Energetic Salts Based on Monoanions of N,N‐Bis(1H‐tetrazol‐5‐yl)amine and 5,5′‐Bis(tetrazole)

High‐density energetic salts that contain nitrogen‐rich cations and the 5‐(tetrazol‐5‐ylamino)tetrazolate (HBTA^?) or the 5‐(tetrazol‐5‐yl)tetrazolate (HBT^?) anion were readily synthesized by the metathesis reactions of sulfate salts with barium compounds, such as bis[5‐(tetrazol‐5‐ylamino)tetrazolate] (Ba(HBTA)₂), barium iminobis(5‐tetrazolate) (BaBTA), or barium 5,5′‐bis(tetrazolate) (BaBT) in aqueous solution. All salts were fully characterized by IR spectroscopy, multinuclear (¹H, ¹³C, ¹⁵N) NMR spectroscopy, elemental analyses, density, differential scanning calorimetry (DSC), and impact sensitivity. Ba(HBTA)₂ ? 4 H₂O crystallizes in the triclinic space group P$\bar 1$ , as determined by single‐crystal X‐ray diffraction, with a density of 2.177 g cm^?3. The densities of the other organic energetic salts range between 1.55 and 1.75 g cm^?3 as measured by a gas pycnometer. The detonation pressure (P) values calculated for these salts range from 19.4 to 33.6 GPa, and the detonation velocities (ν_D) range from 7677 to 9487 m s^?1, which make them competitive energetic materials. Solid‐state ¹³C NMR spectroscopy was used as an effective technique to determine the structure of the products that were obtained from the metathesis reactions of biguanidinium sulfate with barium iminobis(5‐tetrazolate) (BaBTA). Thus, the structure was determined as an HBTA salt by the comparison of its solid‐state ¹³C NMR spectroscopy with those of ammonium 5‐(tetrazol‐5‐ylamino)tetrazolate (AHBTA) and diammonium iminobis(5‐tetrazolate) (A₂BTA).     

The three‐dimensional coordination network in poly[di‐μ3‐cyanido‐μ5‐[5‐(pyridin‐4‐yl)tetrazolato]‐tricopper(I)]

In the title three‐dimensional tetrazolate‐based coordination polymer, poly[bis(μ₃‐cyanido‐κ³N:C:C)[μ₅‐5‐(pyridin‐4‐yl)tetrazolato‐κ⁵N:N′:N′′:N′′′:N′′′′]tricopper(I)], [Cu₃(C₆H₄N₅)(CN)₂]_n, there are two types of coordinated Cu^I atoms. One type exhibits a tetrahedral environment and the other, residing on a twofold axis, adopts a trigonal coordination environment. The closest Cu...Cu distance is only 2.531 (2) Å, involving a bridging cyanide C atom. All four tetrazolate and the pyridine N atom of the 4‐(pyridin‐4‐yl)‐1H‐tetrazolate anion are coordinated to these Cu^I atoms and exhibit a μ₅‐bridging mode. The three‐dimensional coordination network can be topologically simplified as a rarely observed (3,3,4,5)‐connected network with the Schläfli symbol (4.6.8⁴)₂.(4².6.8⁷).(6.8²)₃.     

Remarkable Tuning of the Coordination and Photophysical Properties of Lanthanide Ions in a Series of Tetrazole‐Based Complexes

A series of seven new tetrazole‐based ligands (L1, L3–L8) containing terpyridine or bipyridine chromophores suited to the formation of luminescent complexes of lanthanides have been synthesized. All ligands were prepared from the respective carbonitriles by thermal cycloaddition of sodium azide. The crystal structures of the homoleptic terpyridine–tetrazolate complexes [Ln(Li)₂]NHEt₃ (Ln=Nd, Eu, Tb for i=1, 2; Ln=Eu for i=3, 4) and of the monoaquo bypyridine–tetrazolate complex [Eu(H₂O)(L7)₂]NHEt₃ were determined. The tetradentate bipyridine–tetrazolate ligand forms nonhelical complexes that can contain a water molecule coordinated to the metal. Conversely, the pentadentate terpyridine–tetrazolate ligands wrap around the metal, thereby preventing solvent coordination and forming chiral double‐helical complexes similarly to the analogue terpyridine–carboxylate. Proton NMR spectroscopy studies show that the solid‐state structures of these complexes are retained in solution and indicate the kinetic stability of the hydrophobic complexes of terpyridine–tetrazolates. UV spectroscopy results suggest that terpyridine–tetrazolate complexes have a similar stability to their carboxylate analogues, which is sufficient for their isolation in aerobic conditions. The replacement of the carboxylate group with tetrazolate extends the absorption window of the corresponding terpyridine‐ (≈20 nm) and bipyridine‐based (25 nm) complexes towards the visible region (up to 440 nm). Moreover, the substitution of the terpyridine–tetrazolate system with different groups in the ligand series L3–L6 has a very important effect on both absorption spectra and luminescence efficiency of their lanthanide complexes. The tetrazole‐based ligands L1 and L3–L8 sensitize efficiently the luminescent emission of lanthanide ions in the visible and near‐IR regions with quantum yields ranging from 5 to 53 % for Eu^III complexes, 6 to 35 % for Tb^III complexes, and 0.1 to 0.3 % for Nd^III complexes, which is among the highest reported for a neodymium complex. The luminescence efficiency could be related to the energy of the ligand triplet states, which are strongly correlated to the ligand structures.     

Syntheses and crystal structures of two magnesium–tetrazole compounds in salt and polymeric forms

Two alkaline earth–tetrazole compounds, namely catena‐poly[[[triaquamagnesium(II)]‐μ‐5,5′‐(azanediyl)ditetrazolato‐κ³N¹,N^1′:N⁵] hemi{bis[μ‐5,5′‐(azanediyl)ditetrazolato‐κ³N¹,N^1′:N²]bis[triaquamagnesium(II)]} monohydrate], {[Mg(C₂HN₉)(H₂O)₃][Mg₂(C₂HN₉)₂(H₂O)₆]_0.5·H₂O}_n, (I), and bis[5‐(pyrazin‐2‐yl)tetrazolate] hexaaquamagnesium(II), (C₅H₃N₆)[Mg(H₂O)₆], (II), have been prepared under hydrothermal conditions. Compound (I) is a mixed dimer–polymer based on magnesium ion centres and can be regarded as the first example of a magnesium–tetrazolate polymer in the crystalline form. The structure shows a complex three‐dimensional hydrogen‐bonded network that involves magnesium–tetrazolate dimers, solvent water molecules and one‐dimensional magnesium–tetrazolate polymeric chains. The intrinsic cohesion in the polymer chains is ensured by N—H...N hydrogen bonds, which form R₂²(7) rings, thus reinforcing the propagation of the polymer chain along the a axis. The crystal structure of magnesium tetrazole salt (II) reveals a mixed ribbon of hydrogen‐bonded rings, of types R₂²(7), R₂²(9) and R₂⁴(10), running along the c axis, which are linked by R₂⁴(16) rings, generating a 4,8‐c flu net.     

Topotactic Synthesis of Phosphabenzene‐Functionalized Porous Organic Polymers: Efficient Ligands in CO2 Conversion

Progress toward the preparation of porous organic polymers (POPs) with task‐specific functionalities has been exceedingly slow—especially where polymers containing low‐oxidation phosphorus in the structure are concerned. A two‐step topotactic pathway for the preparation of phosphabenzene‐based POPs (Phos‐POPs) under metal‐free conditions is reported, without the use of unstable phosphorus‐based monomers. The synthetic route allows additional functionalities to be introduced into the porous polymer framework with ease. As an example, partially fluorinated Phos‐POPs (F‐Phos‐POPs) were obtained with a surface area of up to 591 m² g^?1. After coordination with Ru species, a Ru/F‐Phos‐POPs catalyst exhibited high catalytic efficiency in the formylation of amines (turnover frequency up to 204 h^?1) using a CO₂/H₂ mixture, in comparison with the non‐fluorinated analogue (43 h^?1) and a Au/TiO₂ heterogeneous catalysts reported previously (<44 h^?1). This work describes a practical method for synthesis of porous organic phosphorus‐based polymers with applications in transition‐metal‐based heterogeneous catalysis.     

Luminescence‐Functionalized Metal–Organic Frameworks Based on a Ruthenium(II) Complex: A Signal Amplification Strategy for Electrogenerated Chemiluminescence Immunosensors

Novel luminescence‐functionalized metal–organic frameworks (MOFs) with superior electrogenerated chemiluminescence (ECL) properties were synthesized based on zinc ions as the central ions and tris(4,4′‐dicarboxylicacid‐2,2′‐bipyridyl)ruthenium(II) dichloride ([Ru(dcbpy)₃]²⁺) as the ligands. For potential applications, the synthesized MOFs were used to fabricate a “signal‐on” ECL immunosensor for the detection of N‐terminal pro‐B‐type natriuretic peptide (NT‐proBNP). As expected, enhanced ECL signals were obtained through a simple fabrication strategy because luminescence‐functionalized MOFs not only effectively increased the loading of [Ru(dcbpy)₃]²⁺, but also served as a loading platform in the ECL immunosensor. Furthermore, the proposed ECL immunosensor had a wide linear range from 5 pg mL^?1 to 25 ng mL^?1 and a relatively low detection limit of 1.67 pg mL^?1 (signal/noise=3). The results indicated that luminescence‐functionalized MOFs provided a novel amplification strategy in the construction of ECL immunosensors and might have great prospects for application in bioanalysis.     

Lithium‐Doped Silica‐Rich MIL‐101(Cr) for Enhanced Hydrogen Uptake

Metal‐organic frameworks (MOFs) show promising characteristics for hydrogen storage application. In this direction, modification of under‐utilized large pore cavities of MOFs has been extensively explored as a promising strategy to further enhance the hydrogen storage properties of MOFs. Here, we described a simple methodology to enhance the hydrogen uptake properties of RHA incorporated MIL‐101 (RHA‐MIL‐101, where RHA is rice husk ash—a waste material) by controlled doping of Li⁺ ions. The hydrogen gas uptake of Li‐doped RHA‐MIL‐101 is significantly higher (up to 72 %) compared to the undoped RHA‐MIL‐101, where the content of Li⁺ ions doping greatly influenced the hydrogen uptake properties. We attributed the observed enhancement in the hydrogen gas uptake of Li‐doped RHA‐MIL‐101 to the favorable Li⁺ ion‐to‐H₂ interactions and the cooperative effect of silanol bonds of silica‐rich rice‐husk ash incorporated in MIL‐101.     

Thermoplastic Membranes Incorporating Semiconductive Metal–Organic Frameworks: An Advance on Flexible X‐ray Detectors

Semiconductive metal–organic frameworks (MOFs) have emerged in applications such as chemical sensors, electrocatalysts, energy storage materials, and electronic devices. However, examples of semiconductive MOFs within flexible electronics have not been reported. We present flexible X‐ray detectors prepared by thermoplastic dispersal of a semiconductive MOF ( SCU‐13 ) through a commercially available polymer, poly(vinylidene fluoride). The flexible detectors exhibit efficient X‐ray‐to‐electric current conversion with enhanced charge‐carrier mobility and low trap density compared to pelleted devices. A high X‐ray detection sensitivity of 65.86 μCGy_air^?1 cm^?2 was achieved, which outperforms other pelleted devices and commercial flexible X‐ray detectors. We demonstrate that the MOF‐based flexible detectors can be operated at multiple bending angles without a deterioration in detection performance. As a proof‐of‐concept, an X‐ray phase contrast under bending conditions was constructed using a 5×5 pixelated MOF‐based imager.     

Fluorinated pillared-layer metal-organic framework microrods for improved electrochemical cycling stability

Developing metal-organic framework (MOF)-based materials with good cyclic stability is the key to their practical application. Fluorinated organic compounds are usually highly chemically stability due to the high electronegativity of fluorine. Also, the pillared-layer structures based on coordination bonds have better structure and thermal stability than those based on hydrogen bonds. Herein, the fluorinated pillared-layer [Ni(2,3,4,5-tetrafluorobenzoic acid)(4,4′-bipyridine)]_n MOF ([Ni(TFBA)(Bpy)]_n) materials were constructed through a facile room-temperature solution reaction and used as electrode materials for supercapacitors. Surprisingly, the size/morphology of Ni(TFBA)(Bpy)]_n MOFs could be adjusted by varying the synthesis time. Benefting from the short ion diffusion length, unique pillar-layer structure, and strong intercomponent synergy of organic ligands, the Ni(TFBA)(Bpy)]_n MOF microrods showed a higher electrochemical energy storage capability than bulk MOFs. At the same time, compared to the non-fluorinated [Ni(benzoic acid)(Bpy)]_n MOFs (31.5% capacitance decay), the fluorinated Ni(TFBA)(Bpy)]_n MOFs have a higher cycle stability with only 2.6% capacitance loss after 5000 cycles at 3 mA/cm².     

An Improved Method for the Preparation of Energetic Aminotetrazolium Salts

A straightforward way for the preparation of the energetic 5‐aminotetrazolium and 1, 5‐diaminotetrazolium salts is reported. The energetic salts were readily synthesized by the reaction of 5‐aminotetrazolium nitrate or 1, 5‐diaminotetrazolium nitrate with ammonium 5‐nitroiminotetrazolate, ammonium 1‐methyl‐5‐nitroiminotetrazolate, bis(ammonium) ethylene bis(5‐nitroiminotetrazolate), and diammonium iminobis(5‐tetrazolate), respectively, in water under mild conditions. All products were recovered as highly crystalline materials in excellent yields and purities, and were fully characterized by IR spectroscopy, ¹H and ¹³C NMR spectroscopy, DSC measurements as well as elemental analyses.     

The Series of Rare Earth Complexes [Ln2Cl6(μ‐4,4′‐bipy)(py)6], Ln=Y,Pr, Nd,Sm‐Yb: A Molecular Model System for Luminescence Properties in MOFs Based on LnCl3 and 4,4′‐Bipyridine

A series of 12 dinuclear complexes [Ln₂Cl₆(μ‐4,4′‐bipy)(py)₆], Ln=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, ( 1 – 12 , respectively) was synthesized by an anhydrous solvothermal reaction in pyridine. The complexes contain a 4,4′‐bipyridine bridge and exhibit a coordination sphere closely related to luminescent lanthanide MOFs based on LnCl₃ and 4,4‐bipyridine. The dinuclear complexes therefore function as a molecular model system to provide a better understanding of the luminescence mechanisms in the Ln‐N‐MOFs ${\hbox{}{{\hfill 2\atop \hfill \infty }}}$ [Ln₂Cl₆(4,4′‐bipy)₃] ? 2(4,4′‐bipy). Accordingly, the luminescence properties of the complexes with Ln=Y, Sm, Eu, Gd, Tb, Dy, ( 1 , 4 – 8 ) were determined, showing an antenna effect through a ligand–metal energy transfer. The highest efficiency of luminescence is observed for the terbium‐based compound 7 displaying a high quantum yield (QY of 86 %). Excitation with UV light reveals typical emission colors of lanthanide‐dependent intra 4f–4f‐transition emissions in the visible range (Tb^III: green, Eu^III: red, Sm^III: salmon red, Dy^III: yellow). For the Gd^III‐ and Y^III‐containing compounds 6 and 1 , blue emission based on triplet phosphorescence is observed. Furthermore, ligand‐to‐metal charge‐transfer (LMCT) states, based on the interaction of Cl^? with Eu^III, were observed for the Eu^III compound 5 including energy‐transfer processes to the Eu^III ion. Altogether, the model complexes give further insights into the luminescence of the related MOFs, for example, rationalization of Ln‐independent quantum yields in the related MOFs.     

Tetra­aqua­bis­[5‐(4‐pyridyl N‐oxide)­tetrazolato‐κN2]­cadmium: the intermediate in the synthesis of a tetrazole from a nitrile and an azide

The intermediate [Cd(4‐PTZ)₂(H₂O)₄] [4‐PTZ is 5‐(4‐pyridyl N‐oxide)­tetrazolate, C₆H₄N₅O], (I), in the synthesis of 4‐HPTZ, (II), from the cyclo­addition reaction of 4‐cyano­pyridine N‐oxide with NaN₃ in water using CdCl₂ as catalyst, was structurally characterized. The unique Cd atom lies on a twofold axis and the coordination geometry of the Cd atom is that of a slightly distorted octahedron, involving four water mol­ecules and two tetrazolate ligands. The catalytic role of the Cd²⁺ ion in the tetrazole generation reaction stems from the formation of (I). In acidic solution, (I) can be disassociated and the free ligand, (II), can be released.     

Design and Synthesis of a Water‐Stable Anionic Uranium‐Based Metal–Organic Framework (MOF) with Ultra Large Pores

Ionic metal–organic frameworks (MOFs) are a subclass of porous materials that have the ability to incorporate different charged species in confined nanospace by ion‐exchange. To date, however, very few examples combining mesoporosity and water stability have been realized in ionic MOF chemistry. Herein, we report the rational design and synthesis of a water‐stable anionic mesoporous MOF based on uranium and featuring tbo‐type topology. The resulting tbo MOF exhibits exceptionally large open cavities (3.9 nm) exceeding those of all known anionic MOFs. By supercritical CO₂ activation, a record‐high Brunauer‐Emmett‐Teller (BET) surface area (2100 m² g^?1) for actinide‐based MOFs has been obtained. Most importantly, however, this new uranium‐based MOF is water‐stable and able to absorb positively charged ions selectively over negatively charged ones, enabling the efficient separation of organic dyes and biomolecules.     

Organization and Energy Transfer of Fused Aromatic Hydrocarbon Guests within Anion‐Confining Nanochannel MOFs

The self‐assembly of Zn^II ions with 1,3,5‐tris(isonicotinoyloxyethyl)cyanurate produces new topological (4²?12⁴)₃(4³)₄ 2D metal–organic frameworks (MOFs) with anion‐confining cages. The eclipsed assembly of each 2D MOF by π–π stacking of cyanurate moieties (3.352(5) Å) forms 3D MOFs consisting of nanochannels (10.5 Å). Two of the three anions are confined in each peanut‐type cage, resulting in hydrophobicity of the nanochannels. The hydrophobic nanochannel effectively adsorbs a wide range of fused aromatic hydrocarbons (FAHs) as monomers or dimers, rendering it potentially highly useful as an energy‐transfer material.     

Characterization of Zn‐Containing Metal–Organic Frameworks by Solid‐State 67Zn NMR Spectroscopy and Computational Modeling

Metal–organic frameworks (MOFs) are an extremely important class of porous materials with many applications. The metal centers in many important MOFs are zinc cations. However, their Zn environments have not been characterized directly by ⁶⁷Zn solid‐state NMR (SSNMR) spectroscopy. This is because ⁶⁷Zn (I=5/2) is unreceptive with many unfavorable NMR characteristics, leading to very low sensitivity. In this work, we report, for the first time, a ⁶⁷Zn natural abundance SSNMR spectroscopic study of several representative zeolitic imidazolate frameworks (ZIFs) and MOFs at an ultrahigh magnetic field of 21.1 T. Our work demonstrates that ⁶⁷Zn magic‐angle spinning (MAS) NMR spectra are highly sensitive to the local Zn environment and can differentiate non‐equivalent Zn sites. The ⁶⁷Zn NMR parameters can be predicted by theoretical calculations. Through the study of MOF‐5 desolvation, we show that with the aid of computational modeling, ⁶⁷Zn NMR spectroscopy can provide valuable structural information on the MOF systems with structures that are not well described. Using ZIF‐8 as an example, we further demonstrate that ⁶⁷Zn NMR spectroscopy is highly sensitive to the guest molecules present inside the cavities. Our work also shows that a combination of ⁶⁷Zn NMR data and molecular dynamics simulation can reveal detailed information on the distribution and the dynamics of the guest species. The present work establishes ⁶⁷Zn SSNMR spectroscopy as a new tool complementary to X‐ray diffraction for solving outstanding structural problems and for determining the structures of many new MOFs yet to come.     

Cis–trans isomerism in a square‐planar platinum(II) complex bearing bulky fluorinated phosphane ligands

Transition‐metal complexes bearing fluorinated phosphane and thiolate ligands has been an area of study in recent years and the chemical context of the current work is related to the metal‐assisted functionalization of fluorinated derivatives. The cis and trans isomers of the square‐planar complex bis[(pentafluorophenyl)diphenylphosphane‐κP]bis(2,3,5,6‐tetrafluorobenzenethiolato‐κS)platinum(II), [Pt(C₆HF₄S)₂{P(C₆H₅)₂(C₆F₅)}₂], have been crystallized from a single chromatographic fraction and characterized by X‐ray diffraction analysis. The stabilization of the cis isomer results from weak intramolecular π‐stacking interactions and possibly from the formation of a C—F…Pt contact, characterized by an F…Pt separation of 2.957 (6) Å. The natural bond orbital analysis (NBO) for this isomer confirms that the corresponding F → Pt charge transfer accounts for 6.92 kcal mol⁻¹ in the isomer stabilization. Such interactions are not present in the centrosymmetric trans isomer.     

Amorphous Metal–Organic Framework‐Dominated Nanocomposites with Both Compositional and Structural Heterogeneity for Oxygen Evolution

Amorphous metal–organic frameworks (aMOFs) are an emerging family of attractive materials with great application potential, however aMOFs are usually prepared under harsh conditions and aMOFs with complex compositions and structures are rarely reported. In this work, an aMOF‐dominated nanocomposite (aMOF‐NC) with both structural and compositional complexity has been synthesized using a facile approach. A ligand‐competition amorphization mechanism is proposed based on experimental and density functional theory calculation results. The aMOF‐NC possesses a core–shell nanorod@nanosheet architecture, including a Fe‐rich Fe‐Co‐aMOF core and a Co‐rich Fe‐Co‐aMOF shell in the core–shell structured nanorod, and amorphous Co(OH)₂ nanosheets as the outer layer. Benefiting from the structural and compositional heterogeneity, the aMOF‐NC demonstrates an excellent oxygen evolution reaction activity with a low overpotential of 249 mV at 10.0 mA cm^?2 and Tafel slope of 39.5 mV dec^?1.     

Controllable Synthesis of Porphyrin‐Based 2D Lanthanide Metal–Organic Frameworks with Thickness‐ and Metal‐Node‐Dependent Photocatalytic Performance

Synthesizing 2D metal–organic frameworks (2D MOFs) in high yields and rational tailoring of the properties in a predictable manner for specific applications is extremely challenging. Now, a series of porphyrin‐based 2D lanthanide MOFs (Ln‐TCPP, Ln=Ce, Sm, Eu, Tb, Yb, TCPP=tetrakis(4‐carboxyphenyl) porphyrin) with different thickness were successfully prepared in a household microwave oven. The as‐prepared 2D Ln‐TCPP nanosheets showed thickness‐dependent photocatalytic performances towards photooxidation of 1,5‐dihydroxynaphthalene (1,5‐DHN) to synthesize juglone. Particularly, the Yb‐TCPP displayed outstanding photodynamic activity to generate O₂^? and ¹O₂. This work not only provides fundamental insights into structure designing and property tailoring of 2D MOFs nanosheets, but also pave a new way to improve the photocatalytic performance.     

A Flexible Photoactive Titanium Metal–Organic Framework Based on a [TiIV3(μ3‐O)(O)2(COO)6] Cluster

The synthesis of titanium–carboxylate metal–organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium‐based MOFs by the use of titanocene dichloride to synthesize COK‐69, the first breathing Ti MOF, which is built up from trans‐1,4‐cyclohexanedicarboxylate linkers and an unprecedented [Ti^IV₃(μ₃‐O)(O)₂(COO)₆] cluster. The photoactive properties of COK‐69 were investigated in depth by proton‐coupled electron‐transfer experiments, which revealed that up to one Ti^IV center per cluster can be photoreduced to Ti^III while preserving the structural integrity of the framework. The electronic structure of COK‐69 was determined by molecular modeling, and a band gap of 3.77 eV was found.     

Sequential Transformation of Zirconium(IV)‐MOFs into Heterobimetallic MOFs Bearing Magnetic Anisotropic Cobalt(II) Centers

Heterometallic metal–organic frameworks (MOFs) allow the precise placement of various metals at atomic precision within a porous framework. This new level of control by MOFs promises fascinating advances in basic science and application. However, the rational design and synthesis of heterometallic MOFs remains a challenge due to the complexity of the heterometallic systems. Herein, we show that bimetallic MOFs with MX₂(INA)₄ moieties (INA=isonicotinate; M=Co²⁺ or Fe²⁺; X=OH^?, Cl^?, Br^?, I^?, NCS^?, or NCSe^?) can be generated by the sequential modification of a Zr‐based MOF. This multi‐step modification not only replaced the linear organic linker with a square planar MX₂(INA)₄ unit, but also altered the symmetry, unit cell, and topology of the parent structure. Single‐crystal to single‐crystal transformation is realized so that snapshots for transition process were captured by successive single‐crystal X‐ray diffraction. Furthermore, the installation of Co(NCS)₂(INA)₄ endows field‐induced slow magnetic relaxation property to the diamagnetic Zr‐MOF.