Article pubs.acs.org/IC
Shape-Asymmetry Supramolecular Isomerism in Asymmetrical Ligand PCPs and the Expression Method of Three-Level Isomerism Xiaonan Gao,‡,∥ Ai-Yun Fu,*,†,∥ and Yao-Yu Wang§ †
Materials Chemistry Research Centre, Dezhou University, Dezhou 253023, Shandong, P. R. China Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284, United States § Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Material Sciences, Northwest University, Xi’an 710069, P. R. China ‡
S Supporting Information *
ABSTRACT: We show here the supramolecular isomerism, with respect to shape-asymmetry of ligand and the new hierarchical classification for supramolecular isomerism, the three-level isomerism, which was advanced based on a thorough investigation for the four new Ni/dpt24 polymorphs [Hdpt24 = 3-(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole)]. Compounds 1, 2, and 3 are three-dimensional twofold interpenetrated porous coordination polymers with NbO topology, while 4 with two-dimensional grid structure is termed as the primary isomer of 1/2/ 3 due to the difference of dimensionality. Complex 3 possessing different shape-asymmetry of single networks from 1 and 2, is called as the secondary isomer of 1 and 2. Complexes 1 and 2 possess the same topology, single shape-asymmetry networks, but different interpenetration-orientation and interpenetration-asymmetry, and are defined as the tertiary isomers. Distinct differences in H2 and CO2 adsorption capacity were observed among each level of isomers. In addition, the hierarchical classification’s relationship with characteristic classifications has been discussed.
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INTRODUCTION The recent developments of polymorphism1 and supramolecular isomerism have provided massive information about factors that govern the molecular self-assembly and structure−property relationships.2 Accurately analyzing and expressing the supramolecular isomerism is the key for understanding structure−activity relationship. For the traditional classification method,3 the supramolecular isomerism, based on isomeric characteristics, was divided into four categories: structural,4 optical,5 catenane,6 and conformational isomerisms.7 With the development of coordination chemistry, polarity as a factor to induce supramolecular isomerism and different properties of porous coordination polymers (PCPs) has attracted intensive attention.8 Some new concepts for expressing polarity supramolecular isomerism, such as interpenetration-direction isomerism,9 interpenetration classes,8a were put forward with it. Recently, our research discovered that the shape-asymmetry of a ligand is another nonignorable factor to bring about obvious changes of structure and properties. Specifically, isomeric nonpolar and optically inactive PCPs that possess the same topology, interpenetration number, geometry interpenetration mode (related to the angle between interpenetrated networks), but different shape-asymmetry or different metal−ligand interlinkage orders, can still generate rich supramolecular isomerism and provide obviously different adsorption capacity. We defined such isomerism as shapeasymmetry isomerism. It can be considered to be a supplement of structural isomerism but different from traditional structural isomerism, since it can sometimes lead to optical, polar © XXXX American Chemical Society
isomerism but no changes of frameworks. Moreover, the shapeasymmetry isomerism may occur within a single network of interpenetrated PCPs, which belongs to molecular isomerism. Further, it can also arise in the interpenetration relation of multifold interpenetrated PCPs, which belong to supramolecular isomerism. Therefore, we intend to express all the supramolecular isomerism by hierarchical classification. 3-(2-Pyridyl)-5-(4-pyridyl)-1,2,4-triazole) (Hdpt24) was selected as an asymmetric ligand to synthesize PCPs.10 Chen’s group reported the comparative study involving a threedimensional (3D) Co/dpt24 PCP and its isomorphic 3methylated derivative Co/Medpt24, to demonstrate “hot spots” for gas adsorption.10a They also reported a series of twodimensional (2D) Mn/dpt24 polymorphs.10b Fu et al. reported four Co/dpt24 polymorphs and their transformation property.10c However, supramolecular isomerism analysis for all reported M/dpt24 PCPs ended in changes of dimensions/ topologies, and they didn’t thoroughly analyze the changes of shape-asymmetry/metal-dpt24 linkage order. Fortunately, four new Ni/dpt24 polymorphs: three NbO-type PCPs of {[Ni(dpt24)2)]·0.67DMF}n (1), {[Ni(dpt24)2]3·2DMF}n (2), {[Ni(dpt24)2]9·4.5MeCN}n (3), and layer type {[Ni(dpt24)2]· 0.26H2O}n (4), were successfully synthesized (DMF = dimethylformamide). They exhibit hierarchical and progressive isomerism, offering a unique opportunity to investigate hierarchical classification of supramolecular isomerism. Herein Received: January 11, 2016
A
DOI: 10.1021/acs.inorgchem.6b00081 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry we present the new classification method of the three-level isomerism and the relationship between the hierarchical and the characteristic classification.
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EXPERIMENTAL SECTION
Materials and Methods. Commercially available reagents were used as received without further purification. Elemental analysis (C, H, and N) was performed on a Vario EL III elemental analyzer. Thermal gravimetric analysis was performed under N2 using a NETZSCH TG 209 system. Powder X-ray diffraction (PXRD) patterns were recorded on a Bruker D8 Advance diffractometer (Cu K) under N2. Gas sorption isotherms were measured on an automated gas adsorption analyzer (Quantachrome ASIQC 0000−4). Crystal Structure Determination. Intensity data were collected on a Bruker Apex II CCD area-detector diffractometer (Mo K). Absorption corrections were applied by using the multiscan program SADABS. The structures were solved with direct method and refined with a full-matrix least-squares technique with the SHELXTL program package. Anisotropic thermal parameters were applied to all nonhydrogen atoms except the guest molecules. The organic hydrogen atoms were generated geometrically. Synthesis of [Ni(dpt24)2)·0.67DMF (1). A mixture of Hdpt24 (0.044 g, 0.2 mmol), NiCl2·6H2O (0.024 g, 0.10 mmol), and DMF (6 mL) was sealed in a 15 mL Teflon-lined reactor and heated at 120 °C for 2 d, and then cooled by 2 °C/h to room temperature to produce pink block crystals of 1 (39%). Anal. Calcd (%) for C26H20.7NiN10.6O0.67: C, 56.57; H, 3.78; N, 27.07. Found: C, 56.62; H, 3.71; N, 26.92. Synthesis of [Ni(dpt24)]·2DMF (2). A mixture of Hdpt24 (0.044 g, 0.2 mmol), NiCl2·6H2O (0.024g, 0.10 mmol), EtOH (3 mL), and DMF (3 mL) was sealed in a 15 mL Teflon-lined reactor, heated at 120 °C for 2 d, and then cooled to room temperature to attain 2 as baby pink block crystals (47%). Anal. Calcd (%) for the activated sample C78H62N32Ni3O2: C, 56.59; H, 3.77; N, 27.07. Found: C, 56.50; H, 3.75; N, 27.10. Synthesis of [Ni(dpt24)]·4.5MeCN (3). A mixture of Hdpt24 (0.044 g, 0.2 mmol), NiCl2·6H2O (0.024g, 0.10 mmol), MeCN (3 mL), and MeOH (3 mL) was sealed in a 15 mL Teflon-lined solvothermal reactor, heated at 120 °C for 2 d, and then cooled by room temperature to afford 3 as mixture of baby pink block crystals and powder (35%). Anal. Calcd (%) for the activated sample C225.06H157.5N94.56Ni9: C, 57.34; H, 3.37; N, 28.09. Found: C, 57.29; H, 3.35; N, 28.04. Synthesis of [Ni(dpt24)2]·0.26H2O (4). A mixture of Hdpt24 (0.044 g, 0.2 mmol), NiCl2·6H2O (0.024g, 0.10 mmol), DMF (3 mL), and H2O (3 mL) was sealed in a 15 mL Teflon-lined reactor and heated at 120 °C for 2 d, and then it was cooled by 2 °C/h to room temperature to produce 4 as pink block crystals (44%). Anal. Calcd (%) for C24H16.5NiN10O0.26: C, 56.76; H, 3.28; N, 27.58. Found: C, 56.69; H, 3.25; N, 27.51.
Figure 1. (a) Coordination mode of dpt24. (b) The plane of axial ligands parallel to the extending direction of the equatorial ligands gives (c) the structure with NbO topology for 1, 2, and 3. (d) Axial ligands plane perpendicular to the extending direction of the equatorial ligands products (e) the structure with 2D grid topology for 4.
the overall network structure matches the nonpolar NbO topology, whereas, when it is perpendicular to the extending direction, the nonpolar 2D grid structure results as depicted in Figure 1. Thus, the structure change between 1/2/3 and 4 is characterized by primary isomerism. The NbO type structures of 1, 2, and 3 possess the following characteristics in common. First, the NbO-type structure can be viewed as three mutual perpendicular coordination chains that are interconnected by Ni atoms (Figure 2a,b). Each structure
Figure 2. (a) The NbO-I type network and (b) the NbO-II type network, in which the vertexes and edges represent the Ni atom and dpt24 ligand. (c) Azure stick represents a right-handed chain, and purple stick represents left-handed chain.
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possibly has two closely related, mirror-imagelike modes of metal−ligand linkage orders, which are called right- and lefthanded chains (shown in different colors of azure and purple in all Figures below). Second, the parallel chains within a single network are always with the same metal−ligand linkage order (shown in same colors in all Figures below). It has been found that in 1, 2, and 3, there are two types of networks, named NbO-I and NbO-II (Figures 2a,b and 3a,b). NbO-I type network contains left-handed chains in two dimensionalities but right-handed ones in one dimensionality. In contrast, NbO-II type network consists of left-handed chains in one dimensionality but right-handed chains in two dimensionalities. Thus, single networks NbO-I and NbO-II possess significant difference of metal−ligand linkage orders, which is called shape-asymmetry isomerism. Both twofold interpenetrated PCPs 1 and 2 contain NbO-I networks, while 3 is built by two interpenetrated NbO-II networks. So the
RESULTS AND DISCUSSION Analysis and Comparison of the Structures. Ni-dpt24 polymorphs were synthesized under solvothermal conditions with variations of solvents (Supporting Information). Crystallographic studies revealed that compounds 1, 2, and 3 are 3D twofold interpenetrated structures with NbO topology. In contrast, compound 4 has been shown with a 2D square-shaped grid structure. Except for the guest molecules, these four Ni/ dpt24 polymorphs are chemically identical in their host framework composition and in the centrosymmetric formal local coordination environment of the Ni atom. Each Ni atom is chelated by two dpt24 ligands in trans-disposed mode forming the equatorial plane and also coordinated by two dpt24 ligands via terminal 5-pyridyl group along the axial positions. As shown in Figure 1, when the plane of the axial ligands is parallel to the extending direction of the equatorial coordination chains, B
DOI: 10.1021/acs.inorgchem.6b00081 Inorg. Chem. XXXX, XXX, XXX−XXX
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Figure 3. (a) Single NbO-I cage contains (c) NbO-I-A and (d) NbOI-B channels; and (b) single NbO-II cage contains (e) NbO-II-A and (f) NbO-II-B channels. The red and azure balls present N4 and N1 atoms, respectively.
Figure 4. Two NbO-I networks interpenetrated with L-, R-orientation produce NbO-I-A for 1 (a) and NbO-I-B (b) channel for 2. And two NbO-II networks interpeneted with L-, R-orientation give NbO-I-A for 3 (c) and NbO-II-B (d) channels.
relationship between 1/2 and 3 may be termed as secondary isomerism. In addition, NbO-I network has academically four types of channels but possesses actually two types of channels labeled as NbO-I-A and NbO-I-B. NbO-II network, in the same way, contains NbO-II-A and NbO-II-B types channels (Figure 3c3f). The NbO-I-A channel contains six N4 atoms, NbO-I-B channel includes two N4 and four N1 atoms, while NbO-II-A channel contains six N1 atoms on the channels’ surfaces. Since N1 atom is located at the chelated side of ligand (Figure 1a), it is always sheded by neighboring pyridyl groups. In contrast, the N4 atom has larger available space for host−guest interaction. More importantly, the uncoordinated N atoms act as “hot spots” for the gas adsorption in PCPs.10a Taking this into account, the gas adsorption capacity of all sorts of channels should scale with the number of N4 atoms on the channel surface with the order of NbO-I-A > NbO-I-B > NbO-II-A. Because of the twofold interpenetration, each 3D NbO complex only contains one kind of channel. As shown in Figure 4 and 5, complexes 1, 2, and 3 contain NbO-I-A, NbO-I-B, and NbO-II-A types channels, respectively. And the channels of two interpenetrated networks in 1 are staggered arrangement (Figure 5), while those are parallel arrangements in 2 and 3 (Figure 4b,c). Specifically, the channel type depends on the interpenetration orientation (relative orientation of two interpenetrated networks). For 1, two interpenetrated NbO-I networks adopt L-orientation (left network at the front; see Figures 4a and 5) to produce the NbO-I-A type of channel, while two interpenetrated NbO-I networks in 2 adopt R-orientation (i.e., right network at the front), to result the NbO-I-B type of channel (Figure 4b). This kind of difference of interpenetration action is called interpenetration−orientation isomerism. When two NbO-II networks interpenetrate in L-orientation, NbO-IIA type of channels are obtained for 3 (Figure 4c). R-orientation interpenetration of NbO-II networks give NbO-II-B type of channels (Figure 4d).
Figure 5. Two NbO-I networks interpenetrated in L-orientation and asymmetry nonparallel modes (a), which gives the channels in staggered arrangement for complex 1 (b).
However, the two interpenetrated networks in 2 and 3 have identical metal−ligand interlinkage orders in every dimensionality (Figure 4b,c), giving channels in parallel arrangement. It is defined as symmetrical parallel interpenetration. In 1, the two interpenetrated networks have different metal−ligand linkage orders in two dimensionalities (Figure 5), resulting in a staggered arrangement of the channels. This is called symmetrical nonparallel interpenetration. The difference between them is termed interpenetration−asymmetry isomerism. The detailed information on interpenetration action of two NbO-I networks in 1 is displayed in Figure S1. Since 1 and 2 possess identical NbO-I single networks but different interpentration−orientation and interpenetration−asymmetry, the structural difference between them belongs to the tertiary supermolecular isomerism. So 1 versus 2 can be considered as tertiary isomers. Hierarchical Classification’s Relationship with Characteristic Classification of Supramolecular Isomerism. The three-level isomerism (including primary, secondary, and tertiary isomerism), as a new expression method of superC
DOI: 10.1021/acs.inorgchem.6b00081 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry molecular isomerism, covers all kinds of supramolecular isomerism based on characteristic classification. The primary isomerism refers to that isomeric PCPs have the same chemical composition but different dimensions/topologies/interpenetration-number/interpenetration-geometry, which is same as traditional structural isomerism. The secondary isomerism is that the PCPs possess the same type of primary structure but different metal−ligand interlinkage order in single/isolated networks, and it thus includes shape-asymmetry, polarity, and optical isomerism. The tertiary supramolecular isomerism is defined as the primary and secondary isostructural PCPs with different interpenetration modes related to shape-asymmetry, including interpenetration−orientation, symmetrical parallel/ nonparallel interpenetration, interpenetration−direction (polarity), polarity class, optics, and conformation, as shown in Scheme 1.
Figure 6. Hydrogen adsorption/desorption isotherms for 1, 2, and 3 at 77 K show hydrogen adsorption abilities order of 1 > 2 > 3.
is less of 60.5 and 21.7 cm3·g−1 than that of 1 and 2, respectively; but it is higher of 20 cm3·g−1 than isostructural [Co(dpt24)2] reported elsewhere.11b Virial analysis12 of the hydrogen adsorption isotherms measured at 77 and 87 K (Figures S9 and S10) revealed that the adsorption enthalpies at zero surface coverage are 8.2, 7.3, and 6.7 kJ·mol−1 for 1, 2, and 3, respectively, appearing in the same order of 1 > 2 > 3 as adsorptive capacity (Figure S11). Notice the ratios of adsorption/surface area of 0.34 for 1 and 0.27 for 2, indicating higher sorption capacity than 2. Therefore, the experimental facts and BET surface area analysis are in agreement with each other. Shown in Figure 7 is the CO2 adsorption isotherms measured at 195 K for 1, 2, and 3, all of which exhibit type I
Scheme 1. An Illustration for the Relationship between the Three-Level Isomerism and Property-Based Classifications of Supramolecular Isomerism
Gas Adsorption Properties. Compelexes 1, 2, 3, and 4 each possess different channel shapes (Figures S2 and S3) and number of N4 atoms, which encouraged us to explore their gas adsorption properties. Thermogravimetric analysis and variabletemperature PXRD studies showed that 1, 2, and 3 can be readily activated while maintaining the structural integrity of the frameworks with high thermostability up to 430 °C (1) and 440 °C (2 and 3) under N2 atmosphere (Figures S4−S7). In addition, the void volumes are 28.9% for 1, 28.9% for 2, and 25.8% for 3 as calculated by PLATON.11a In contrast, 4 is a 2D structure, and the free volume is 3.3% calculated by Materials Studio 4.0,11b which indicates that 4 with the lowest gas adsorption ability lacks space for gas molecules to penetrate. To evaluate the microporosity of 1−3, N2 adsorption measurements at 77 K were measured (Figure S8). The data observed were fit by Brunauer−Emmett−Teller (BET) model to estimate the surface area of 1, 2, and 3 as 461, 429, and 421 m2 g−1, respectively. H2 adsorption measurements of 1, 2, and 3 were also investigated at 77 K, which indicates a diminishing absorption trend as predicted above (Figure 6). The hydrogen sorption for 1 shows an unsaturated behavior with a maximum adsorption capacity of 155.9 cm3·g−1 or 1.0 wt % at 1 atm. In contrast, 2, as the tertiary supramolecular isomer of 1, shows hydrogen sorption capacity of 117.1 cm3·g−1 or 1.2 wt %, which is 39 cm3·g−1 less than that of 1, while compound 3, as the secondary isomer of 1/2, only presents 95.4 cm3·g−1 or 0.85 wt %, which
Figure 7. CO2 adsorption/desorption isotherms for 1, 2, and 3 at 77 K within 1 atm and at zero surface coverage show CO2 adsorption abilities order of 1 > 2 > 3.
isotherm. The saturated adsorption amount of 138.4 cm3 (STP)·g−1 was measured for 1, and the unsaturated adsorption amount of 126.4 (saturated value of 136) and 107.3 (saturated value of 124) cm3·(STP)·g−1 were obtained for 2 and 3, respectively. It is showing the order of CO2 adsorption abilities is 1 > 2 > 3. From the adsorption isotherms of 1, 2, and 3 at zero surface coverage, it is found that the equilibrium pressures of 2 and 3 are 1.36 and 1.97 times of 1, respectively, at the same adsorption amount. The adsorption enthalpy of 1 at zero surface coverage was calculated13 by Clausius−Clapeyron equation to be 0.51 and 1.1 kJ·mol−1 higher than that of 2 D
DOI: 10.1021/acs.inorgchem.6b00081 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
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and 3, respectively. It indicates that the differences of adsorption capacities among 1, 2, and 3 are derived from not only the structural change but also the level of exposure of uncoordinated N atoms.
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CONCLUSIONS In conclusion, it has been found from the structural analysis of new Ni/dpt24 polymorphs that shaped asymmetry isomerism is a nonignorable factor to bring about supramolecular isomerism. To express such phenomenon, the three-level isomerism (the primary, secondary, and tertiary isomerism) was proposed for the first time. And a range of innovative concepts, including interpenetration−orientation isomerism and interpenetration− asymmetry isomerism also were put forward with it. The hierarchical classification includes all the supramolecular isomerism involved in characteristic classifications. The drastic difference of H2 and CO2 adsorption capacities among each level isomer indicates the effect of the subtle structural variation on the material function and also proves the necessity of the new classification method. The present work significantly extends the connotation of supramolecular isomerism, which should be instructive for expressing of shape-asymmetry isomerism as well as for understanding the relationship among all kinds of supramolecular isomerism.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b00081. X-ray crystallographic information for CCDC Nos. 907782−907784 and 789383. (CIF) Materials, methods, synthesis, and characterization procedures, crystallographic data and collection parameters, selected bond lengths and angles, EA, variabletemperature PXRD patterns, illustrated networks A and B, illustrated one-dimensional channels of compounds 1−4, and additional sorption isotherms. (PDF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Phone: (+86) 0534-8985561. Author Contributions ∥
These authors contributed equally. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS The research was supported by the National Natural Science Foundation of China (Grant Nos. 20771021 & 21171031) and Dezhou Science Foundation, China (2011B11).
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REFERENCES
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DOI: 10.1021/acs.inorgchem.6b00081 Inorg. Chem. XXXX, XXX, XXX−XXX
