Metal-Organic Frameworks with Heterogeneous Structures. Группа авторов
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5.3 The incorporated BPDC, RuDCBPY, and PtDCBPY into Zr-MOF (UiO-67) through the solvothermal method. Red balls: SBUs. Gray rod: BPDC. Purple rod: RuDCBPY. Yellow rod: PtDCBPY. This figure is copied with the permission of the mentioned reference.
32 Figure 5.4 (a) Powder x-ray diffraction patterns, (b) IR spectra, and (c) TGA analysis of UIO-67black, Pt@ UIO-67red, and Ru-Pt@UIO-67blue. (d) Connolly-surface-filling model demonstrates mother MOFs of UIO-67 (pore size: 8–10 Å).
33 Figure 5.5 (a–c) SEM and (d–j) HAADF-STEM images of the considered samples (top). UV-vis of bpdc, RuDCBPY (aqueous solution), and PtDCBPY (MeOH). (a, b) Diffuse reflectance of the considered samples (middle). (c) Powdery samples photographs under natural light (bottom).
34 Figure 5.6 The formation of coordination polymers from the corresponding metals [4 to 8]/[Cu(2,2′-bpy)]2+[9]/[10] and metalloligand [LCu].
35 Figure 5.7 The epitaxial growth of the trimetallic and bimetallic hetero-(Ln)-MOFs from the crystal seed with one type of metal.
36 Figure 5.8 Transmetalation in porph@MOM-10 (a) and MSO-MOF (b). [Panel (b): metalation after demetalation of MOF].
37 Figure 5.9 (a) 3D structure of [Gd3Cu12I12(IN)9(DMF)4]n. nDMF. (structure I) (b) [Cu12I12] cluster. (c) Tri-nuclear [Gd3(IN)9(DMF)4] units (top). (a) 3D structure of [Gd4Cu4I3(CO3)2(IN)9(HIN)0.5(DMF) (H2O)]n.nDMF.nH2O. (structure I) (b) [Cu3I2] cluster. (c) Gd4(CO3)2 chains (bottom).
38 Figure 5.10 The solid-state luminescent properties of MOFs with diverse SBUs.
39 Figure 5.11 (a and b) MOF 1 structure showing Co3 SBU supported by Co1 and Co2 viewing from two directions. (c) Three-dimensional network viewing along the [010] direction.
40 Figure 6.1 (a) Two types of chiral tetrahedral SBUs. (b) A perspective view of microporous framework: zinc, azury; carbon, gray; oxygen, red. Water molecules of lattice are eliminate for clarity (left). Adsorption isotherm of methane at 298 K, and H2 adsorption desorption isotherms (77 K, inset) activated at 100°C (blue) and 175°C (red) (right and top). Polarization (P) versus applied field (E) hysteresis loops from a single crystal sample (right and bottom).
41 Figure 6.2 (a) Schematic representation of a chiral MOF catalyst by PSM. (b) The chemical structures of the used chiral ligands based on tetracarboxylic acids.
42 Figure 6.3 Crystal structure of chiral MOF-1a. (a)Paddle-wheels clusters based on Cu and their connectivity with chiral L1a ligands. (b) L1a: blue distorted tetrahedro; Cu-paddle-wheel cluster: red square. (c) Connectivity of L1a organic ligands and Cu-paddle-wheel node. (d) Stick model. (e) Representation of a simplified connectivity (top). (a–h) Space-filling models of CMOF-1b to -4b with pores size (bottom).
43 Figure 6.4 (a and b) Views of connectivity around metallic centers in structure 2, highlighting D,L-enantiomeric Cd2+ ions. (c) The one-dimensional zigzag coordination chain structure in 2. Cyan: Cd(1); pink: Cd(2) atom; red: oxygen atom; blue: nitrogen atom; gray: carbon atom; yellow: hydrogen atom. α-methyl groups of D-HCam organic ligands: green-colored balls (similar to Zn-analogous 3).
44 Figure 6.5 Total synthesis of CMOF with chiral axial ligand.
45 Figure 6.6 Different cavity sizes in CMOFs.
46 Figure 6.7 Stick/polyhedra models of CMOF-1-5 with the presence of interpenetration along with connectivity of ligands and SBUs.
47 Figure 7.1 An example of the chiral templating effect origin.
48 Figure 7.2 Synthesis method of Ni-PYI1, guest exchange, and the considered asymmetric catalysis.
49 Figure 7.3 Examples of the post-chiral modification of achiral MOF-NH2 as capillary columns for chiral GC.
50 Figure 7.4 (a–d) GC chromatograms based on chiral MOF-based columns to separate racemates under different conditions. (a) MIL-101-S-2-Ppa coated column A: 2-methyl-2,4-pentanediol (160°C, 2 ml min−1 N2); 1,2-pentanediol (160°C, 2 ml min−1 N2); citronellal (165°C, 2 ml min−1 N2). (b) MIL-101-R-Epo coated column B: 2-butanol (150°C, 2 ml min−1 N2); 1-heptyn-3-ol (200°C, 2 ml min−1 N2); citronellal (180°C, 2 ml min−1 N2). (c) MIL-101-(+)-Ac-L-Ta coated column C: 1-amino-2-propanol (210°C, 2 ml min−1 N2); 2-amino-1-butanol (210°C, 2 ml min−1 N2); 1,2-pentanediol (210°C, 3 ml min−1 N2). (d) MIL-101-L-Pro coated column D: Mandelonitrile (200°C, 1.8 ml min−1 N2); 1-phenylethylamine (180°C, 2 ml min−1N2); methyl-2-chloropropionate (180°C, 2 ml min−1 N2).
51 Figure 7.5 The example of modified MOF with chiral species through post-chiral modification.
52 Figure 7.6 Asymmetry unit in Zn-DPYI crystal structure (left). Crystal structure of Zn-DPYI (right).
53 Figure 7.7 The preparation steps of one kind of chiral Zn-MOF through post-synthesis modification by using two chiral compounds with the opposite chirality.
54 Figure 8.1 A plot based on the number of published articles about the defect of MOFs.
55 Figure 8.2 MOF with interpenetration.
56 Figure 8.3 Different cases of MOFs with various mixed linkers. (a) The parent MOF, (b) the different mixed linker structurally, and (c and d) the large and truncated mixed organic linkers.
57 Figure 8.4 MIL to different forms: (a) without any defect, (b) dangling organic linker, and (c) linker vacancy. The orange polyhedral: cationic units. C atom: black. O atom: blue.
58 Figure 8.5 Defective UiO-66(Zr)-(OH)2 framework for CO2 capture.
59 Figure 9.1 (a) H4PANAD structure. (b) HHU-1 network with varying size pores (two brown atoms illustrate one ellipsoid-like pore). For clarity, H atoms have not been shown.
60 Figure 9.2 Heterogeneous pores due to missing node or ligand.
61 Figure 9.3 An example of MOF-based porous carbon (NHOPC) with multiporosity synthesis as a supercapacitor.
62 Figure 9.4 Examples of Cr-MILs as mesoMOFs with two types of mesocages.
63 Figure 10.1 Schematic representation of bio-MOF composite.
64 Figure 10.2 Heteroepitaxially grown hybrid IRMOF-3@1 and structures of IRMOF-1 and IRMOF-3 (zinc: purple; nitrogen: blue; oxygen: red; carbon: gray. Hydrogen atoms have not been shown).
65 Figure 10.3 Optical micrographs: (a) hybrid IRMOF-3@1, (b) IRMOF-1@3. (IRMOF-1: transparent; IRMOF-3: brownish).
66 Figure 10.4 Isostructural Eu/Tb mixed MOFs with different triplet energy levels.
List of Tables
1 Table 3.1 Examples of mixed ligands metal-organic frameworks.
2 Table 3.2 Determination of catalytic conditions for Biginelli reaction.
3 Table 5.1 Optimization of the carboxylation of phenylacetylene.
4 Table 5.2 Carboxylation of terminal alkynes with CO2.
5 Table 5.3 Crystallographic data and refinement parameters of the considered MOF.
6 Table 5.4 Various applications of mixed-metal MOFs.
7 Table 6.1 Diethylzinc additions to aromatic aldehydes.
8 Table 6.2 Alkynylzinc additions to aromatic aldehydes (similar conditions with Table 6.1).
9 Table 7.1 Asymmetric dihydroxylation of aryl olefins.
10 Table 7.2 Aldol reactions catalyzed by Zn-MOF1.
11 Table 7.3 Aldol reactions by using Zn-MOF1 and Zn-MOF2.
12 Table 7.4 Control reactions for asymmetric epoxidation of styrene.
13 Table 7.5 Asymmetric epoxidation of several olefins and methanolysis of styrene oxide.
14 Table 8.1 Some of the published papers about defects in metal-organic frameworks.
15 Table 8.2 Some of defective MOF-based materials.
16 Table 10.1 Carbon dioxide cycloaddition with various epoxides by using CZ-BDO.