMOFs were thoroughly characterized by NMR, IR, PXRD, and TGA/DSC analyses. Compounds 1 and 2 show excellent thermal decomposition Td = 344 and 337 °C, respectively, compared to the presently used benchmark explosives RDX (210 °C), HMX (279 °C), and HNS (318 °C), which is attributed to structural reinforcement induced by extensive coordination. They also show remarkable detonation performance (VOD = 8500 m s-1, 7320 m s-1, DP = 26.74 GPa, 20 GPa for 1 and 2, respectively) and insensitivity toward impact and friction (IS ≥ 40 J, FS ≥ 360 N for 1; IS ≥ 40 J, FS ≥ 360 N for 2). Their excellent synthetic feasibility and energetic performance suggest that they are the perfect blend for the replacement of present benchmark explosives such as HNS, RDX, and HMX.

Effect of Electrolytic Cations on a 3D Cd-MOF for Supercapacitive Electrodes.

A cadmium-based metal-organic framework (Cd-MOF) is synthesized in a facile manner at ambient temperature by an easy slow diffusion process. The three-dimensional (3D) structure of Cd-MOF is authenticated by single-crystal X-ray diffraction studies and exhibits a cuboid-shaped morphology with an average edge length of ∼1.13 µm. The prepared Cd-MOF was found to be electroactive in nature, which resulted in a specific capacitance of 647 F g-1 at 4 A g-1 by maintaining a retention of ∼78% over 10,000 successive cycles in the absence of any binder. Further, to distinguish the efficiency of Cd-MOF electrodes, different electrolytes (NaOH, KOH, and LiOH) were explored, wherein NaOH revealed a higher capacitive response due to its combined effect of ionic and hydrated ionic radii. To investigate the practical applicability, an asymmetric supercapacitor (ASC) device is fabricated by employing Cd-MOF as the positive electrode and activated carbon (AC) as the negative electrode, enabling it to light a commercial light-emitting diode (LED) bulb (∼1.8 V). The as-fabricated ASC device delivers comparable energy density and power density.

Construction of a Cu-Based Metal-Organic Framework by Employing a Mixed-Ligand Strategy and Its Facile Conversion into Nanofibrous CuO for Electrochemical Energy Storage Applications.

Recently, metal-organic frameworks (MOFs) have been widely employed as a sacrificial template for the construction of nanostructured materials for a range of applications including energy storage. Herein, we report a facile mixed-ligand strategy for the synthesis of a Cu-MOF, [Cu3(Azopy)3(BTTC)3(H2O)3·2H2O]n (where BTTC = 1,2,4,5-benzenetetracarboxylic acid and Azopy = 4,4'-azopyridine), via a slow-diffusion method at room temperature. X-ray analysis authenticates the two-dimensional (2D)-layered framework of Cu-MOF. Topologically, this 2D-layered structure is assigned as a 4-connected unimodal net with sql topology. Further, nanostructured CuO is obtained via a simple precipitation method by employing Cu-MOF as a precursor. After analysis of their physicochemical properties through various techniques, both materials are used as surface modifiers of glassy carbon electrodes for a comparative electrochemical study. The results reveal a superior charge storage performance of CuO (244.2 F g-1 at a current density of 0.8 A g-1) with a high rate capability compared to Cu-MOF. This observation paves the pathway for the strategic design of high-performing supercapacitor electrode materials.

Recent highlights and future prospects on mixed-metal MOFs as emerging supercapacitor candidates.

Mixed-metal metal-organic frameworks (M-MOFs) consist of at least two different metal ions as nodes in the same framework. The incorporation of a second or more metal ions provides structural/compositional diversity, multi-functionality and stability to the framework. Moreover, the periodical array of different metal ions in the framework may alter the physical/chemical properties of M-MOFs and result in fascinating applications. M-MOFs with exciting structural features offer superior supercapacitor performances compared to single metal MOFs due to the synergic effect of different metal ions. In this review, we summarize several synthetic methods to construct M-MOFs by employing various organic ligands or metalloligands. Further, we discuss the electrochemical performance of several M-MOFs and their derived composite materials for supercapacitor applications.

Mixed-Ligand Architected Unique Topological Heterometallic Sodium/Cobalt-Based Metal-Organic Framework for High-Performance Supercapacitors.

A new Na/Co-based heterometallic metal-organic framework, [Na2Co(SDCA)(µ2-OH)2(µ2-H2O)2(Azopy)]n (where Azopy = 4,4'-Azopyridine and SDCA = 2,5'-thiophenedicarboxylic acid) (1) with nanorod-shaped morphology was synthesized using mixed-ligand approach via slow-diffusion technique under ambient conditions. The crystal structure study demonstrates the proportion of Co(II) and Na(I) metal node to be 1:2 and the acquired coordination network reveals as a 3D architecture. Topologically, the 4-c Na(I) ion directs in situ assembly of 4-c SDCA linker and 6-c Co(II) ion, resulting in the formation of 4,4,6-c net with a topology named as smm3. Additionally, 1 was incorporated as a binder-free material for a glassy carbon electrode (1-GCE) to explore its supercapacitor performance, which reveals a high specific capacitance of 321.8 F g-1 at 4 A g-1 and notable rate performance (∼78.9% of initial capacitance up to 16 A g-1) as well as excellent cycling stability (retains 97.4% after 5000 cycles). The demonstrated strategy of employing different heterometallic clusters with mixed ligands markedly increases MOF's complexity and induces synergistic properties, which is highly favorable for electrochemical applications. Hence, the present approach can be extended to build a wide range of MOFs and synergistically enhanced electrochemical performance can be achieved.

Dy(III)-Based Metal-Organic Framework as a Fluorescent Probe for Highly Selective Detection of Picric Acid in Aqueous Medium.

A dysprosium metal-organic framework, {[Dy(µ2-FcDCA)1.5(MeOH)(H2O)]·0.5H2O}n (1), where FcDCA = 1,1'-ferrocene dicarboxylic acid, was prepared by slow-diffusion technique at room temperature. The crystal structure analysis of 1 by single-crystal X-ray diffraction reveals different binding modes of FcDCA linkers coordinated with Dy(III) metal ions, which forms continuous porous two-dimensional (2D) infinite framework. The resulting 2D layers are linked by π···π interactions to build three-dimensional (3D) supramolecular framework. Observably, this thermally stable 3D architecture was topologically simplified as a three-connected uninodal net with fes topology. Furthermore, the practical applicability of 1 was investigated as a fluorescence sensor for the sensitive detection of picric acid in aqueous medium with an impressive detection limit of 0.71 µM with quenching constant (KSV) quantified to be 8.55 × 104 M-1. The distinguished selectivity in the presence of other nitroaromatics suggests the possible incorporation of 1 in real-world futuristic diagnostic kits. Additionally, the electrochemical behavior of 1 exhibits reversible in nature attributed to the ferrocene/ferrocenium cation.