Review pubs.acs.

org/cm

Functional Hybrid Porous Coordination Polymers

Maw Lin Foo,, Ryotaro Matsuda,*,, and Susumu Kitagawa*,,,

Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan ERATO Kitagawa Integrated Pores Project, Kyoto Research Park Bldg #3, Shimogyo-ku, Kyoto 600-8815, Japan Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan ABSTRACT: Porous coordination polymers (PCPs) have attracted vast interest in recent years because of their possibility for rational design of crystal structures and functional properties. An emerging trend in PCP research is hybridization, which is the subject of this review. We have divided hybrid PCPs into three broad classes: class I, isomorphous mixed metal/ligand PCPs; class II, core@shell PCPs; class III, PCPguest or PCPs with accommodated guests. In this Review, we examine 62 representative hybrid PCPs in the area of gas adsorption/separation/ storage, luminescence, catalysis, drug delivery, and ionic conductivity with representative examples of each class to understand the underlying principles of hybridization for PCPs and their advantages over conventional PCPs. The future directions and applications of hybrid PCPs are postulated. KEYWORDS: porous coordination polymers, metalorganic frameworks, hybrid materials, porous frameworks orous coordination polymers (PCPs) or metalorganic frameworks (MOFs) are porous, polymeric (1-D, 2-D, or 3-D) solids held by coordination bonds between metal centers and organic ligands. Growth in this area has been explosive since the rst PCPs were reported in the late 20th century.1 Their potential applications have been explored in diverse areas, such as gas storage/separations,2 drug delivery,3 catalysis,4 luminescence,5 sensing,6 and ionic/electronic conductivity.7 The synthesis of new PCPs for new/improved functions is still an ongoing activity. There are currently a few approaches to the synthesis of new PCPs. One approach is the design and synthesis of new functional ligands.8 Another approach to PCP synthesis is to obtain isomorphous structures of a certain crystal structure type by using either dierent metals with the same charge, coordination environment, or dierent ligands with the same denticity. Prototypical examples of structure types include (but are certainly not conned to) MOF-59 or [M4O(1,4BDC)3] (M = Zn2+, Co2+, Be2+; H2BDC = benzendicarboxylic acid), MOF-7410 series or [M2(DOBDC)] (M = Mg2+, Zn2+, Mn2+, Fe2+, Ni2+, Co2+; H2DOBDC = 2,5-dihydroxyterephthalic acid), MIL-5311 or [M(OH)(BDC)] (M = Al3+, Fe3+, In3+, Cr3+, Sc3+, V3+, Ga3+), MIL-10112 or [M3F(H2O)2O(BDC)]3 (M = V3+, Cr3+, Al3+, Fe3+, In3+), HKUST-113 series or [M3(BTC)2] (M = Cr2+, Fe2+, Ni2+, Cu2+, Mo2+, Ru2+; H3BTC = trimesic acid). Another family utilizes both carboxylates and pillaring pyridyls such as JAST-1 or [M(1,4-BDC)(Pillar)]14 (M = Cu2+, Zn2+, Ni2+), CID-1 or [M(1,3-BDC)(bipy)]15 (M = Zn2+, Mn2+, Cd2+, Ni2+). Isoreticular synthesis is yet another approach: ligands of the same denticity but with longer girths are employed to obtain the same crystal structure type with increased pore dimensions. This approach has been used successfully to extend the pore dimensions of structure types such as CPL16 or [Cu2(pzdc)2(L1)](H2pzdc = pyrazine-2,3-

dicarboxylic acid, L1 = pyrazine or dipyridyl pillar ligands), IRMOF,17 HKUST-1,18 MOF-74,19 and UIO-66.20 Recently, another approach, hybridization, has been in the forefront to increase diversity and functions of PCPs. From past experiences with other traditional materials such as metals, ceramics and polymers, the hybridization (mixing) of dierent components at the atomic, molecular, nanoscale, and mesoscale allows the physical properties of the resultant composite to be tuned. PCPs are no exceptions and recent works have demonstrated that hybridization allows for the exquisite control of physical properties between that of pure end members (law of mixing), and sometimes intriguingly, synergism (sum of the parts is greater than sum of individual) may occur. It is the purpose of this Review to cover this exciting new frontier of functional PCPs. The scope of this review is conceptual and not meant to be exhaustive. We dene hybridization for the scope of this Review to belong to three broad classes (Figure 1). Class I: Isomorphous Mixed Metal/Ligand PCPs. Since a PCP consists of metal centers and organic ligands, there are two possible routes for formation of mixed frameworks. An isomorphous mixed metal PCP (IMM-PCP), is dened as a PCP in which there are more than one type of metal in equivalent sites, that is, [M1xMx(L)] (0 x 1), where M(L) is the parent framework and M is the metal ion dopant. It is noted that dierent metals need to occupy
Special Issue: Celebrating Twenty-Five Years of Chemistry of Materials Received: July 1, 2013 Revised: October 15, 2013 Published: November 4, 2013
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Review

Figure 1. Schematic of the three classes of hybrid PCPs discussed in this Review.

equivalent sites, thus PCPs which contain metallo-ligands21c or dierent metals occupying distinct sites are not inherently IMM-PCPs. An isomorphous mixed ligand PCP (IML-PCP) is dened as a PCP in which more than one ligand is present with equivalent denticity, that is, [M(L)x(L)1x] (0 x 1), in this case L is the ligand dopant. It is stressed that the doping ligand has to be of equivalent denticity as there are a signicant number of pillared PCPs14,15 that inherently contain two ligands of unequivalent denticity and thus are not IML-PCPs. It is noted that the terminology is still unclear in this arena, depending on the authors it can be referred to as solid solution, mixed component, mixed MOF, or multivariate MOF (MTV). We prefer to use the denition isomorphous mixed (IM) because it denotes that mixing of the metal/ligand sites has occurred with preservation of topology. The term solid solution, in theory can only be used when rigorous structural evidence is present, that is, Vegards Law (see Characterization section) is obeyed, and this may or may not be detected for porous PCPs compared to purely close-packed inorganic compounds. The eld of mixed PCPs has been the subject of recent comprehensive reviews.21 Class II: CoreShell (A@B). Another eective way of hybridizing PCPs is the formation of coreshell structures. Unlike the formation of IMM/IML-PCPs, where mixing is present at the intimate (atomic/molecular) scale, there are two or more distinct phases in a coreshell system. The convention A@B where A is the core and B is the shell will be used. The core and shell may be both coordination polymers (i.e., PCP@ PCP) or only one of them is a coordination polymer and the other is wholly inorganic (i.e., Au nanoparticle). Class III: PCP w ith A ccommodated Guest (PCPguest). Because of the inherent porosity of PCPs with well-dened pores and cavities, PCPs are well suited for accommodation of functional guests, such as monomers, polyoxometallates, and enzymes upon removal of solvent guests. Because of the uniform, typically angstrom sized channels of the PCPs, the guests are conned in nanospace and do not interact with each other, creating unique properties via nanoconnement. This form of accommodation is represented by the convention PCPguest whereupon the guest is residing in the pores/cavities of the PCP.

MOF-5 structure type has been reported with BDC-NO2 (H2BDC-NO2 = 2-nitro-1,4-benzene-dicarboxylic acid) as a ligand. However, on adding BDC as a coligand, an IML-PCP [Zn4O(BDC)2.14(BDC-NO2)0.86] 1, with MOF-5 structure type could be synthesized. Another key concept is the control of interpenetration with doping level. For example, [Zn4O(L2)3] (H2L2 = 9,10-bis(triisopropylsilyloxy)phenanthrene-2,7dicarboxylic acid or H2TPDC) is noninterpenetrated because of the bulky TIPS (triisopropylsilyloxy) group, and [Zn4O(L3)3] (H2L3 = 3,3,5,5-tetramethyl-4,4-biphenyldicarboxylic acid or H2Me4BPDC) is interpenetrated because of the length of the linker. Thus, both these frameworks have relatively low surface areas due to pore blockage and framework interpenetration respectively. Using an IML-PCP, [Zn4O{(L2)x(L3)1x}3] 2 (Figure 2), the level of framework interpenetration and the degree of pore blockage is modulated, resulting at x = 0.40.5 the largest surface areas.22

Figure 2. Variation in surface area with x for [Zn4O{(L2)1x(L3)x}3] 2, where H2L2 = H2Me4BPDC and H2L3 = H2TPDC. Reprinted with permission from ref 22. Copyright 2011 American Chemical Society.

UTILITY OF HYBRID PCPS IMM or IML-PCPs allow the chemist to obtain intermediate properties between its end members (the law of mixing). In other instances, the reason is purely synthetic: for IML-PCPs, sometimes with a particular ligand, the PCP with the required structure type does not result despite being of suitable denticity, perhaps due to steric or electronic constraints. For example, no
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For coreshell frameworks, it allows for the incorporation of PCPs with two dierent ligands of dierent lengths but identical denticity, which is not possible in an IML-PCP. For example, in JAST type frameworks, a shell layer of [Zn(1,4NDC)(DPNI)] (H2NDC = naphthalene dicarboxylic acid, DPNI = 1,4-dipyridyl-naphthalenediimide) could be grown on top of a [Zn(1,4-NDC)(DABCO)] core,23 that is, [Zn(1,4NDC)(DABCO)]@[Zn(1,4-NDC)(DPNI)] 3. Another function of a PCP shell, especially those with a nanoparticle core is to serve as a size selective molecular sieve, only allowing target molecules of a certain size or shape to reach the nanoparticle core. Nanoparticle cores also endow on the PCP hybrid properties of inorganic nanoparticles such as catalytic activity, magnetism and light emission. The fabrication and applications of inorganic nanoparticles in PCPs/MOFs has been recently reviewed.24 For frameworks with functional guests, it allows the incorporation of other classes of materials with dierent properties from typical coordination compounds, such as porrphyrins, polymers, polyoxometallates, and enzymes. Because of nanospace connement of guests in angstromsized pores, physical properties such as magnetic/dielectric/ catalysis/luminescence/transport properties may be strongly enhanced. In addition, monomeric guests can be polymerized in the pores to yield polymers with unique properties strictly dictated by pore size, pore geometry, and pore chemistry of the host PCP.25
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SYNTHESIS OF HYBRID PCPS Direct Addition. Direct addition is perhaps the most straightforward method for obtaining IMM/IML-PCPs (Class I, Figure 3). The metals and ligand dopants are added directly

Review

Figure 3. Synthesis of classical PCP and class I, II, and III hybrid PCPs.

to the reactant solution. As the actual ratio of metals/ligands in the obtained product may not have a composition similar to the feed ratio, it is of utmost importance to characterize the actual composition of the obtained product (see Characterization section). Postsynthesis. Postsynthesis is another powerful synthetic method or obtaining IMM/IML-PCPs if direct addition is not successful. The precursor PCP is synthesized rst, in single crystal or powder form, and then the metal sites/and or ligand sites modied by soaks in solutions, either at room temperature or elevated temperatures. This method exploits the inherent dynamic nature of the coordination bond. Depending on the system, there may be complete or partial exchange of ligands or metals. For example, MOF-5 crystals could be soaked in a NiCl2/ DMF solution to obtain IMM-PCP, [(Zn 1 x Ni x ) 4 O(BDC)3(DEF)2x] 4, a pale-yellow solid can be obtained with a maximum value of x = 1 after one year of soaking.26 The same
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concept can be applied to ligands, using MOF-5 but exposure to a solution of organic ligands can yield IML-PCPs. [Zn4O{(BDC)1x(BDC-Br)x}3] 5 (H2BDC-Br = 2-bromo-1,4benzene-dicarboxylic acid) can be synthesized via treatment of the ligand solution in DMF at 85 C with no signicant degradation.27 Up to 50% ligand exchange is possible. Covalent Postsynthetic Modication. Another alternative to the synthesis of IML-PCPs is covalent postsynthetic modication on the ligands, typically on aromatic NH2 handles.28 Some examples of postsynthetic modication reactions include the formation of amide29 and urea30 linkages via reaction with acetic anhydrides and isocyanates respectively; ring-opening reactions via reaction with 1,3-propanesultone or 2-methylaziridine.31 The aromatic NH2 group can also be transformed into isocyanides32 and azido functional groups33 for further reactions. IML-PCPs can be produced by postsynthesis as such reactions typically does not usually go to completion, either due to steric hindrance, or the reaction time being controlled for preservation of crystallinity, Thus, almost any postsynthetic reaction will result in IML-PCPs. This best manifestation of this concept is for [Zn4O(BDC-NH2)3] (H2BDC-NH2 = 2-amino-1,4-benzene-dicarboxylic acid) or IRMOF-3, in which four additional ligands is grafted by postsynthesis. Thus, the resultant IML-PCP 6 contains f ive distinct ligands, corresponding to the unmodied NH2BDC, two amide-modied linkers, and two urea-modied linkers.34 For coreshell PCPs consisting of coordination polymers in both core and shell or PCP@PCP, they are usually synthesized via postsynthesis (Class II, Figure 3), that is, adding crystals of one PCP into the mother liquor of another PCP. This approach allows the epitaxial growth of the second PCP on top of the rst.18,35 Direct one-pot addition of metal ions, ligands to form coreshell PCP structures is also possible, albeit rare as illustrated in [Zn(5-NO2-ip)(bpy)]@ [Mn(5-NO2-ip)(bpy)] 7 or Zn-CID-5@Mn-CID-5 (5-NO2-ip = 5-nitroisophthalate, bpy =4,4-bipyridine).36 For nanoparticles(NPs)@PCP hybrids, the preformed nanoparticles can be placed in the growth solution and the PCP will grow around the nanoparticles. Alternatively, deposition of nanoparticle precursors by chemical deposition, followed by decomposition can be performed. We note that another powerful method of forming core shell PCP thin lms is via step-by-step liquid phase epitaxial (LPE) approach for the fabrication of surface attached MOF crystallites forming PCP thin lms or SURMOFs (surface mounted metalorganic frameworks).37 As the synthesis of SURMOFs is in a layer-by-layer fashion, it is possible to achieve a high degree of control the PCP architecture. Because of space constraints, this Review will focus only on bulk materials. Light-induced structural change with pore surface modication is a powerful tool for both syntheses of Class I and II hybrid PCP. In this method, the PCP is synthesized with a light responsive module and then subsequent light irradiation achieves structural change or pore surface activation. This method renders it possible to generate highly active sites which are otherwise impossible to synthesize directly. In addition, the conversion ratio can be controlled by irradiation time, and moreover anisotropic conversion is also possible. Recently the postsynthetic synthesis of a reactive nitrene intermediate that could activate oxygen was demonstrated (Figure 4).38 UV activation of [Zn2(5-N3-isop)2(bpy)] (5-N3isop = 5-azido-isophtalate) occurred in a single-crystal to singlecrystal fashion, converting some of the azide groups into nitrenes, and giving a product that was crystallographically
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Figure 4. Photoactivation of [Zn2(5-N3-isop)2(bpy)] to obtain IMLPCP with nitrene moiety, followed by reaction with oxygen to aord a mixture of NO2 and NO groups. From ref 38. Reprinted with permission from AAAS.

characterized as an IML-PCP: [Zn2(5-N3-isop)1.38(5-N-isop)0.62(bpy)] 8 (5-N-isop = 5-nitrene-isophtalate) The photogenerated nitrene reacts with oxygen to form a mixture of nitro (NO2) and nitroso (NO) groups (Figure 4). Reaction with carbon monoxide is also possible. Thus removal of these gases with photoirradiation is rendered possible. [2 + 2] cycloaddition reaction between CC double bonds is also another useful photochemical module.39 For the synthesis of PCPs with accommodated guests in pores (Class III, Figure 3), one-pot synthetic reaction of the preformed guest and PCP growth solution is possible. It has been observed in certain cases such as Cu-HKUST1H3PW12O40 9 that the Keggin cluster actually facilitates the formation of the hybrid PCP at room temperature.40 More commonly, the inf iltration route is used. The guest or precursor is in ltrated into the guest-free PCP framework via sublimation,41 vacuum assisted inltration from melt42 or solution.43

not as pronounced compared to close packed metals/inorganic solids. Nevertheless, this consistent shift in lattice parameters has been observed in the literature. Baiker and co-workers used high-resolution synchrotron radiation to verify that Vegards Law was observed in the IML-PCP or MIXMOF [Zn4O{(BDC)1x(BDC-NH2)x}3] 10 (x = 0, 0.2, 0.3, 0.9).45 A linear correlation between BDC-NH2 content and peak shift was observed (Figure 5). A linear shift in the lattice parameter versus x was observed for the IML-PCPs of UiO-66 derivative [Zr6O4(OH)4{(BDC-HSO3)x(BDC)1x}6] 11 (x = 0, 0.18, 0.40, 0.69, and 1.0).46

CHARACTERIZATION For hybrid PCPs, meticulous characterization is important to prove that mixing has occurred at the molecular level for class I materials; for class II materials, the coreshell architecture has been successfully formed; and for class III materials, there are no extraneous guests located outside the pore. Class I. By mixing two or more components of metal or ligands, the onus is to show that the resultant frameworks are truly mixed at the molecular level instead of a mixture of phases at the microscale. Hence a variety of characterization techniques are employed as detailed below and can be employed on both single crystal and powders. Optical Microscopy. Optical microscopy is perhaps the easiest to perform given the easy access of optical microscopes. This is most useful on single-crystals which exhibit a color change on metal or ligand exchange. A uniform color change occurring in a single crystal is strong evidence that exchange has occurred homogeneously and only a single domain is present. SEM-EDX and TEM-EDX. SEM-EDX and TEM-EDX is a useful characterization technique for IMM-PCPs, especially for metallic elements. Energy dispersive X-ray maps of elements can be constructed to show that the distribution of metals in each PCP particle is identical and uniform if IMM-PCPs are synthesized. Powder XRD. When powder X-ray diraction is used as a characterization technique, the fulllment of Vegards Law44 is a good indication that solid-solution formation has occurred. Commonly employed in metallurgy and solid-state chemistry, Vegards law is an empirical rule that there is a linear relationship between crystal lattice parameters (or cell volume for low symmetry solids) and the degree of substitution. If no isomorphous substitution has occurred, each peak may be split into two individual peaks belonging to the pure end members. As PCPs are porous materials, the shift in lattice parameters are
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Figure 5. High resolution synchrotron X-ray of 10 for x = 0, 0.2, 0.3, and 0.9. (inset) A linear relationship is established between BDC-NH2 content and peak position, proving random mixing of ligands in crystal structure. Reprinted with permission from ref 45. Copyright 2009 Wiley VCH.

Liquid and Solid-State NMR. From the previous techniques, if it is proven that the metals or ligands are truly mixed at the molecular scale with no contaminating side phases, liquid NMR can be employed to examine digested powders/crystals to yield the actual proportion of organic ligands present in the crystal. As mentioned previously, this actual composition may be dierent from the starting (feed) composition depending on the system. For example, even though equimolar concentrations of both BDC and BDC-NH2 were used in the synthetic solution, the composition of the resultant multivariate (MTV) MOF-5 crystal obtained is [Zn4O(BDC)1.92(BDC-NH2)1.08] 10a. To prove that no macroscopic domains of pure members exist, separate sections of a large single crystal were analyzed via liquid NMR of digested samples. All had the same composition of ligands, suggesting that no macroscopic domains of pure end members exist.19 Solid-state 13C NMR was also employed to prove the MTV-MOFs had dierent chemical shifts from the free ligand. In addition, for the copper paddlewheel system [(ZnxCu1x)3(BTC)2] 12 (x 0.07), solid-state 1H NMR was used to quantify the amount of Zn2+ doped into the parent CuHKUST-1 structure.47 Mass Spectrometry. For powders, ATOFMS (aerosol timeof-ight mass spectrometry) can be used to analyze the chemical composition of powders on the single particle level, which is very useful for determining whether an IML-PCP has been formed. This technique was used to prove that a mixture of UIO-66-Br or [Zr6(OH)4O4(BDC-Br)6] and UIO-66-NH2 or [Zr6(OH)4O4(BDC-NH2)6] in water gave [Zr6(OH)4O4{(BDC-Br)x(BDC-NH2)1x}6] 13 by examining 1976 particles in total, out of which 97% had both Br and CN fragments detected. ATOFMS can also be employed to prove that ligand exchange has occurred instead of dissolution by monitoring particle size.48
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Chemistry of Materials Class II. In a coreshell system, direct visualization of the core/shell heterostructure is important. Optical microscopy was used to demonstrate that MOF-5@IRMOF-3 14 coreshells have been obtained as the color of MOF-5 is colorless compared to orange IRMOF-3.35 In the same fashion, elemental maps using SEM/TEM can be used to prove coreshell formation in powder samples of Zn-CID-5@MnCID-5 or 7.36 NPs@PCPs can be visualized directly by TEM, however it is noted that PCPs are extremely sensitive to electron beam imaging and agglomeration of nanoparticles may occur. Confocal laser scanning microscopy (CLSM) to verify the presence of face-selective monolayer growth of BODIPY (boron dipyrromethene)carboxylate shell on [Zn2(BDC)2(DABCO)] or Zn-JAST-1 (Figure 6).72

Review

Hybridization oers a powerful method to enhance gas adsorption selectivity/amounts from the existing library of PCPs. An early example of IML-PCP was published with JAST structure [Zn2(BDC)2(TMDC)(DABCO)] 17 (H2TMDC = 2,3,5,6-tetramethyl-1,4-dicarboxylic acid) via direct synthesis, for investigation of its hydrogen uptake.14e The IML-PCP had a slightly higher hydrogen uptake (20.8 mg/g) at 77 K compared to its end members Zn-JAST-1 (20.1 mg/g) or [Zn2(TMBDC)2(DABCO)](18.5 mg/g). This is probably due to ne turning of pore apertures as Zn-JAST-1 has larger pore apertures (7.5 ) than [Zn2(TMDC)2(DABCO)] (narrowest portion over 3 ).

In an exhaustive study, 18 dierent MOF-5 derivatives, termed multivariate (MTV) frameworks were synthesized using a combination of terepthalate linkers with dierent functionalities attached to 2-position or 2,5-positions on the same zinc framework. 19 Up to 8 di erent linkers with dierent functionalities can be incorporated into a single framework. The isotherms demonstrate that the uptake capacity of [Zn4O(BDC)1.52(L4)0.73(L5)0.75] 18 or MTV-MOF-5-AHI for H2 at 77 K is greater than that of [Zn4O(BDC)2.04(L4)0.96] 19 or MTV-MOF-5-AH, [Zn4O(BDC)2.13(L5)0.87] 20 or MTVMOF-5-AI, and MOF-5 by a maximum of 84% (Figure 7). For
Figure 6. Representations of surface-modied crystals (left), CLSM images (middle), and transmission images (right) (a) c-axis orientation and (b) a-axis orientation. Reprinted with permission from ref 72. Copyright 2010 Wiley VCH.

Class III. For guests that are accommodated in the pores of the PCP, the main thrust of characterization is to prove that all guests are inside the pores and negligible amounts of guests are left outside/on the surface of the PCP. From SEM, the presence of guest agglomerates can be observed. If guests are inside the pores, the N2 BET surface area should be greatly reduced compared to the pristine PCP. In addition, as the guest is trapped inside the pores and interacting with the walls of the PCP, the thermal characteristics of the guests are markedly dierent. In the Zn-JAST-1PEO 15 (PEO = polyethylene glycol) hybrid, the glass transition temperature of the polymeric guest is dramatically dierent from bulk depending on the pore size, chemistry and molecule weight.42 2D solid state NMR was used in the Zn-JAST-1PSt 16 (PSt = polystyrene) to prove unambiguously that intermolecular correlations exists between the single chain PSt guest and PCP host, thus demonstrating successful accommodation of the guest molecule in the PCP.49

Figure 7. Hydrogen uptake at 77 K of MOF-5 and MTV-MOF-5-(AI, AH, AHI). From ref 19. Reprinted with permission from AAAS. (right) Crystal structure of MOF-5 with emphasis on the Zn4O tetrahedra (blue). Carbon atoms are represented by gray spheres; oxygen atoms represented by red spheres. Hydrogen atoms are omitted for clarity.

TYPES OF FUNCTIONS Gas Adsorption, Separation, and Storage. Because of their porosity, the most prominent property of PCPs investigated is undoubtedly their gas adsorption behavior. Since the discovery of PCPs being able to store gases which can be used for alternative energy purposes such as methane,50 gas storage in PCP has been a heavily researched topic.
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selectivity of CO2 over CO at 298 K, 400% better selectivity was observed in the case for [Zn4O(BDCNO2)1.19(L4)1.07(L5)0.74] 21 compared with MOF-5. This shows that the performance of some MTV-MOF-5 derivatives is more than a linear combination of its constituents. The authors hypothesized that this may be due to the synergistic interactions between proximal functional groups or formation of nanodomains which may be benecial for gas adsorption. Another utility of the formation of IML-PCPs, namely, the stabilization of the evacuated framework was recently demonstrated. [Zr6O4(OH)4(HSO3-BDC)6] or UiO-66-SO3H is not stable to evacuation but [Zr6O4(OH)4(BDC)6] is, thus by mixing the two ligands during synthesis aords the series [Zr6O4(OH)4{(HSO3-BDC)x(BDC)1x}6]. At x = 0.18, the
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Chemistry of Materials resultant IML-PCP 11a was robust to evacuation with incorporation of the sulfonate group. 11a compared to its parent UiO-66 had higher initial heats of adsorption for CO2.46 The gate opening phenomena refers to the abrupt increase in gas adsorption of PCP upon achievement of a certain gate opening pressure (Pgo), this is correlated to a structural transition occurring. As the amount of gas adsorption is negligible before the gate opening pressure, these soft PCPs are ideal for selective gas capture with low energy penalty for release.51 Fine tuning the Pgo is thus of importance both for fundamental research and industrial applications. One way of achieving this is via IMM/IML-PCPs. By using an IML-PCP, [Cu(bpy)(BF4)(CF3BF3)] 22 or ELM-12/13, its gate pressure is lower than that of its end members, [Cu(bpy)(CF3SO3)2] (ELM-12) and [Cu(bpy)(CF3BF3)2] (ELM-13).52 Zn-CID-5 or [Zn(5-NO2-ip)(bpy)] exhibits gate opening behavior whereas Zn-CID-6 or [Zn(5OMe-ip)(bpy)] (5-OMe-ip = 5-OMe-isophtalate) does not. By formation of solid solution Zn-CID-5/6 or [Zn(5-NO2ip)1x(5-OMe-ip)x(bpy)] 23 with 0.13 x 0.92, the Pgo of carbon dioxide and water can be tuned. Separation of CO2 from CO2/CH4 mixture (1:1) under breakthrough conditions at 273 K with good capacity is achieved using the x = 0.13 member because of the combination of the properties of CID-5 (selective gas adsorption for CO2) and CID-6 (high capacity for gases). The same principle was utilized for CH4/ C2H6 separations as well. In this case, C2H6 can be selectively separated from a 9:1 (v/v) mixture under breakthrough conditions at 273 K using the x = 0.1 member.53 [2 + 2]-Cycloaddtion reaction is a useful method for tuning of surface properties.54 UV irradiation of [Zn2(5-OMeisop)2(bpe)] (bpe = 1,2-bis(4-pyridyl)ethylene) occurred in a single-crystal to single-crystal fashion (Figure 8), coupling between adjacent pillar bpe pillars, and giving not only a perfect converted product but also partially converted PCP characterized as an IML-PCP 24. The converted PCP had a smaller

Review

channel compared to that of the original compound, resulting in change in sorption behavior. IML-PCPs of [Zn{(mtz)x(mim)1x}2] 25 (Hmim = 2methylimidazole, Hmtz = 3-methyl-1,2,4-triazole) with sodalite topology can be synthesized for x = 0, 0.23, 0.49, 0.76, 1.0 by direct synthesis.55 Because of the dierence between hydrophobic [Zn(mIm)2] (MAF-4 or ZIF-8) and hydrophilic [Zn(mtz)2] (MAF-7), the gate opening pressure for water adsorption of the resultant mixed PCPs can be systematically turned from p/p0 = 0.33, 0.43, and 0.63 for x = 0.23, 0.49, and 0.76 (Figure 9). No hysteretic behavior was also observed in the water adsorption for the mixed members, compared to pure MAF-7.

Figure 9. Water adsorption isotherms at 298 K for [Zn{(mtz)x(mim)1x}2] for x = 0.0 (1), 0.23, (2) 0.49(3), 0.76 (4), 1.0 (5). Reprinted with permission from ref 55. Copyright 2011 Wiley VCH. (right) Crystal structures of MAF-4 and MAF-7. Zinc atoms are represented by blue spheres, carbon atoms are represented by gray spheres, nitrogen atoms are represented by brown spheres and oxygen atoms represented by red spheres. Hydrogen atoms are omitted for clarity.

Figure 8. Change of pore interior in PCP via [2 + 2] cyloaddition. From ref 54, reproduced by permission of The Royal Society of Chemistry.
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For IMM-PCPs, Co-doped MOF-5 [(Zn 1 x Co x ) 4 O(BDC)3(DEF)2x] 26 for x 1 can be synthesized via direct synthesis.56 At maximum doping level, only one of the Zn atoms in the Zn4O cluster can be substituted for Co. The Co ion is incorporated into the cluster in an octahedral geometry with two coordinated DEF molecules but changes its geometry to tetrahedral upon evacuation as manifested by a dramatic color change from pink to blue. The resultant IMM-PCP had higher adsorption capacity for H2 (7.4% more) than MOF-5 at 77 K at a pressure of 10 bar. [Cr0.6Fe0.4(OH)0.7F0.3(BDC)]57 or (Cr,Fe)-MIL-53 27 and demonstrated from high pressure CO2 adsorption isotherms that the NP to LP transformation occurs at a pressure (10 bar at 283 K) intermediate between the pure Cr-MIL-53 (3 bar)58 and pure Fe-MIL-5359 (>20 bar) solid (Figure 10). Thus, in terms of ease of pore opening behavior, the mixed phase is intermediate between the pure Cr and Fe solids. As a consequence, the control of the metal ratio in mixed-cation MIL-53 materials might appear as a promising method to rationally ne-tune the sorption behavior. Several postsynthetically modied PCPs were examined for hydrogen uptake at 77 K.60 It was found that IRMOF-3 PCPs modied with amide/urea linkages had increased hydrogen uptake capacity and heat of adsorption compared to unmodied IRMOF-3. For example, with 63% converted
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Figure 10. (left) High pressure CO2 isotherms of Fe-MIL-53, Cr-MIL53, Cr0.6Fe0.4-MIL-53 27 and calculated isotherm for a mixture of FeMIL-53 and Cr-MIL-53. From ref 57, reproduced by permission of The Royal Society of Chemistry (right) Crystal structure of assynthesized Cr-MIL-53 and Fe-MIL-53 with emphasis on the CrO6 (green) and FeO6 (yellow) octahedra. Hydrogen atoms are omitted for clarity.

IRMOF-3-AMPh [Zn4O{(BDC-NH2)0.37(BDCNHCOPh)0.63}3] 28 the hydrogen uptake increased from 1.51 to 1.69 wt % and the heat increased from 5.3 to 7.0 kJ/ mol. The enhancement of H2 uptake by these modied MOFs is probably due to specic interaction of H2 molecules with additional phenyl groups. Ti-substituted members of UIO-66 or [Zr6(1x)Ti6xO4(OH)4(BDC)6] 29 (x = 0.32, 0.44, 0.56) had enhanced CO2 storage properties such as greater capacity (enhancement of 81%), larger heats (enhancement of 10 kJ/ mol across all loadings); larger surface area (1844 vs 1390 m2/ g) compared to native UIO-66.61 The authors attribute this to smaller pore size arising from exchange to a smaller cation, and greater charge transfer for metal center to ligand. The formation of either coreshell PCP or IMM-PCP for the same system may be feasible, via exquisite control of the kinetics of formation of the PCPs. Due to the dierence in kinetics of formation of Zn-CID-5 and Mn-CID-5, in a one pot system with reactants Zn(ClO4)2, Mn(ClO4)2, 5-NO2-isophtalic acid, and 4,4-bipyridine, coreshell PCP 7 was formed due to the dierent nucleation speeds of each framework. In contrast, using the sodium salt 5-NO2-isophtalate as a precursor, both metals reacted simultaneously to form a solid solution framework Zn/MnCID-5 or [Zn1xMnx(NO2-ip)(bpy)] 30. For methanol adsorption, the members of 30 had intermediate values for their total uptake with a value dependent on metal ratio. Interestingly, for coreshell PCPs, anomalous sorption behavior was exhibited, which cannot be explained by a simple law of mixtures between the two pure end members. The phase-separated type frameworks exhibited a constant uptake of 2.5 molecules/unit cell, independent of the metal ratio in the framework. In addition, the coreshell type frameworks exhibited an anomalous gate-opening behavior with the Pgo higher than the solid-solution type frameworks and the end members. The authors attribute these behaviors to the coupling between the Zn and Mn interfaces in the coreshell structure. Mg nanocrystals (NC) were accommodated in a PCP, SNU90 or [Zn4O(ATB)2] (H3ATB = aniline-2,4,6-tribenzoic acid) via chemical vapor deposition of bis(cyclopentadienyl) magnesium (MgCp2) precursor, and demonstrated the resultant Mg NCs@SNU-90 31 hybrid is an eective hybridized hydrogen-storage material. It has both physical
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adsorption and chemisorption properties, and exhibits synergistic e ects with increased isosteric heat of the H 2 physisorption62 (Qst = 11.4 vs 4.55 kJmol1 of unhybridized SNU-90). Inorganic hydrides such as NH3BH3 (amine borane, AB), LiBH4, Mg(BH4)2 and NaAlH4 are potentially useful as solidstate hydrogen carriers for automobile and on-site hydrogen delivery applications.63 However, they suer from sluggish dehydrogenation kinetics <100 C and byproduct(s) formation. There has been considerable body of work done on encapsulation these hydrides into the pores of PCPs such as ZIF-8,64 Mg-MOF-74,65 Fe-MIL-53,66 and Cr-MIL-101.67 The results show that the kinetics of dehydrogenation and byproduct formation is greatly reduced, probably due to nanoscale con nement of the hydrides and favorable interactions with the PCP pore surface. For example, the decomposition temperature for the hydride in Cu-HKUST1NaAlH4 32 is 100 C lower than bulk NaAlH4.68 Luminescence. Because of their strong emission in the visible regime, Eu2+/3+ and Tb3+ are commonly used lanthanide metals in PCPs for luminescent applications. For example, in [EuxIn1x(BTB)2/3(C2O4)3/2] 33, where x = 0.024, 0.049, 0.09 (H3BTB = benzene-1,3,5-trisbenzoic acid) the incorporation of red-emitting Eu3+ at x = 0.09 improved the intrinsic broad-band direct white emission, suitable for solid-state lighting purposes.69 In another example, the IMM-PCP concept was used creatively for synthesizing luminescent thermometers.70 The IMM-PCP [Eu0.0069Tb0.9931(DMBDC)] 34 (H2DMBDC = 2,5-dimethoxy-1,4-benzenedicarboxylic acid) based on two visible light emissive lanthanide ions, Tb3+ (ex = 545 nm) and Eu3+ at (ex = 613 nm) exhibits temperature dependent emission changing from the green-yellow to red from 10 to 300 K (Figure 11). This temperature dependence is linear over 10 200 K, suggesting applications as a self-referencing luminescent thermometer.

Figure 11. (a) Photograph of luminescent 33 at 10 K (left) and 300 K (right), excitation at 312 nm. Reprinted with permission from ref 70. Copyright 2012 American Chemical Society.

Uncommon NIR emission with IMM-PCP ErxYb1x-PVDC 35 (x = 0.32, 0.58, 0.70, 0.81) was demonstrated by using a carefully designed antenna ligand, H2PVDC, L6. Excitation at a single wavelength (370 or 470 nm) produced concurrent Yb3+ and Er3+ emission bands that are linearly correlated to the lanthanide metal ratio.71 This suggests the potential application of these IMM-PCPs as luminescent barcoded materials for use in as labels in multiplexed bioanalytical assays and as encryption tags. Nonemitting PCPs can be decorated with a shell monolayer of uorescent BODIPY dye (monocarboxylate terminated) via ligand exchange to render the composite emitting.72 This concept was demonstrated for two frameworks, that is, ZnJAST-1 and Cu-HKUST-1. Using confocal microscopy, they
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demonstrated that only the carboxylate terminated {100} faces of the modied Zn-JAST-1 36 are selectively decorated, in contrast for modied Cu-HKUST-1 37 no face-selective decoration is present as all faces are carboxylate terminated. If the PCP is not luminescent, strongly emitting inorganic nanomaterials or organic moieties can be accommodated via hybridization. Nanoparticles can be incorporated into MOF-5 via micrometer-sized -hopeite or DRM (Desert Rose Material) akes which forms when surfactant F127 is added into the MOF-5 growth solution, i.e. NPs@DRM@MOF-5 38.73 The function of DRM akes is to serve as heterogeneous nucleation seeds for MOF-5 single crystals. This allows seeding of MOF-5 growth on any substrate and the spatial control of growth as well. Metallic (Pt and Pd), polymeric (PTFE) and semiconducting (CdSe-CdS-ZnS quantum dots) nanoparticles were successfully incorporated into MOF-5 via DRM method. As proof of the functionality of the hybrid PCP, the quenching of CdSe-CdS-ZnS coreshell QDs emitting at 576 nm could be controlled in the hybrid PCP depending on the size of the thiols employed. This is due to the MOF-5 shell acting as a size-selective sieve. Well-de ned NPs@ZIF-8 hybrids 39 can be easily synthesized via room temperature stirring of nanoparticles, zinc precursor and 2-methylimidazole ligand.74 This versatile method is able to encapsulate nanoparticles of various shape, sizes, and compositions such as Pt, CdTe, Fe3O4, and lanthanide-doped NaYF4, and Ag nanocubes. As a result, depending on the type of nanoparticle, various functions (catalytic, optical, magnetism) can be introduced into the hybridized material. The key to this strategy is decoration of the nanoparticle surface with poly(vinylpyrrolidone) (PVP), whereupon it chelates with Zn2+ ions of the PCP. By merely controlling the time of addition of the nanoparticles, the distribution of nanoparticles inside the PCP can be regulated. The hybrid material demonstrated unprecedented absolute regioselectivity in hydrogenation reactions such as the hydrogenation of n-hexene over trans-2-hexene for Pt@ZIF-8 39a. Size selectivity was also demonstrated as octene was not hydrogenated, suggesting that no free Pt nanoparticles were present on the exterior and the PCP shell was acting as a sizeselective molecular sieve. A hybrid PCP, Zn-JAST-1distyrylbenzene (DSB) selectively adsorbed CO2 over other atmospheric gases with concomitant structural change of the framework (Figure 12).41 This structural change induced conformational variations of the accommodated DSB which caused a critical change of DSB uorescence at a specic threshold pressure. Thus the ZnJAST-1DSB composite 40 is intelligent and the hostguest coupled transformations converts gas adsorption events into easily detectable output signals. Catalysis. Becasue of their rich chemistry, well-dened and regular pores, PCPs are uniquely suitable for catalysis.5 Hybrid PCPs can extend this capability further by incorporation of catalytically active ligands, accommodation of nanoparticles, and encapsulation of catalytic complexes/biomolecules in the cavities of PCPs.
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Figure 12. Brief schematic of the introduction of reporter molecule DSB into the pores of Zn-JAST-1 causing transformation to Zn-JAST1(1in gure). The introduction of CO2 induces structural change back to Zn-JAST-1 (1 in gure) with corresponding uorescence change at 195 K. Reprinted by permission from Macmillan Publishers Ltd.: Nature Materials, ref 41, copyright 2011.

Postsynthesis on ZIF-8 was applied to target the highly porous sodalite topology using imidazole (Im) as ligand.75 SALEM-2 or [Zn(mIm)0.3(Im)1.7)] 41 is highly porous and shows remarkable water stability in boiling water. Upon treatment with n-butyllithium, it exhibits Brnsted base catalysis as exemplied by the conjugate addition of methanol or benzyl alcohol to the ,-unsaturated ketone, 4-hex-en-3one. The parent ZIF-8 in contrast, is noncatalytic in nature. In addition, SALEM-2 could incorporate toluene and cyclohexane compared to ZIF-8 because of widening of pore apertures. In a comprehensive study, six dierent IML-PCPs based on UiO-67 structure type, [Zr6O4(OH)4{(BPDC)1x(L712)x}6] 42 (H2BPDC = 4,4-biphenyldicarboxylic acid) were synthesized for photocatalytic reactions. The ligands employed were H2BPDC and catalytically active Ir, Re, and Ru complexes with dicarboxylic acids.76 Approximately 28 wt % of functional ligands can be incorporated. With IML-PCPs constructed with ligands such as H2L7 42a, H2L8 42b, and H2L9 42c, the resultant PCPs were eective water oxidation catalysts. The H2L10 functionalized IML-PCP 42d served as an active catalyst for photocatalytic CO2 reduction with a total turnover number (TON) of 10.9, three times higher than that of the corresponding homogeneous complex. IML-PCPs based on H2L11 42e and H2L12 42f were used in three photocatalytic organic transformations (aza-Henry reaction, aerobic amine coupling, and aerobic oxidation of thioanisole) with high activities.

In nanoparticle catalysis, controlling the sintering and aggregration of metal nanoparticles is essential in maintaining high selectivity and activity. By encapsulating the nanoparticles with PCPs, aggregration is curbed. If the coating is free of defects, size selectivity can occur due to the well-dened pore size of the PCP acting as molecular sieve. Because of its high porosity, MOF-5 was utilized as a host framework to support Au, Cu, Pd nanoparticles.77 The
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Chemistry of Materials nanoparticles were synthesized via vacuum inltration of volatile metal precursors such as [(CH3)Au(PMe3)],[(5C5H5)Cu(PMe3)] and [(5-C5H5)Pd(3-C3H5)] into the pores of MOF-5 followed by reduction in hydrogen. The Cu@MOF-5 hybrid 43a could produce methanol from syn gas at 220 C with good activity. This is surprisingly considering the absence of Zn2+ or ZnOx. The authors speculate that the MOF-5 framework itself might be contributing to the catalysis. Pd@MOF-5 43b was a moderately active catalyst for the hydrogenation of cyclooctene. Interestingly, Au@MOF-5 43c was inactive for CO oxidation, a typical reaction observed for Au nanoparticles. Au@ZIF-8 44 for CO oxidation was synthesized by solidstate grinding of (CH3)2Au(acac) gold precursor78 with ZIF-8, followed by reduction of the precursor to Au nanoparticles.79 The amount of Au loading could reach up to 5 wt % of PCP. Due to ZIF-8 being a con nement medium, the Au nanoparticles are close to monodisperse (3 nm) and no signicant change in size because of sintering was observed, even after multiple runs at 340 C with preservation of catalytic activity. Pd@ZIF-8 45 coreshell hybridized PCP was obtained via Cu2O as a sacricial template to obtain yolk-shell architectures (Figure 13).80 The nanostructures were applied as catalysts for

Review

In a systematic work, six isomorphous PCPs having HKUST-1 structure type but with dierent Keggin POMs encapsulated were synthesized via hydrothermal synthesis: [Cu2(BTC)4/3(H2O)2]6[POM](TMA)2 47 (TMA = trimethyl ammonium cation, POM = [H2SiW12O40]2, [H2GeW12O40]2, [HPW12O40]2, [H2SiMo12O40]2, [HPMo12O40]2, and [HAsMo12O40]2) or NEU-n (n = 16).82 The presence of the polyoxometallate was veried by single crystal crystallography. The hydrolysis of esters was examined for POM = [HPW12O40]2, and high catalytic activity was demonstrated and the composite could be recycled at least 15 times. No leaching of the POM and decomposition of the framework was observed after catalytic reactions. In a related work, a related POM, K5CuPW11O39 was encapsulated into Cu-HKUST-1 or MOF-199 to aord [Cu3(BTC)2]4[{(TMA)}4CuPW11O39H] 48.83 The resulting PCP was catalytically active in air, breaking down sulfur-based toxic industrial chemicals to harmless products (Figure 14).

Figure 14. Schematic showing the conversion of sulfur-based toxic industrial chemicals to harmless products in air via 48. Reprinted with permission from ref 83. Copyright 2011 American Chemical Society. Figure 13. Formation of yolkshell Pd@ZIF-8 structure. Reprinted with permission from ref 80. Copyright 2012 American Chemical Society.

the gas phase hydrogenations of ethylene, cyclohexene, and cyclooctene. The ZIF-8 shell showed interesting size selectivity in ethylene hydrogenation versus cyclooctene hydrogenation. For cyclohexene hydrogenation, the measured activation energy for the yolkshell nanostructure was dierent from that for the coreshell nanostructure, which demonstrates the inuence of the cavity structure in the yolkshell structure. A bottom up approach to the synthesis of Pd@MIL-101 hybrids 46 was adopted by grafting ethylenediamine (ED) onto the open metal sites of MIL-101, followed by deposition of [PdCl4]2, [PtCl6]2, or [AuCl4] precursors and reduction using NaBH4.81 TEM showed that the nanoparticles are in the range of 24 nm, similar to cage diameters, although some nanoparticles were observed on the surface of the PCP. The activity of 46 was comparable to commercial Pd/C catalyst (1.09 wt % Pd) after a certain induction period (0.51 h), probably owing to diusion constraints. Polyoxometallates clusters such as phosphotungstic acid or H3PW12O40 are excellent solid acids for catalysis but are inherently constrained by their low surface areas (<10 m2/g). In addition, due to their solubility in water, the immobilization on a suitable solid support such as in the cavity of a PCP will be extremely useful for its applications in heterogeneous catalysis.
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The POM or the MOF by itself is catalytically slow or inactive, thus 48 is an excellent example of a hybrid PCP exhibiting synergistic properties. The authors postulate that POM activation by encapsulation in the MOF likely involves electrostatic interactions between the two components resulting in a higher reduction potential of the POM. Porphyrins and enzymes are active molecular species for catalysis, but for their widespread use, their stability and recyclability needs to be improved. The encapsulation of these species in the well-dened cavities of PCPs84 demonstrate remarkable enhancement in stability and activity and recovery of the hybrid is extremely easy via ltration. Metalloporphyrins such as (either Fe(III) tetrakis(4-sulphonatophenyl)porphyrin, Fe4SP, or Mn(III) tetrakis(sulphonatophenyl)porphyrin, Mn4SP) into the octahemioctahedral pores of Cu-HKUST-1 49a,b in well-dened orientations for monooxygenation of organic substrates with activity reminiscent of biological heme enzymes. Compare to the free porphyrin, the hybrid (MOMzyme) had successive turnovers without signicant reduction in catalytic activity.85 An enzyme, microperoxidase-11 (MP-11) was accommodated into a mesoporous MOF to aord [Tb(TATB)]MP-11 50 (H3TATB = triazine-1,3,5tribenzoic acid),86 and it was used for oxidation of 3,5-di-tbutylcatechol to o-quinone, and observed that this hybrid out performed mesoporous silica MCM-41 hybrid.87 Drug Delivery. Given their inherent tunability, large void volumes, surface areas and nontoxicity if judicious choice is
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Chemistry of Materials made of metals and ligands, PCPs are highly suitable for drug delivery.3 The simplest method to achieve this goal is to encapsulate drugs in the pores/cavities of PCPs. In a groundbreaking study, the use of MIL-100 and MIL-101ibuprofen 51 for drug delivery was explored. It was demonstrated that loading can reached the unprecedented level of 1.4 g/g PCP of ibuprofen for MIL-101 with favorable delivery period under physiological conditions.88 In another study by the same group, exible frameworks such as Fe-MIL-53 and Cr-MIL-53 were used.89 Predictable zero-order kinetics was obtained and complete delivery of ibuprofen for both Fe,Cr-MIL-53 52 a,b took up to 3 weeks, which highlight the utility of exible hybrid solids for adaptation of pore opening to optimize drug-matrix interactions. For in vivo applications in drug delivery, the PCP particles should be nanosized and constructed with a nontoxic metal. In an exhaustive work, the authors demonstrate the synthesis of nontoxic and biocompatible nanosized Fe MOFs (MIL-89, MIL-88A, MIL-100, MIL-101-NH2, and MIL-53) in ethanol.90 The encapsulation and progressive release of drugs of dierent polarities, sizes and functional groups, such as busulfan, azidothymidine triphosphate, cidofovir, and doxorubicin were also demonstrated. It is noted that the encapsulated drug molecule does not necessarily need to be neutral. Sometimes, the desired pharmaceutical cargo is present as a hydrochloride salt. A negatively charged PCP, bio-MOF-1 or [2Me 2 NH 2 ][Zn8(Ad)4(BPDC)6O] (HAd = adenine; H2BPDC = 4,4biphenyldicarboxylic acid) was employed to accommodate procainamide HCl, an antiarrythmia drug via cation exchange.91 Bio-MOF-1procainamide HCl 53 can release the drug in PBS buer in a controlled fashion (72 h for quantitative release) via cation exchange with Na+ present in the buer. In contrast, when the PCP is placed in distilled water, only 20% release was observed. A variety of strategies discussed in this review was employed for loading nanosized Fe-MIL-101 with an anticancer drug (cisplatin derivative ESCP) or an optical contrast agent (BODIPY dye) (Figure 15).92 First, an IMM-PCP was synthesized with FeCl3, H2BDC and H2BDC-NH2 using microwave techniques. First, an IMM-PCP was synthesized with FeCl3, H2BDC and

Review

Figure 15. Synthetic scheme for obtaining 54b@SiO2 (1c@SiO2 in gure) or 54c@SiO2 (1c@SiO2 in gure). Reprinted with permission from ref 92. Copyright 2009 American Chemical Society.
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H2BDC-NH2 using microwave techniques. NMR of the digested sample veried that the composition was [Fe3(O)Cl(H2O)2{ (BDC)0.83(BDC-NH2)0.17}] 3 54a. It is noted that the pure amino functionalized PCP could not be synthesized under the same conditions. Subsequently, the cargo, either a derivative of cis-platin or BODIPY was attached postsynthetically via amine linkages to aord 54b, 54c. This functionalized IMMPCP was then covered with a thin shell of silica to form a core shell PCP, that is, 54b@SiO2 or 54c@SiO2 to retard the rate of release of cargo for biological applications. Thus these PCP nanomaterials employed the mixed ligand approach, postsynthesis and coreshell modication, a scientic tour de force indeed. Superparamagnetic particles can be encapsulated into PCPs such as Fe3O4@DUT-4 55a, DUT-4 = [Al(OH)(2,6-ndc)], Fe3O4@DUT-5 55b, DUT-5 = [Al(OH)(BPDC)], and Fe3O4@Cu-HKUST-1 55c.93 The amount of maghemite Fe2O3 particles (1020 nm) in the composites can be adjusted by using dierent volumes of magnetite dispersion and range between 5 and 15 wt %. The composites are still porous with minimal loss of surface area and can be loaded with ibuprofen to aord Fe3O4@PCPiburpofen 55d hybrids. The authors exploited the heating of magnetic nanoparticles in an AC eld and demonstrated that the encapsulated ibuprofen can be released with an alternating magnetic eld. Photoinduced gas release shown above38 is one of the promising methodologies for drag delivery. Photothermal delivery of anthracene via near-IR irradiation was achieved by obtaining a coating of [Al(OH)(1,4-NDC)]94 selectively around single Au nanorods (GNR) to aord a GNR@[Al(OH)(1,4-ndc)]anthracene composite 56.95 The synthesis of the [Al(OH)(1,4-ndc)] coating is only possible via the transformation of an aluminum oxide coating on the PCP via the coordination-replication96 method. Au NRs were chosen because of the presence of a length tunable longitudinal plasmon band in the near IR window. The successful incorporation of the composite into biocompatible polymethylglutarimide (PMGI) nanobers was demonstrated as well. Transport. The transport properties (ions/holes/electrons) of PCPs and their hybrids is an emerging area of research.7 Present work is currently focused on ionic conductivity. IMLPCP [(Na3L1)0.66(Na3H3L2)0.34(H2O)0.75] 5797 (Na3L14 = trisodium 2,4,6-trihydroxy-1,3,5-trisulfonate benzene and H6L15 = 1,3,5-benzenetriphosphonic acid) was synthesized with the rationale of proton doping. It is hypothesized if isovalent substitution has occurred, a free proton will be present in the dopant hydrogen phosphonate group, that is, [PO2(OH)] compared to the original sulfonate group [SO 3], thus the nal hybrid will possess a higher conductivity. 57 had an ionic conductivity 1.5 times higher than its undoped member, with a value of 2.1 102 S cm1 (85 C, 90% RH). The high chain mobility (depression of melting point, Tm) of encapsulated PEG in Zn-JAST-142 was exploited into the arena of lithium conductivity (Figure 16). LiBF4 was complexed onto polyethylene glycol and the PEG-complex was subsequently encapsulated to form Zn-JAST-1PEG(LiBF4) 58. The Li+ ions in the resultant composite was shown via solid state 7Li NMR to be highly mobile (liquid-like) with an activation energy, Ea of 0.18 eV.98 In another work, photoconductive polymer, poly(N-vinylcarbazole) (PVCz) was introduced into the pores of [La(BTB)] (H3 BTB = 1,3,5-benzene-trisbenzoic acid) via
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Figure 16. Schematic of hybrid formed by accommodation of PEG and LiBF4 in channels of Zn-JAST-1 (1 in gure). (right) 7Li solidstate NMR of hybrid 60. From ref 98, reproduced by permission of The Royal Society of Chemistry.

polymerization of the inltrated monomer to form [La(BTB)]PVCz 59.99 It was shown by uorescence and excitation spectroscopy that due to pore connement eect, the side carbazolyl groups of the conned PVCz are eectively -stacked. This ideal conformation of PVCz chains contributed to a drastic increase in hole mobility, which was 5 orders of magnitude higher than that in the bulk state. Imidazole was accommodated into the pores of [Al(OH)(NDC)] and [Al(OH)(BDC)] for applications in anhydrous proton conductivity.100 It was demonstrated that although both PCPs can be inltrated with Im as guests, the pore environment has a direct role in the conductivity obtained, with proton conductivities at 120 C of 2.2 105 Scm1 for [Al(OH)(ndc)]Im 60 and 1.0 107 Scm1 for [Al(OH)(bdc)]Im 61. In a subsequent work,43 the guest was changed from Im to histamine (His) and the resultant [Al(OH)(bdc)]His 62 hybrid had a conductivity of 1.7 103 S cm1 at 150 C (Figure 17). This large increase in conductivity was attributed to the higher thermal stability, greater packing density, and the presence of intramolecular proton exchange in histamine.

synergistic interactions between components in hybrid PCPs. For class I hybrids, it is anticipated that more exotic, functional ligands will be synthesized and be incorporated in known structure types (i.e., MOF-5, UiO-66) for other applications beyond gas storage. For Class II hybrids, more work has to be performed on understanding the role of interfaces in coreshell crystals for modulation of physical properties. Because of the presence of interfaces, it is postulated that are many interesting discoveries to be uncovered in the area of coreshell PCPs For Class III hybrids, highly specialized guests such as enzymes and functional complexes will be placed inside the pores to perform various functions with high specicity and activity. For example, very recently, phosphine complexes and hemicyanine chormophores have been ion-exchanged into {(Me2NH2)3(In3(BTB)4)} or ZJU-28 for catalysis101 and nonlinear optical behavior,102 respectively. It can be predicted with certainty that the functions of hybrid PCPs will be increasingly more diverse and sophisticated. They are also anticipated to render important contributions to our current environmental challenges, such as carbon dioxide capture/ conversion,103 solar energy harvesting,104 and water purication.105

AUTHOR INFORMATION

Corresponding Authors

*E-mail: ryotaro.matsuda@gmail.com. *E-mail: kitagawa@sbchem.kyoto-u.ac.jp.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS This work was supported by Japan Science and Technology Agencys ERATO (Exploratory Research for Advanced Technology) program , by JSPS KAKENHI Grant Number 25620187 and 25870360, and by a Grant-in-Aid from the Ministry of Education, Culture, Sport (MEXT). The authors would like to thank the past, present technicians, undergraduate/graduate students, post-doctoral fellows, visitors and sta of the Kitagawa Laboratory who have contributed much to the work mentioned in this review. The aid of Tomohiro Fukushima for illustration of gures is much appreciated.
(1) (a) Kitagawa, S.; Kitaura, R.; Noro, S.-I. Angew. Chem., Int. Ed. 2004, 43, 2334. (b) Yaghi, O. M.; OKeeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature 2003, 423, 705. (2) (a) Li, J.-R.; Sculley, J.; Zhou, H.-C. Chem. Rev. 2012, 112, 869. (b) Ma, S.; Zhou, H.-C. Chem. Commun. 2010, 46, 44. (c) Sculley, J.; Yuan, D.; Zhou, H.-C. Energy Environ. Sci. 2011, 4, 2721. (d) Murray, L. J.; Dinca, M.; Long, J. R. Chem. Soc. Rev. 2009, 38, 1294. (e) Rowsell, J. L. C.; Yaghi, O. M. Angew. Chem., Int. Ed. 2005, 44, 4670. (3) (a) Huxford, R. C.; Della Rocca, J.; Lin, W. B. Curr. Opin. Chem. Biol. 2010, 14, 262. (b) Della Rocca, J.; Liu, D. M.; Lin, W. B. Acc. Chem. Res. 2011, 44, 957. (c) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Ferey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232. (4) (a) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450. (b) Farrusseng, D.; Aguado, S.; Pinel, C. Angew Chem., Int. Ed. 2009, 48, 7502. (c) Corma, A.; Garca, H.; Llabres i Xamena, F. X. Chem. Rev. 2010, 110, 4606. (5) (a) Rocha, J.; Carlos, L. D.; Almeida Paz, F. A.; Ananias, D. Chem. Soc. Rev. 2011, 40, 926. (b) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. Chem. Soc. Rev. 2009, 38, 1330.
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REFERENCES

Figure 17. Accomodation of histamine in the channel of [Al(OH)(ndc)] resulting in a proton conductor 62.

CONCLUSIONS We have reviewed the current state of the art for functional hybridized PCP frameworks for the purpose of gas adsorption/ storage, luminescence, catalysis, drug delivery and transport. It is clear that with judicious choice of framework structure type, ligands, metals, or guests, hybridization allows the ne control of framework properties, and at times the hybrids display superior/radical new properties not found in an unhybridized framework. Clearly, much work remains to be done and surprises to be uncovered, especially on understanding

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