Framework Cavities Research Articles

Strain coupling and dynamic relaxation in multiferroic metal-organic framework [(CH3)2NH2][Mn(HCOO)3] with perovskite structure

Abstract Strain coupling with ferromagnetism and ferroelectricity plays an important role in the development of multiferroic metal-organic frameworks (MOFs) with strong magnetoelectric coupling, but the underlying mechanisms have not been well understood. Strain coupling and dynamic relaxation in multiferroic MOF with perovskite structure [(CH3)2NH2][Mn(HCOO)3] were investigated using X-ray diffraction (XRD), Raman spectroscopy, Infra-red (IR) spectroscopy, differential scanning calorimetry (DSC), magnetic measurements and dynamic mechanical analysis (DMA). DSC results showed peaks at 183 K and 190 K at the rate of 5 K/min during cooling and heating processes, respectively. Magnetic measurements showed magnetic transition at ∼8.5 K at the heating rate of 2 K/min. Temperature and frequency dependences of elastic properties studied by DMA at frequencies of 0.5 Hz–10 Hz between 140 K and 300 K at heating rate of 2 K/min indicated that the minimum in storage modulus and the maximum in loss modulus and loss factor occurred near 190 K. The peak height of loss modulus and loss factor decreased at higher frequency, and the peak temperature was independent of frequency, showing the features of first-order phase transition. Near 190 K, paraelectric to ferroelectric phase transition triggered by disorder–order transition of alkylammonium cations located in the framework cavities occurred accompanied by the structural phase transition from rhombohedral space group R 3 - c to monoclinic space group Cc. The elastic anomalies and large energy loss near 190 K were associated with the coupling of the local strain with the freezing of dimethylammonium cation and the freezing of twin walls.

New triple molybdate Rb2AgIn(MoO4)3: synthesis, framework crystal structure and ion-transport behaviour.

A new triple molybdate, Rb2Ag1+3xIn1-x(MoO4)3 (0 ≤ x ≤ 0.02), was found in the course of a study of the system Rb2MoO4-Ag2MoO4-In2(MoO4)3 and was synthesized as both powders and single crystals by solid-state reactions and spontaneous crystallization from melts. The structure of Rb2Ag1+3xIn1-x(MoO4)3 (x ≉ 0.004) is of a new type crystallizing in the centrosymmetric space group R-3c [a= 10.3982 (9), c = 38.858 (4) Å, Z = 12 and R = 0.0225] and contains (In,Ag)O6 octahedra and distorted Ag1O6 trigonal prisms linked by common faces to form [Ag(In,Ag)O9] dimers connected to each other via MoO4 tetrahedra into an open three-dimensional (3D) framework. Between two adjacent [Ag(In,Ag)O9] dimers along the c axis, an extra Ag2O6 trigonal prism with about 1% occupancy was found. The Ag1O6 and Ag2O6 prisms are located at levels of z ≉ 1/12, 1/4, 5/12, 7/12, 3/4 and 11/12, and can facilitate two-dimensional ionic conductivity. The 12-coordinate Rb atoms are in the framework cavities. The structure of Rb2AgIn(MoO4)3 is a member of the series of rhombohedral 3D framework molybdate structure types with a ≉ 9-10 Å and long c axes, which contain rods of face-shared filled and empty coordination polyhedra around threefold axes. Electrical conductivity of ceramics is measured by impedance spectroscopy. Rb2AgIn(MoO4)3 undergoes a `blurred' first-order phase transition at 535 K with increasing electrical conductivity up to 1.1× 10-2 S cm-1 at 720 K. Thus, the compound may be of interest for developing new materials with high ionic conductivity at elevated temperatures.

Gold-Nanoparticle-Encapsulated ZIF-8 for a Mediator-Free Enzymatic Glucose Sensor by Amperometry

A novel method has been developed for the encapsulation of gold nanoparticles (AuNPs) and glucose oxidase (GOx) together into the cavity of a zeolitic imidazolate framework (ZIF-8) in aqueous media and subsequently used for amperometric glucose sensing application. ZIF-8 is a highly efficient, stable (thermally and chemically) microstructure and possesses a large surface area with a unique cavity to accommodate both AuNPs and GOx. The as-synthesized composite is thoroughly characterized by various physicochemical methods and confirms the uniform distribution of AuNPs within the metal–organic framework cavity. The presence of highly conducting AuNPs enhances the activity of GOx and facilitates the mediator-free tandem electrocatalytic reactions of both glucose oxidation and oxygen reduction. Further, the nanocomposite exhibits admirable stability with low-level detection of glucose in aqueous media (50 nM glucose) by using a very low concentration of GOx (62 μg in 1 mL).

Se–Cl Interactions in Selenite Chlorides: A Theoretical Study

The Se–Cl interactions in five selenite chlorides (α,β-Zn2(SeO3)Cl2 (sofiite and its polymorph), α,β-Cu5O2(SeO3)2Cl2 (georgbokiite and parageorgbokiite), and KCdCu7O2(SeO3)2Cl9 (burnsite)) have been investigated by means of the analysis of their theoretical electron density distributions. The analysis reveals the existence in the structures of two basic types of interactions: intermediate interactions with essential covalent contribution and closed-shell interactions. In Zn2(SeO3)Cl2 polymorphs and burnsite, all metal-oxide and metal-chloride interactions are of the first type, whereas in georgbokiite and parageorgbokiite, the Jahn–Teller distortion results in the elongation of some of the Cu–X bonds and their transition to the closed-shell type. All anion–anion interactions are of the closed-shell type. The energy of the closed-shell Se–Cl interactions can be estimated as 1.4–2.6 kcal.mol−1, which is comparable to weak hydrogen bonds. Despite their weakness, these interactions provide additional stabilization of structural architectures. The Se4+–Cl− configurations are localized inside framework channels or cavities, which can be therefore be viewed as regions of weak and soft interactions in the structure.

Water-Stable Metal-Organic Framework with Three Hydrogen-Bond Acceptors: Versatile Theoretical and Experimental Insights into Adsorption Ability and Thermo-Hydrolytic Stability.

A new microporous cadmium metal-organic framework was synthesized both mechanochemically and in solution by using a sulfonyl-functionalized dicarboxylate linker and an acylhydrazone colinker. The three-dimensional framework is highly stable upon heating to 300 °C as well as in aqueous solutions at elevated temperatures or acidic conditions. The thermally activated material exhibits steep water vapor uptake at low relative pressures at 298 K and excellent recyclability up to 260 °C as confirmed by both quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) method as well as adsorption isotherm measurements. Reversible isotherms and hysteretic isobars recorded for the desorption-adsorption cycles indicate the maximum uptake of 0.19 g/g (at 298 K, up to p/p0 = 1) or 0.18 g/g (at 1 bar, within 295-375 K range), respectively. The experimental isosteric heat of adsorption (48.9 kJ/mol) indicates noncoordinative interactions of water molecules with the framework. Exchange of the solvent molecules in the as-made material with water, performed in the single-crystal to single-crystal manner, allows direct comparison of both X-ray crystal structures. The single-crystal X-ray diffraction for the water-loaded framework demonstrates the orientation of water clusters in the framework cavities and reveals their strong hydrogen bonding with sulfonyl, acyl, and carboxylate groups of the two linkers. The grand canonical Monte Carlo (GCMC) simulations of H2O adsorption corroborate the experimental findings and reveal preferable locations of guest molecules in the framework voids at various pressures. Additionally, both experimental and GCMC simulation insights into the adsorption of CO2 (at 195 K) on the activated framework are presented.

The earliest evolutionary link of metazoan bioconstruction: Laminar stromatoporoid–bryozoan reefs from the Middle Ordovician of Korea

Sub-metre-scale patch reefs composed primarily of stromatoporoids and bryozoans are reported from the Duwibong Formation (upper Middle Ordovician), Taebaeksan Basin, Korea, in the eastern margin of the Sino-Korean Block. The reef framework is constructed of alternating thin laminae of the primitive labechiid stromatoporoid Cystostroma, the bryozoan Nicholsonella, subordinate Solenopora and minor siliceous sponges. Alternating laminae of stromatoporoids and bryozoans are largely responsible for the formation of a globular framework composed of columnar, branching, bulbous to irregular masses. Solenopora sporadically occurring as tiny patches or thin laminae attached to the stromatoporoid–bryozoan framework is considered to be subordinate encrusters. Siliceous sponges occur within the stromatoporoid–bryozoan framework and within the growth framework and bored cavities, interpreted as subordinate encrusters and cryptic dwellers. The compact globular framework of the Duwibong stromatoporoid–bryozoan consortium represents a new type of Ordovician skeletal bioconstruction, but with a certain structural similarity to Lower Ordovician bryozoan reefs in the South China Block. Together with coeval labechiid reefs occurring near the current study area, the Duwibong reefs suggest that incursion of the primitive stromatoporoids into the earliest bryozoan reefs resulted in the dominance of reef-building stromatoporoids in peri-Gondwana in contrast to coeval reefs in Laurentia, which commonly contain tabulate corals.

New Solid Electrolyte Na9Al(MoO4)6: Structure and Na+ Ion Conductivity

Solid electrolytes are important materials with a wide range of technological applications. This work reports the crystal structure and electrical properties of a new solid electrolyte Na9Al(MoO4)6. The monoclinic Na9Al(MoO4)6 consists of isolated polyhedral [Al(MoO4)6]9– clusters composed of a central AlO6 octahedron sharing vertices with six MoO4 tetrahedra to form a three-dimensional framework. The AlO6 octahedron also shares edges with one Na1O6 octahedron and two Na2O6 octahedra. Na3–Na5 atoms are located in the framework cavities. The structure is related to that of sodium ion conductor II-Na3Fe2(AsO4)3. High-temperature conductivity measurements revealed that the conductivity (σ) of Na9Al(MoO4)6 at 803 K equals 1.63 × 10–2 S cm–1. The temperature behavior of the 23Na and 27Al nuclear magnetic resonance spectra and the spin-lattice relaxation rates of the 23Na nuclei indicate the presence of fast Na+ ion diffusion in the studied compound. At T<490 K, diffusion occurs by means of Na+ ion jumps exclus...

Crystal structure of new triple molybdate AgMg3Ga(MoO4)5 from Rietveld refinement

A polycrystalline sample of a new triple molybdate AgMg3Ga(MoO4)5 was obtained by solid-state reaction techniques. Structural refinement based on X-ray powder diffraction data showed that the crystal structure is isotypic with NaMg3In(MoO4)5 (sp. gr. P$\bar 1$). In the structure pairs of edge-shared (Mg, Ga)O6, octahedra are connected by common vertices to form a three-dimensional framework. Large framework cavities involve Ag+ cations. The title compound was found to melt at 1079 K.

The effect of pressure on open-framework silicates: elastic behaviour and crystal–fluid interaction

The elastic behaviour and the structural evolution of microporous materials compressed hydrostatically in a pressure-transmitting fluid are drastically affected by the potential crystal–fluid interaction, with a penetration of new molecules through the zeolitic cavities in response to applied pressure. In this manuscript, the principal mechanisms that govern the P-behaviour of zeolites with and without crystal–fluid interaction are described, on the basis of previous experimental findings and computational modelling studies. When no crystal–fluid interaction occurs, the effects of pressure are mainly accommodated by tilting of (quasi-rigid) tetrahedra around O atoms that behave as hinges. Tilting of tetrahedra is the dominant mechanism at low-mid P-regime, whereas distortion and compression of tetrahedra represent the mechanisms which usually dominate the mid-high P regime. One of the most common deformation mechanisms in zeolitic framework is the increase of channels ellipticity. The deformation mechanisms are dictated by the topological configuration of the tetrahedral framework; however, the compressibility of the cavities is controlled by the nature and bonding configuration of the ionic and molecular content, resulting in different unit-cell volume compressibility in isotypic structures. The experimental results pertaining to compression in “penetrating” fluids, and thus with crystal–fluid interaction, showed that not all the zeolites experience a P-induced intrusion of new monoatomic species or molecules from the P-transmitting fluids. For example, zeolites with well-stuffed channels at room conditions (e.g. natural zeolites) tend to hinder the penetration of new species through the zeolitic cavities. Several variables govern the sorption phenomena at high pressure, among those: the “free diameters” of the framework cavities, the chemical nature and the configuration of the extra-framework population, the partial pressure of the penetrating molecule in the fluid (if mixed with other non-penetrating molecules), the rate of P-increase, the surface/volume ratio of the crystallites under investigations and the temperature at which the experiment is conducted. An overview of the intrusion phenomena of monoatomic species (e.g. He, Ar, Kr), small (e.g. H2O, CO2) and complex molecules, along with the P-induced polymerization phenomena (e.g. C2H2, C2H4, C2H6O, C2H6O2, BNH6, electrolytic MgCl2·21H2O solution) is provided, with a discussion of potential technological and geological implications of these experimental findings.

Neutron Diffraction and EXAFS Studies of K2x/3Cu[Fe(CN)6]2/3·nH2O

The crystal structure of copper hexacyanoferrate (CuHCF), K2x/3Cu[Fe(CN)6]2/3·nH2O, with nominal compositions x = 0.0 and x = 1.0 was studied by neutron powder diffraction (NPD) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The compound crystallizes in space group Fm3m, with a = 10.1036(11) A and a = 10.0588(5) A for x = 0.0 and x = 1.0, respectively. Difference Fourier maps for x = 0.0 show that the coordinated water molecules are positioned at a site 192l close to vacant N positions in the −Fe–C–N–Cu– framework, while additional zeolitic water molecules are distributed over three sites (8c, 32f, and 48g) in the −Fe–C–N–Cu– framework cavities. The refined water content for x = 0.0 is 16.8(8) per unit cell, in agreement with the ideal 16 (n = 4). For x = 1.0, the refinement suggests that 2.6 K atoms per unit cell (x = 0.98) are distributed only over the sites 8c and 32f in the cavities, and 13.9(7) water per unit cell are distributed over all the four positions. The EXAFS data for Fe...

An energy gap functional: Cavity identification in linear elasticity

Abstract The aim of this work is an analysis of some geometrical inverse problems related to the identification of cavities in linear elasticity framework. We rephrase the inverse problem into a shape optimization one using an energetic least-squares functional. The shape derivative of this cost functional is combined with the level set method in a steepest descent algorithm to solve the shape optimization problem. The efficiency of this approach is illustrated by several numerical results.

Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D

Single metal atoms and metal clusters have attracted much attention thanks to their advantageous capabilities as heterogeneous catalysts. However, the generation of stable single atoms and clusters on a solid support is still challenging. Herein, we report a new strategy for the generation of single Pt atoms and Pt clusters with exceptionally high thermal stability, formed within purely siliceous MCM-22 during the growth of a two-dimensional zeolite into three dimensions. These subnanometric Pt species are stabilized by MCM-22, even after treatment in air up to 540 °C. Furthermore, these stable Pt species confined within internal framework cavities show size-selective catalysis for the hydrogenation of alkenes. High-temperature oxidation-reduction treatments result in the growth of encapsulated Pt species to small nanoparticles in the approximate size range of 1 to 2 nm. The stability and catalytic activity of encapsulated Pt species is also reflected in the dehydrogenation of propane to propylene.

Nitrosonium nitratometallates NO[M(NO3)3] (M = Co, Ni): new synthetic approach and crystal structures

Monoclinic and triclinic modifications of nitrosonium nitratonickelate NO[Ni(NO3)3] as well as triclinic modification of nitrosonium nitratocobaltate NO[Co(NO3)3] (isostructural to triclinic NO[Ni(NO3)3]) have been synthesized by a new synthetic approach. Single crystal XRD studies revealed the similarity of all these structures in which octahedrally coordinated metal atoms are connected through N O 3 − bridges forming three-dimensional distorted cubic framework with NO+ cations located in the framework cavities.

Synthesis, phase formation, and thermal expansion of sulfate phosphates with the NaZr2(PO4)3 structure

The NaFeZr(PO4)2SO4 and Pb2/3FeZr(PO4)7/3(SO4)2/3 sulfate phosphates with the NaZr2(PO4)3 (NZP) structure were synthesized and studied using X-ray diffraction, electron microprobe analysis, IR spectroscopy, and simultaneous differential thermal and thermogravimetric analysis. The phase formation and thermal stability of the compounds were studied by powder X-ray diffraction and DTA–TG. The Pb2/3FeZr(PO4)7/3(SO4)2/3 structure was refined by full-profile analysis. The structure framework is composed of randomly occupied (Fe,Zr)O6 octahedra and (P,S)O4 tetrahedra; the Pb2+ ions occupy extra-framework sites. The thermal expansion of Pb2/3FeZr(PO4)7/3(SO4)2/3 in the temperature range from–120 to 200°C was studied by temperature X-ray diffraction. In terms of the average linear coefficient of thermal expansion (αav = 1.7 × 10–6°C–1), this compound can be classified as having low expansion. The combination of different tetrahedral anions (a phosphorus and a smaller sulfur one) in the NZP resulted in a decrease in the framework size and cavities and enabled the preparation of low-expansion sulfate phosphate with a smaller extra-framework cation (cheap Pb) instead of larger cations (Cs, Ba, Sr) used most often in the monoanionic phosphates.

New series of triple molybdates AgA3R(MoO4)5 (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) with framework structures and mobile silver ion sublattices

Triple molybdates AgA3R(MoO4)5 (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg3In(MoO4)5 type were synthesized and single crystals of AgMg3R(MoO4)5 (R=Cr, Fe) were grown. In their structures, the MoO4 tetrahedra, pairs and trimers of edge-shared (Mg, R)O6 octahedra are connected by common vertices to form a 3D framework. Large framework cavities involve Ag+ cations disordered on three nearby positions with CN=3+1 or 4+1. Alternating (Mg, R)O6 octahedra and MoO4 tetrahedra in the framework form quadrangular windows penetrable for Ag+ at elevated temperatures. Above 653–673K, the newly obtained molybdates demonstrate abrupt reduction of the activation energy to 0.4–0.6eV. At 773K, AgMg3Al(MoO4)5 shows electric conductivity 2.5·10−2S/cm and Ea=0.39eV compatible with characteristics of the best ionic conductors of the NASICON type.

Order-disorder phase transition and multiferroic behaviour in a metal organic framework compound (CH3)2NH2Co(HCOO)3

We have investigated the multiferroic and glassy behaviour of metal-organic framework (MOF) material (CH3)2NH2Co(CHOO)3. The compound has perovskite–like architecture in which the metal–formate forms a framework. The organic cation (CH3)2NH2+ occupies the cavities in the formate framework in the framework via N–H···O hydrogen bonds. At room temperature, the organic cation is disordered and occupies three crystallographically equivalent positions. Upon cooling, the organic cation is ordered which leads to a structural phase transition at 155 K. The structural phase transition is associated with a para-ferroelectric phase transition and is revealed by dielectric and pyroelectric measurements. Further, a PE hysteresis loop below 155 K confirms the ferroelectric behaviour of the material. Analysis of dielectric data reveal large frequency dispersion in the values of dielectric constant and tanδ which signifies the presence of glassy dielectric behaviour. The material displays a antiferromagnetic ordering below 15 K which is attributed to the super-exchange interaction between Co2+ ions mediated via formate linkers. Interestingly, another magnetic transition is also found around 11 K. The peak of the transition shifts to lower temperature with increasing frequency, suggesting glassy magnetism in the sample.

Cs2CuP2O7, a novel low-density open-framework structure based upon an augmented diamond net

AbstractThe crystal structure of Cs2CuP2O7[monoclinic,Cc,a=7.460(6),b=12.973(10),c=9.980(8) Å, β=111.95(2)°,V=895.8(12) Å3] prepared by solid-state reactions is based upon open framework formed by corner sharing between CuO4distorted squares and P2O7groups. The framework is porous and has a very low framework density of 13.4 Cu+P atoms per 1 nm3. Cs+cations reside in large framework cavities. The heteropolyhedral network in the title compound is based upon three-dimensional (3;4)-connected net that has a three-membered CuP2ring as its elementary unit. In terms of reticular chemistry, this net should be considered as an augmented diamond (dia) net. The Cu–P net can be obtained from the latter by the replacement of its nodes by the CuP2triangles. This replacement is strongly non-centrosymmetric, since all CuP2triangles are oriented along the same direction, which provides a crystal chemical explanation for the absence of a symmetry centre in the structure. Cs2CuP2O7is the first compound in the A2CuP2O7family (A=alkaline metal), which is based upon three-dimensional copper pyrophosphate framework.

Order–disorder phase transition in the antiperovskite-type structure of synthetic kogarkoite, Na3SO4F

High-temperature phase transition of synthetic kogarkoite, Na3SO4F, has been studied by high-temperature X-ray powder and single-crystal diffraction. The temperature of the phase transition can be estimated as 112.5±12.5°C. The low-temperature phase, α-Na3SO4F, at 293K, is monoclinic, P21/m, a=18.065(3), b=6.958(1), c=11.446(1)Å, β=107.711(1)°, Z=12. The structure contains thirteen symmetrically independent Na sites with coordination numbers varying from 6 to 8, and six independent S sites. The high-temperature β-phase at 423K is rhombohedral, R-3m, a=6.94(1), c=24.58(4)Å, Z=9. The crystal structure of both polymorphs of Na3SO4F can be described as a 9R antiperovskite polytype based upon triplets of face-sharing [FNa6] octahedra linked into a three-dimensional framework by sharing corners. In the α-modification, the SO4 tetrahedra are completely ordered and located in the framework cavities. In the β-modification, there are only two symmetrically independent Na atoms in the structure. The main difference between the structures of the α- and β-phases is the degree of ordering of the SO4 tetrahedra: in the α-modification, they are completely ordered, whereas, in the β-modification, the complete disorder is observed, which is manifested in a number of low-occupied O sites around fully occupied S sites. The phase transition is therefore has an order–disorder character and is associated with the decrease of structural complexity measured as an information content per unit cell [577.528 bits for the low- (α) and 154.830 bits for the high- (β) temperature modifications].

Synthesis, structural and spectroscopic properties of acentric triple molybdate Cs2NaBi(MoO4)3

New ternary molybdate Cs2NaBi(MoO4)3 is synthesized in the system Na2MoO4–Cs2MoO4–Bi2(MoO4)3. The structure of Cs2NaBi(MoO4)3 of a new type is determined in noncentrosymmetric space group R3c, a=10.6435(2), c=40.9524(7)Å, V=4017.71(13)Å3, Z=12 in anisotropic approximation for all atoms taking into account racemic twinning. The structure is completely ordered, Mo atoms are tetrahedrally coordinated, Bi(1) and Bi(2) atoms are in octahedra, and Na(1) and Na(2) atoms have a distorted trigonal prismatic coordination. The Cs(1) and Cs(2) atoms are in the framework cavities with coordination numbers 12 and 10, respectively. No phase transitions were found in Cs2NaBi(MoO4)3 up to the melting point at 826K. The compound shows an SHG signal, I2w/I2w(SiO2)=5 estimated by the powder method. The vibrational properties are evaluated by Raman spectroscopy, and 26 narrow lines are measured.

Series of solvent-induced single-crystal to single-crystal transformations with different sizes of solvent molecules.

A highly stable soft porous coordination polymer (PCP), namely [Cu3(TP)4(N3)2(DMF)2]·2H2O·2DMF (1), has been synthesized via an in situ synthesis of 4-tetrazole pyridine (TP) under solvothermal conditions (DMF = N,N'-dimethylformamide). Remarkably, the solvent molecules in 1 can be respectively exchanged with cyclohexane (C6H12), cyclopentane (C5H10), decahydronaphthalene (C10H18), 1,4-dioxane (C4H8O2), and tetrahydropyrane (C5H10O) in single-crystal to single-crystal (SCSC) manners to yield [Cu3(TP)4(N3)2(DMF)2]·3C6H12 (1a), [Cu3(TP)4(N3)2(DMF)2]·2C5H10 (1b), [Cu3(TP)4(N3)2(DMF)2]·H2O·C10H18 (1c), [Cu3(TP)4(N3)2(DMF)2]·C4H8O2 (1d), [Cu3(TP)4(N3)2]·3C4H8O2 (1e), and [Cu3(TP)4(N3)2]·2H2O·C5H10O (1f). Further, the occluded cyclohexane molecules in 1a can be removed by heating to give its porous guest-free form [Cu3(TP)4(N3)2(DMF)2] (1g). Particularly, in water, 1 can lose its coordinated N3(-) anions to generate [Cu(TP)2(H2O)4]·4H2O (1h). More interestingly, the soft PCP (1) demonstrates the guest selectivity for the cycloalkane solvents, namely cyclohexane, cyclopentane, and decahydronaphthalene, in SCSC manners for the first time, attributed to the synergy effect between the size and geometry of the solvent and the shape of the framework cavity. Moreover, the desolvated samples of 1e show the highly selective gas adsorption of CO2 over N2, indicating its potential application in the separation of the CO2/N2 mixture.