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This article was published as part of the

2009 Metal–organic frameworks issue
Reviewing the latest developments across the interdisciplinary area of metal–organic frameworks from an academic and industrial perspective
Guest Editors Jeffrey Long and Omar Yaghi

Please take a look at the issue 5 table of contents to access the other reviews.

Introduction Heterogeneous catalysis was one of the earliest proposed applications for crystalline metal–organic frameworks (MOF) materials.) that can be accomplished under milder conditions.e. Joseph T. ways. their catalytic niche may be high-value-added reactions (production of fine chemicals.2 A defining characteristic of functional MOF materials is porosity. Then he joined Rutgers. Third. 2145 Sheridan Road. 1. Hupp* Published on 17 March 2009. as well as for applications such as gas separations and gas storage.northwestern. separations and Fax: +1 847-467-1425.2 Although MOF-based catalysis was proposed nearly 20 years ago and experimentally demonstrated 15 years ago. (b) designed catalysis with framework nodes. First. Indeed. He carried out postdoctoral studies with Prof.. however. Northwestern University. Evanston. Nguyen and Joseph T. Los Angeles. they are extraordinarily robust and. JeongYong Lee received his BS (1994) and MS (1996) degrees in Chemistry from Yonsei University in Karl A. Second. where he earned his PhD under the supervision of Professor Jing Li. and early-on the analogy between MOFs and another class of catalytic porous materials.CRITICAL REVIEW www. they also differ in important Department of Chemistry. Discussed are examples of: (a) opportunistic catalysis with metal nodes. (d) catalysis by MOF-encapsulated molecular species. 2009. it may not be essential. For catalysis of condensed-phase reactions. and (f) catalysis by MOF-encapsulated clusters (66 references). E-mail: j-hupp@northwestern. Frederick Hawthorne.rsc. 1450–1459 Omar Farha is currently a Research Assistant Professor in the Chemistry Department at Northwestern University. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18. He was a National Science Foundation Fellow during his PhD studies.1039/b807080f A critical review of the emerging field of MOF-based catalysis is | Chemical Society Reviews View Article Online Metal–organic framework materials as catalystsw JeongYong Lee. This journal is c The Royal Society of Chemistry 2009 . He earned his PhD in Chemistry from the University of California. Hupp at Northwestern’s Institute for NanoOmar K. (c) catalysis by homogeneous catalysts incorporated as framework struts.chem. was noted.4 0 -bipyridine and cadmium nitrate) that likely would not have survived solvent removal. individual enantiomers. The uniformity of their pore and channel sizes accounts for much of their catalytic selectivity. USA. thereby facilitating their catalytic reactivity. Scheidt. (e) catalysis by metal-free organic struts or cavity modifiers. Tel: +1 847-491-3504 w Part of the metal–organic frameworks themed issue.. etc. Soc. Farha technology. Although crystalline MOFs share some of the catalytically relevant features of zeolites (large internal surface areas and uniform pore and cavity sizes). Their porosity yields internal surface areas that are relatively large. one of the earliest reported examples of MOF catalytic behavior (i. Zeolites. Rev. John Roberts. while many MOFs exhibit zeolite-like permanent microporosity.5—none approach the stability of zeolites. gas storage and gas separation. because they also contain organic components. His current research focuses on the rational design of metal–organic framework materials for catalysis. under the direction of Prof. Received 26th January 2009 First published as an Advance Article on the web 17th March 2009 DOI: 10. 38. Instead. The State University of New Jersey. Web: www. are among the most commercially important classes of catalyst. of course. 1450 | Chem. He carried out industrial research for six years as a materials scientist on Li-ion batteries in the R&D division at Samsung.1 as well as one of the earliest demonstrated applications. while many MOFs show good thermal stability—a few even showing stability to substantially above 500 1C4. This suggests that MOFs will likely not be competitive with zeolites as catalysts for reactions requiring forcing conditions. therefore well suited to catalysis under extreme conditions. cyanosilylation of various aldehydes) was based on a material (a 2D polymer of 4. Farha. Omar K. The persistence of microporosity after solvent evacuation is essential for gas-phase catalysis. MOFs can be synthesized in much greater chemical variety than zeolites. Illinois 60208-3113.3 As purely inorganic materials. SonBinh T. others collapse when solvent is removed. aluminosilicate zeolites. M. He is now a Postdoctoral Fellow in the Department of JeongYong Lee Chemistry at Northwestern University with Professor Joseph Hupp. His current research is focusing on metal–organic frameworks and their applications in catalysis. delicate molecules.

38 .13 the way forward—in view of (a). Hupp recently by awards from the Electrochemical Society. He did postdoctoral work at the University of North Carolina.6 framework-encapsulation of molecular catalysts. For the rest of this report. He is currently engaged in graduate research focusing on the incorporation of N-heterocyclic carbenes into metal–organic frameworks and coordination polymers and the catalytic applications of these materials. Prior to joining NU in 1986.12 Despite the many exciting and compelling recent developments. where he is now a Professor of Chemistry. an Alfred P. Chem. only recently has there been extensive experimental exploration. (b) metal coordination environments.6. Professor Scheidt’s contributions to the areas of carbene catalysis and synthesis have been recognized by awards from Abbott.6 framework-stabilization of otherwise short-lived catalysts. 2009. He also serves as an Associate Editor for J. Yet to be demonstrated. and the McCormick Professorship of Teaching Excellence. Ohio in 1984. Am. Sloan Fellowship. SonBinh SonBinh T. While zeolites have offered an interesting conceptual starting point.View Article Online Published on 17 March 2009. BoehringerIngelheim. for the most part. in our view the area of MOF-based catalysis is still in an immature phase. This journal is c Joseph Hupp holds a Morrison Professorship at Northwestern University where he serves as the chair of the University’s Department of Chemistry. that can be achieved in no other way. for example. Nguyen began his independent career at Northwestern. His research accomplishments have been recognized most Joseph T. He is also the recipient of an NSF CAREER award. With a significant amount of such chemistry now in place. is catalytic chemistry that fully exploits the remarkable features of MOFs to accomplish unique chemistry. and (c) reactivity-defining microenvironments that can be achieved in few other ways. he earned a BS degree from Houghton College and a PhD from Michigan State. however. Scheidt AstraZeneca. are: (a) useful multi-catalyst architectures that are very difficult to access otherwise. SonBinh Nguyen carried out research with Gregory Geoffroy at Penn State and in the groups of Henry Bryndza and Steve Ittel at duPont Central Research. Amgen. an American Cancer Society Scholar Award and a Distinguished Teaching Award from Northwestern University. In the fall of 2007. Soc. born in Cleveland. (b) and (c)—may instead be to think of catalytic MOFs as analogues of enzymes. His current research is focused on photochemical energy conversion and on the design and synthesis of functional molecule-derived materials.2. John Roberts His doctoral studies are currently supported by a Bordwell Fellowship from the NU Chemistry Department. the Inter-American Photochemical Society. GlaxoSmithKline and Novartis. post-synthesis incorporation of catalytic metal sites. Klotz Research Chair in Chemistry. Possible to envision. The reason for the long delay is clear: it has been necessary first to develop a substantial foundation of MOF synthetic chemistry. Karl A. Our decision here again reflects the relatively early John Roberts. Chem. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18.2. and the US Dept of Defense. 1450–1459 | 1451 The Royal Society of Chemistry 2009 . Soc. the Dow Chemical Company Research Professorship. We look forward to participating in the development of MOF catalytic chemistry along the lines of an ‘‘artificial enzyme’’ paradigm. After an NSF postdoctoral fellowship with Barry Sharpless at Scripps.9–11 and substrate-size-selective catalysis. with an eye more towards highlighting demonstrations of concepts rather than scopes of reactivity. He received a doctoral degree in Chemistry under Robert Grubbs and Nathan Lewis at Caltech where he was an NSF and NDSEG predoctoral fellow. 3M. During his undergraduate years. Professor Karl Scheidt received his PhD from Indiana University under the direction of Professor William R. it has proven possible for researchers in this area to envision a variety of catalysis ideas (strategies) that can be evaluated experimentally in rapid fashion. Among the now-demonstrated concepts are: heterogenization of welldefined homogeneous catalysts. but yet to be demonstrated. He holds the Directorship of the Integrated Science Program. and therefore reactivity. Roush and was an NIH Postdoctoral Fellow with Professor David Evans at Harvard University. Rev. received his bachelor’s degree at Michigan State University in 2007.1. He is currently an Associate Professor and holds the Irving M.9.7 coupling of catalysis to chemical separations. he joined the laboratory of Prof.8 demonstration of ‘‘adventitious’’ catalysis by nominally coordinatively saturated nodes (metal ions or clusters2). we have limited ourselves to surveying what has already been accomplished in MOF catalysis.. Karl Scheidt at Northwestern University.

and size-selectivity implies that the catalytic reactions are heterogeneous and are indeed occurring within the MOF. terminal ligands can present Lewis basic sites. but also MOFs possessing similar overall structures but lacking designed catalytic sites. the palladium centers in this MOF proved capable of catalyzing alcohol oxidation.34 Despite initial coordinative saturation. while for others the controls appear to be lacking. These are used in several instances below. have extended studies of ‘‘opportunistic’’ MOF-based catalysis to the archetypal cubic compound. 38.2 This investigation centered mainly on size. The porous-framework material [Cu3(btc)2(H2O)3]. Catalogued in Table 1 are the majority of the known catalytic MOFs.e. The observation of substrate shape.14 we have largely excluded them—except where they also serve to illustrate an idea not directly related to enantioselectivity. appropriate control experiments have been done. 2009. along with their abbreviations.g. Catalysis Only a few dozen reports of chemical catalysis by crystalline. Ravon et al. In contrast. If residual catalytic activity is detected with a nominally non-catalytic MOF. is non-selective as an alkylation catalyst. square-grid MOF containing single Pd(II) ions as nodes and 2-hydroxypyrimidinolates as struts. (bpy = bipyridine). which would certainly lead to destabilization and potential destruction of the original framework if all the Pd centers are catalytically active. At a minimum. i.4-dicarboxylate). yet it apparently catalyzes the Friedel–Crafts tert-butylation of both toluene and biphenyl (butylating agent = tert-butyl chloride). The catalytic activity of ‘‘MOF-5’’ in Friedel–Crafts alkylation is tentatively ascribed to encapsulated zinc hydroxide clusters (known contaminants in rapidly synthesized samples of MOF-540) or to a hydrolytically degraded form of the parent material (presumably the MOF of formula [Zn3(OH)2(bdc)2]41). In some of the work reviewed below..15. was the catalytic cyanosilylation of aldehydes (eqn (1)). rather than on demonstrating catalytic chemistry that may prove useful to chemists working in areas other than porous materials. ´s i A second set of examples are those reported by Llabre Xamena et al. as shown for example.16 cyanosilylation of aldehydes by a 2D MOF (layered square grids) of formula Cd(4.e. ð1Þ The active sites are Cd(II) ions. indicating that aldehydes must enter the materials pores to reach catalytic sites. and Suzuki C–C coupling... its importance can often be corroborated and exaggerated by fragmenting the MOF (e. at least for hydrogenation. the presence of size selectivity does constitute good circumstantial evidence for heterogeneous reactivity. PIZA = Porphyrinic Illinois Zeolite Analogue.g. the nodes of most MOFs are reasonably good Lewis acids. for example). Nevertheless. it is difficult to rule out the possibility that catalysis is occurring at the surface of MOF-encapsulated palladium clusters/nanoparticles (i. in Fig.4 0 -bpy)2(NO3)2. etc. Notably. Furthermore. rather than at transiently labile. Soc. stage of development of the field: most reports have focused on simply documenting catalytic behavior. Furthermore. substrate-shape-selectivity was observed. As emphasized especially in subsection A. single-atom MOF nodes. based on a two-dimensional. (Nevertheless. While the absence of size selectivity does not prove that the catalyst is homogeneous (catalysis could be limited to the MOF exterior. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18. microporous metal–organic frameworks have appeared to date. We caution the reader that catalysis ascribed to heterogeneous entities is sometimes instead caused by dissolved material. but otherwise intact. 1 are the structures of several organic struts used in the synthesis of catalytically active MOFs. The simplest control is to separate the putative catalyst from the reaction mixture by filtration and then monitor the filtrate to see if catalysis persists. Following in the tradition of zeolite chemistry. 2 for o-dibromobenzene. which obviously lacks the well-defined cavities of MOF-5. HKUST = Hong Kong University of Science and Technology. while in other cases materials are described according to empirical formulae. these acid sites will tend to be exposed at MOF surfaces and may well function as catalysts. AlCl3. MOF-5. many researchers have devised informal menomic names for their materials (e. these reactions necessarily entail redox oscillations of the metal nodes between Pd(II) and Pd(0) intermediates accompanying by drastic changes in coordination number. Rev.37 This material comprises coordinatively saturated Zn4O nodes and a fully complexed bdc struts (bdc = benzene1. axially coordinated water molecules rather than equatorially bound dipyridyl struts. Finally. (Similarly. Finally. B: Designed catalysis with framework nodes 2.). homogeneous catalysts. we have limited our review to MOFs that are crystalline. with Lewis-acid catalysis presumably occurring via substrate displacement of labile. Since these processes are the focus of an excellent review by Lin and co-workers elsewhere in this issue.42 contains large cavities having windows of This journal is c The Royal Society of Chemistry 2009 . Also valuable are studies of substrate size selectivity. Also reported. however.View Article Online Published on 17 March 2009.and shape-selective clathration. by stirring) and exposing additional metal sites and/or ligand termini. POST = Pohang University of Science and Technology.) Among the most exciting developments are those in the area of enantioselective catalysis. para alkylation is strongly favored over ortho alkylation. together with descriptions of the specific catalyzed. olefin hydrogenation. 1450–1459 Lewis acid catalysis. not all heterogeneous catalysis is caused by the intended MOF catalytic site. also known as HKUST-110 and as MOF-199.) Useful control experiments are to examine not only putative catalytic MOFs. included in the section that follows is a table organized in terms of substrates and reactions. a behavior thought to reflect the encapsulation of reactants by the MOF. Shown in Fig. partial decomposition sites) or defect sites. A: Opportunistic catalysis with metal nodes Among the earliest reports of MOF-based catalysis was a description in 1994 by Fujita and co-workers on the 1452 | Chem.

The Lewis-acid-catalyzed cyanosilylation of aromatic aldehydes (eqn (1)) has also been carried out by Long and co-workers using a MOF of the formula Mn3[(Mn4Cl)3BTT8(CH3OH)10]2 (H3BTT = 1. cyclization.2-bis(4pyridyl)ethylene). ethylene acetal of 2-bromopropiophenone Olive oil and mill waste waters Benzaldehyde (or acetone) and cyanotrimethylsilane Benzaldehyde and a-methylbenzeneacetaldehyde Nitrobenzene and 2-methyl-1-nitronaphthalene. the Kaskel group observed that the catalytic sites of MIL-101. Suzuki–Miyaura coupling.3-Epoxybutane and methanol Linear and cyclic olefins 2.2 0 -dihydroxy-1.4-bis(4 0 -pyrazolyl)benzene.4 0 -bipyridine. pbbm = 1. and [PW11CoO39]5À@[Cr3F(H2O)2O(bdc)3] [Cu(2-pymo)2] and [Co(PhIM)2] [Cu(bpy)(H2O)2(BF4)2(bpy)] [Cu(D-asp)bpe0. rearrangement Oxidation of polyphenol Cyanosilylation of aldehyde Acetalization of aldehyde Reduction of nitroaromatic. Lewis acid-catalyzed pathways.12 This material contains a three-dimensional pore structure.5-benzenetris(tetrazol-5-yl)).6 0 -dichloro-2. ˚ .4-benzenedicarboxylate. pymo = 2-hydroxypyrimidinolate.5] [Cu(L2)2(H2O)2]. either of the two types of diameter equaling 10 A Mn(II) sites could function as a catalyst. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18. Noteworthy features of this catalyst are high conversion yields (for small substrates) Chem.2.5-tricarboxylate. Mukaiyama-aldol Oxidation to CO2 Oxidation of alcohol.R)-(À)-1.Nbis(3-tert-butyl-5-(4-pyridyl)salicylidene)MnIIICl.1 0 -binaphthyl-4. aryl halides and arylboronic acids.2-cyclohexanediamino-N. btc = benzene-1.5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]. TpCPP = tetra-(p-carboxyphenyl)porphyrin. Heck coupling Oxidation of olefin Aerobic oxidation of olefin Ring-opening of epoxide Methanolysis of epoxide Epoxidation of olefin Oxidative self-coupling Isomerization. benzaldehyde and methyltrimethylsilyldimethylketene acetal CO Cinnamyl alcohol.6-Dimethylphenol a-Pinene oxide. are immune to unwanted reduction by benzaldehyde. TCPB = 1. BTT = 1. cyclic/linear alkanes Aldehydes and cyanotrimethylsilane. bdc = 1. Py2(PhF5)2Por = 5.5] Mn(porphyrin)@[In48(HImDC)96] [Ln(OH)(1.5-benzenetris(tetrazol-5-yl). 17 2 9 18 19 20 21 22 23 24 25 26 27 28 29 30 7 31 32 12 33 34 39 6 35 36 37 38 Table 1 MOF materiala [Cd(4-btapa)2(NO3)2] [Cd(bpy)2](NO3)2)] [Cd3Cl6L13] [Co(BPB)] [Cr3F(H2O)2O(bdc)3] [PW11TiO40]5À@[Cr3F(H2O)2O(bdc)3].3. Soc. Bpy = 4. PhIM = phenyl imidazolate. caryophyllene and cyclohexene Tetralin Various epoxides cis-2.20-bis(pentafluorophenyl)porphyrin. nds = naphthalenedisulfonic acid. L4 = 4.5] and [Cu(L-asp)bpe0. [In(OH)(hippb)] [In2(OH)3(bdc)1.3. Additionally. methylphenyl sulfide. bpe = trans-1. 3). oxidation of sulfide Oxidation of alkane Epoxidation of olefin Epoxidation of olefin. Based on experimental data. 2009. L5 = (R.15-dipyridyl-10. 1450–1459 | 1453 The Royal Society of Chemistry 2009 . cyclization of citronellal. these researchers concluded that [Cu3(btc)2] indeed functions primarily as a Lewis acid catalyst. Kaskel and co-workers43 also evaluated the behavior of MIL-101. L1 = (R)-6. hippb = 4. whose product selectivity patterns differ significantly for Brønsted vs.26 Recognizing the potential for opportunistic catalysis at defect sites (such as exposed carboxylic acids).4. [Cu(L3)2(H2O)(Py)2]. As one might expect. btapa = 1.28 Alaerts et al.5-tetrakis(4-carboxyphenyl)benzene. HImDC = 4.5-imidazoledicarboxylic acid. investigated the behavior of the anhydrous version of HKUST-1 as an acid catalyst. a large-cavity MOF having the formula This journal is c [Cr3F(H2O)2O(bdc)3] (Fig. L3 = 2-[2-[[(2-aminoethyl)imino]methyl]phenoxy]acetic acid. MIL-101 is much more active than HKUST-1 as a catalyst for the cyanosilylation of aldhydes. as a cyanosilylation catalyst. The coordinated water molecules in MIL-101 are easily removed to expose Cr(III) sites. BPB = 1.3. cyclododecene Propanethiol 2.5)(C3H7NO)Á5C3H7NO] [Mn3((Mn4Cl)3BTT8(CH3OH)10)]2 [(Na20(Ni8L412)(H2O)28)(H2O)13(CH3OH)2] [Pd(2-pymo)2] Tb[V6O13{(OCH2)3C(NH2CH2C6H4-4CO2)}{(OCH2)3C-(NHCH2C6H4-4-CO2)}2]4À [Zn2(bpdc)2L5] [Zn2(Py2(PhF5)2PorZn)(TCPB)] [Zn3(m3-O)(O2CR)6(H2O)3]n+ [Zn4O(bdc)3] and [Zn4O(ndc)3] [(Zn4O)(bdc-NH2)3]ÁVsal0.4 0 -(hexafluoroisopropylidene)bis(benzoic acid). oxidation of alkane Cyanosilylation of aldehyde.5-pentanediyl)bis(1H-benzimidazole). The coordinated water molecules are easily diameter B6 A removed.View Article Online Catalogue of known catalytic MOFs and summary of reactions catalyzed Substrate(s) Benzaldehyde and malononitrile Benzaldehyde and cyanotrimethylsilane Aryl aldehyde and diethyl zinc Cyclohexene Benzaldehyde and ethyl cyanoacetate.4 0 -bipyridine. Kaskel and co-workers showed that these Lewis acid sites could catalyze the cyanosilylation of benzaldehyde or acetone (eqn (1)). hydrogenation of olefin Oxidation of sulfide Epoxidation of olefins Intermolecular transfer of acyl Transesterification Friedel–Crafts alkylation Oxidation of olefin Ref. and rearrangement of a-bromoacetals. L2 = (4-formylphenoxy)acetic acid. Rev. citronellal. [Cu(L3)3(H2O)Cl] and [Co(sal)(H2O)(Py)3] [Cu(SO4)(pbbm)] and [(Cu(Ac)2(pbbm))Á CH3OH] [Cu3(btc)2] Published on 17 March 2009.. in contrast to those of HKUST-1. 1-octene.4 a Ac = acetyl. In principle.5-imidazole dicarboxylic acid. sal = salicylidene moiety.2-Dimethyl-2H-chromene Acetyl imidazole and pyridyl carbinols Esters and alcohols tert-Butyl chloride and toluene Cyclohexene Reaction(s) catalyzed Knoevenagel condensation Cyanosilylation of aldehyde Alkylation of aldehyde Oxidation of olefin Knoevenagel condensation. they examined three reactions: isomerization of a-pinene oxide. (2-ethylbutyl)phenyl sulfide Cyclohexane Linalool Cyclic alkenes.3. leaving open Cu(II) sites.10-(1. given the greater Lewis acidity of Cr(III) vs. 38 . bpdc = biphenyldicarboxylate. with the pore ˚ . D-asp = D-aspartate. iodobenzene and acrylic acid a-Pinene. Cu(II).5-NDS)H2O] [(Mn(TpCPP)Mn1.

2009. Interestingly.12 ð2Þ These reactions generally require stronger Lewis acids than do cyanosilylations. Mn3[(Mn4Cl)3BTT8(CH3OH)10]2 was also found to catalyze the Mukiyama aldol reaction (eqn (2)). (BPB = 1.29 a 2D MOF containing susbtrate-accessible higly Lewis acidic In(III) sites has been used to catalyze the acetalization of benzaldehyde with trimethyl orthoformate.View Article Online Published on 17 March 2009. Fan and co-workers have recently shown that MOFs with copper metal centers can catalyze the oxidative coupling of 2.4phenylene ether).6-dimethylphenol to form poly(1. albeit with some degradation of the MOF after a few dozen turnovers. Fig.. Soc. 1450–1459 Alkene oxidation. and good substrate-size-selectivity. 1 Structures of various organic struts employed in the synthesis of catalytically active MOFs. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18. 1454 | Chem.18 As shown in Fig. recently examined the oxidative catalytic behavior of a porous three-dimensional MOF having the formula [Co(BPB)]Á3DMF.4-bis(4 0 -pyrazolyl)benzene). 4. the Co(II) ions are organized as one-dimensional chains via tetrahedral coordination with pyrazolyl nitrogens. Rev. an industrially significant polymer.25 These systems are capable of yielding C–O/C–C oxidative coupling This journal is c The Royal Society of Chemistry 2009 . consistent with channellocalized catalysis. Lu et al. 38. In another report. Exposure to tert-butyl hydroperoxide is believed to convert Co(II) to Co(III). Addition of cyclohexene results in the formation of tert-butyl-2-cyclohexenyl peroxide in 83% yield. Oxidative coupling.

both in artificial systems and as active sites in many metallo-enzymes. while the free porphyrin ligand is used in the synthesis. N = blue segment. and the tetratopic ligand H4TCPB (= 1.46 from Zn(NO3)2. DPyDPhF5Por (= 5. and therefore permanent microporosity. to date there exist only two reports of catalysis by porphyrin struts in well-defined MOFs. Noro and Nakamura have extensively discussed this strategy. Unfortunately.32. (2) it is difficult to prevent porphyrin metal sites from doubling as nodes for strut coordination. despite selectivity in vapor sorption studies. Rev. in addition to catalysis. 2009. The first report of porphyrin-strut-based catalysis concerns PIZA-3. Hydrogen atoms are omitted for clarity. 4 A crystallographic illustration of the framework structure of [Co(BPB)]Á3DMF. Co = blue polyhedron. C: to catalyst ratios as well as short Homogeneous catalysts incorporated as MOF struts Published on 17 March 2009. PIZA-3. porphyrin complexes are obvious candidates for incorporation into MOFs as catalytically functional struts. Fig. the absence of substrate size and shape selectivity.View Article Online good substrate reaction times. DMF molecules and hydrogen atoms are omitted for clarity. Cd = gold segment. lacking in many porphyrinic MOFs. catalysis-relevant structural and synthetic notions.15-dipyridyl-10. led the researchers to conclude that catalysis is dominated by reactivity on the MOF exterior. 3 A crystallographic illustration of the pore structure of MIL-101. Fig. First. The tetratopic strut also serves to inhibit framework catenation—both in ZnPO-MOF and in other frameworks. Cr = orange polyhedron. Given their enormous utility as molecular catalysts. the intentional mismatch of dimensions for the two molecules used as struts. shown along the crystallographic a axis.20-bis(pentafluorophenyl)porphyrin).4 0 -bpy)2(NO3)2. some of the earliest reports on crystalline MOFs emphasized the potential of porphyrins as building blocks. N = blue segment. and display This journal is c Metalloporphyrins. C = gray segment.32 a MOF featuring trinuclear manganese clusters as nodes and [tetrakis(phenylcarboxylate)porphyrin]Mn(III) as struts. Secondly. 1450–1459 | 1455 The Royal Society of Chemistry 2009 . Kitagawa. C = gray segment. the tetratopic strut (TCPB4À) provides the structural stability. Soc. Fig. An attractive and straightforward approach to MOF-based catalyst design is to heterogenize known homogeneous molecular catalysts by employing them as struts. thereby blocking potential catalytic sites. together with the comparatively Chem. C = gray segment. which is stable to solvent evacuation. Shultz et al. 38 .2.and heterogeneous catalysts (up to B90% C–O/C–C coupling under optimized reaction conditions).5-tetrakis(4-carboxyphenyl)benzene) (Fig. 5) and used it for the catalysis of an intermolecular acyl-transfer reaction.35 The near absence of catalytically active porphyrin-strut-based MOFs can be attributed to three design challenges: (1) porphyrinic MOFs featuring large open pores are unusually susceptible to collapse upon removal of solvent. Hydrogen atoms are omitted for clarity. In the second report. 2 A crystallographic illustration of the shape selective clathration of dibromobenzene within a square cavity of Cd(4. it is spontaneously metallated (with Zn(II)) during MOF formation.11 Additionally. is capable of catalytically hydroxylating both linear and cyclic alkanes as well as epoxidizing olefins (oxidant = iodosylbenzene). Br = red segment.. chemical sensing and preferential chemisorption.45 However. (3) attempts to incorporate free-base porphyrins as struts (which would then be available for post-synthesis metallation) are generally frustrated by the tendency of the porphyrin ligand to scavenge and coordinate metal ions present in the initial MOF synthesis. a highly porous pillared paddlewheel MOF. O = red segment.35 ZnPO-MOF illustrates several interesting. successfully synthesized ZnPO-MOF. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18. Indeed.4.44 noting that strut-centered incorporation of coordinatively unsaturated metal centers could lead to applications in separations. selectivities that are comparable to those obtained for other homo.

N 0 -bis(3-tert-butyl-5-(4-pyridyl)salicylidene)MnIIICl52.53 (LKJ in Fig. however. the use of H4TCPB enabled Shultz et al. As illustrated in Fig. catalysis studies using these potentially interesting materials have not been reported. and ‘‘mainly inside’’ catalysis subsequently. right). 2009. Recognizing the importance of Schiff base complexes as homogeneous molecular catalysts. 5. C = gray segment. small : large) that increased greatly as the catalytic reaction proceeded (18 : 1 small : large at 45% conversion). Binaphthyl complexes. 1). 6). Studies of substrate size selectivity (2 : 1. have described a two-fold catenated. This. 1). they present to candidate reactants large pores and cofacial Zn(II)porphyrin sites (potential binding sites) spaced ˚ (Fig. effectively raising its local concentration and tremendously enhancing the catalytic rate (Fig.15-dipyridyl-10. Schiff-base complexes. Solvent molecules and hydrogen atoms are omitted for clarity.6 4. in turn. Cho et al. the porphyrin struts in ZnPO-MOF are oriented in parallel 1D.2. to overcome the aforementioned design challenges (1) and (2). This unusual behavior was attributed to mixed ‘‘inside/outside’’ catalysis initially. In the supramolecular systems.20-bis(pentafluorophenyl)porphyrin struts. The cofacial arrangement of binding by B12 A sites is reminiscent of that found in discrete Zn-based supramolecular assemblies that are catalytically active for acyl transfer between N-acetylimidazole (NAI) and various pyridylcarbinols (PCs) (eqn (3))47. 5. Fig. Zn = yellow polyhedron. 1450–1459 The Royal Society of Chemistry 2009 . This in turn leads to greatly increased selectivity for the small substrate. a key factor (eqn (3)) is proper alignment of the substrate molecules (and therefore. As the reaction proceeds. pillaredpaddlewheel MOF46 featuring pairs of zinc ions as nodes and (salen)Mn species as struts. Fig.N 0 -phenylenebis(salicylideneimine)dicarboxylate (H4salphdc) struts. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18. ˚ distance between Right: A view of the unit cell highlighting the 11.9 The struts are connected to chloride-bridged chains of cadmium ions to yield a 3D structure containing sizeable This journal is c ð3Þ 1456 | Chem. Thus. formed from 1.4 0 -Biphenyldicarboxylate (bpdc) struts define robust square grids that are separated by pillars consisting of a pyridine-derivatized version of the well-known Katsuki–Jacobsen epoxidation catalysts. 5 Left: A crystallographic view of a single network unit for ZnPO-MOF. N = blue segment.6 A cofacial porphyrins. Additional experiments reveal that preferential substrate alignment is not a major contributing factor to the catalysis seen with ZnPO-MOF. Fig. As such. necessitating substrate permeation of the MOF to access active catalytic sites. they can be engineered into welldefined. fashion. 6 A schematic view showing a unit cell of ZnPO-MOF that effectively pre-concentrates and Lewis-acid activates N-acetylimidazole for catalytic acyl transfer to pyridylcarbinol species. Soc. Ni(II) or Co(II) complexes of N.5-tetrakis(4-carboxyphenyl)benzene) and (5.50. strong carboxylate–Zn(II) (paddlewheel) bonding.View Article Online Published on 17 March 2009. reactant-accessible MOF-based catalytically active sites comprising high local metallo-porphyrin concentrations.2-cyclohexanediamino-N. prevents the available porphyrinic Zn(II) sites from functioning as secondary nodes. Studies of olefin epoxidation revealed that heterogenization substantially increases the activity of the catalyst. Kitagawa and co-workers reported the synthesis of a series of MOF materials comprising trinuclear zinc hydroxyl species as nodes and Cu(II).47. Lin and co-workers reported the synthesis of a catalytically active MOF containing pyridinefunctionalized hydroxybinaphthyl units as struts (LBin-OH.4.48 which much more effectively catalyze the transfer of an acyl group to the 3-PC and 4-PC isomers than to 2-PC. 38..48—suggesting that ZnPO-MOF should be similarly catalytically active. This surprising observation is in stark contrast to that observed with discrete supramolecular catalysts.51 (1. oxidantinduced damage of the outermost struts of the framework occurs.49 To date. no significant rate difference was observed among the three isomers of PC. stabilization of the transition state) by the porphyrinic assemblies. O = red segment. While ZnPO-MOF is indeed catalytically competent for this transformation (B2400-fold rate enhancement compared to the uncatalyzed process). Rev. the catalysis is primarily due to pre-concentration of NAI in the MOF. rather than box-like 2D. These observations highlight a design characteristic that make MOF-heterogenized porphyrin catalysts different from homogeneous monomeric and supramolecular analogues: while the former may not possess the flexibility of their soluble counterparts. F = cyan segment. leaves the sites open for subsequent catalytic chemistry. Rather.

it is conceivable that oxidation proceeds via both oxygen transfer from a manganese oxo intermediate as well as a manganese-initiated radical chain reaction pathway. cavityaccessible epoxide at up to 65% yield. Lin and co-workers were able to effect catalytic ZnEt2 additions to aromatic aldehydes with high enantioselectivities. the cavities are large enough to encapsulate porphyrins. The coordination chemistry (see Fig.View Article Online 1D channels. 7. the approach is a promising one for isolating and thereby stabilizing the porphyrins against both oxo-bridged dimer formation and oxidative degradation. are too small to enable porphyrins to pass through. Eddaoudi. 8 A schematic view of the coordination environment around the Cu center in a MOF with D-aspartate struts. Solvent molecules and hydrogen atoms are omitted for clarity.23 These compounds employ amino acids (L. Briefly. Consequently. rather than TPHP as oxidant.17 The MOF is three-dimensional.59 Regardless of mechanism.7 Under certain conditions.23 This journal is c The Royal Society of Chemistry 2009 Chem. are only marginally accelerated.or D-aspartate) together with dipyridyls as struts.7 As illustrated in Fig. The pores surrounding these cavities. Kitagawa and co-workers have reported the synthesis of a catalytic MOF having the formula [Cd(4-btapa)2(NO3)2] (4-btapa = 1. the most interesting feature of this material is the presence of guest-accessible amide functionalities. The nodes consist of single cadmium ions. The difference is likely mechanistically significant. While the nickel-based compounds are marginally porous. octahedrally ligated by pyridyl nitrogens. 1). for the MOF-based system. 7 The pore structure of rho-ZMOF (left). the copper versions are clearly porous. In addition. (Figure courtesy of Prof. on account of tiny channel dimensions. The researchers showed that the amides are capable of base-catalyzing the Knoevenagel condensation of benzaldehyde with malononitrile.and two copper-containing MOFs synthesized by Rosseinsky and co-workers. the strategy allows for the encapsulation of the porphyrin as a free base.57. The MOF encapsulation approach invites comparison to earlier studies of oxidative catalysis by zeolite-encapsulated Fe(porphyrin)54–56 as well as Mn(porphyrin) systems. Additionally. Among the few exceptions are two nickel. 38 .. M. while TBHP is capable of more complex behavior. however. E: Catalysis by metal-free organic struts or cavity modifiers The unusual post-synthesis functionalization strategy works because of the marginal affinity of the naphthoxide site for Cd(II). present at high concentration during the initial synthesis. Most examples of MOF-based catalysis make use of metal ions or atoms as active sites. 8) is such that the amine group of the aspartate cannot be protonated by added HCl. they showed that the manganese version could be used to facilitate the oxidation of cyclohexane to cyclohexanol and cyclohexanone using tert-butyl hydroperoxide (TPHP) oxidant. consisting of an identical catenated pair of networks. Once the MOF was assembled. 2009. With the titanium-functionalized MOF in hand. Published on 17 March 2009. 1450–1459 | 1457 . but one of the aspartate carboxylates can. loadings of 460 wt% were achieved. the framework-incorporated amino acid can exist in a form that is not accessible for the free amino acid.) Fig. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18. Reactions with larger nitriles. Rev. D: MOF-encapsulated molecular catalysts Eddaoudi and co-workers have used 4. zinc or copper ions. thus complicating comparisons. Thus. From a catalysis standpoint. but emphasize that the catalyst formed here is unique to the MOF environment.58 The zeolite studies generally employed iodosylbenzene (PhIO). PhIO is a single oxygen atom donor.5-imidazole dicarboxylic acid (H3ImDC) and In(NO3)3 to create an unusually robust anionic framework (termed rho-ZMOF) that can be formulated as [In48(HImDC)96]. thus representing an interesting proof of concept. The Eddaoudi group demonstrated that the encapsulated free-base porphyrin could be metallated subsequently with manganese. yet still featuring pores of molecular dimensions. however. These researchers point out that superior homogeneous catalysts exist. cationic porphyrins can be electrostatically encapsulated and incarcerated during MOF synthesis. these researchers were able to introduce Ti(IV) sites via coordination by secondary functional groups as shown below. see Fig. and encapsulated [H2TMPyP]4+ porphyrin in rho-ZMOF a-cage (right). implying Fig. however. cobalt. Importantly.5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]. The Rosseinsky group showed that the carboxylic acids behave as Brønsted acidic catalysts. facilitating (in the copper cases) the ring-opening methanolysis of a small.3. Soc.

to a fledgling ‘‘real’’ application encompassing more than two dozen experimental examples. however. Fair turnover frequencies were observed (80 hÀ1 at 50 1C for [PW11Co39]5À@MIL-101.36 Using a pyridine-functionalized derivative of tartaric acid (LTaPy. For a general review of post-synthetic modification of MOFs see the article by Wang and Cohen in this issue of Chem. While three of the six pyridines are coordinated by zinc ions. to demonstrate that clusters/nanoparticles are actually encapsulated within well-defined MOF cavities. 1450–1459 The Royal Society of Chemistry 2009 . was observed to be catalytically competent for the same reaction. The future of the field clearly lies in demonstrating advantageous catalytic behavior that is unique to MOFs. Hydrogen peroxide was ultimately found to degrade the MOF framework. POST-1 possesses 1D channels whose cross sections are defined by six trinuclear zinc clusters and six struts. 9 A hexagonal large-pore structure of POST-1 with three pyridyl groups pointing to the pore. Rev. A noteworthy finding is the lack of catalysis by the free strut in homogeneous solution. while clearly important for reactions in living systems. based chiefly on metals or metal oxides. MOFs allow for easier post-reaction separation and recyclability than homogeneous catalysts.66 The encapsulation is electrostatic.62–65 and a number of intriguing preliminary results. Soc. This journal is c 1458 | Chem. the notion of metal–organic frameworks as catalysts has advanced from being a largely hypothetical one. Many more remain to be discovered. Fe workers19 were able to modify the interior of MIL-101 via Cr(III) coordination of one of the two available nitrogen atoms of each of several ethylenediamine molecules.. When neutralized. a small number of examples of unique catalyst structures and product distributions have begun to appear. O in red. Soc. and 40 hÀ1 at 30 1C for [PW11TiO40]5À@MIL-101). DTRA. evidently due to intermolecular H-bonding between bptda molecules. DOE. Rev.) Kholdeeva and coworkers showed that by employing either titanium. 3). The absence of significant catalysis when large alcohols are employed strongly suggests that the catalysis occurs within the channels of the MOF. see Fig. [PW11CoO39]5À@MIL-101.60 Thus. Indeed. ARO. Conclusions Over the past five years. again for Knoevenagel condensation of benzaldehyde with nitriles. entailing the displacement of initially present fluoride ions. and the Northwestern Institute for Catalysis in Energy Processes for financial support of our work.or cobalt-substituted Keggin ions. As noted above. Solvent molecules and hydrogen atoms have been omitted for clarity. post-synthetic tailoring of MOF cavities has been described for materials featuring open Cu(II)10 or Zn(II)11 sites. 38. [PW11TiO40]5À@MIL-101 was found to be capable of facilitating the oxidation of a-pinene to the corresponding alcohol and ketone using hydrogen peroxide oxidant. such as eqn (4). AFOSR. the MOF architecture elicits catalytic activity not otherwise encountered. ´ rey and coIn an interesting alternative approach.20 For example. and C in gray. The only unambiguous examples of (exclusively) singlecavity encapsulation of well-defined clusters appear to be Keggin-type polyoxometallates within the rather sizeable cavities of MIL-101 (Fig. Additionally. that catalysis takes place chiefly within the material’s channels rather than on its exterior. the remaining three are protonated and directed toward the channel interior. with catalyst particle sizes clearly exceeding the dimensions of single MOF cavities. but O2 was not. but with O2 as the oxidant. selectivity on the basis of substrate size is of limited value in abiotic catalysis. It has generally proven difficult. the Northwestern Nanoscale Science and Engineering Center. 3. ð4Þ Acknowledgements Fig. (Related coordination-based. the composite cluster@MOF materials could be rendered catalytic. A third approach has been described by Kim and coworkers. as reasonably pure feedstocks are generally available. N in blue. (The clusters are small enough to enter the MIL-101 cavities through the available ports. In some cases. presumably by facilitating deprotonation of the reactant alcohol. in some instances the opposite has been shown. F: Catalysis by MOF-encapsulated clusters Controlled growth of catalytic clusters or nanoparticles within MOF cavities is an idea that has captured the attention of several research groups. Nevertheless. 1) and a Zn(II) source they were able to synthesize a 2D MOF termed POST-1. 9. on the other hand.61) The free non-coordinated ends of the ethylenediamines were then used as Brønsted basic catalysts. As illustrated in Fig. have been obtained. the noncoordinated pyridyl groups are found to catalyze transesterification reactions. Zn atoms are shown in yellow. We gratefully acknowledge the US NSF.View Article Online Published on 17 March 2009. Downloaded by Universidade Tecnica de Lisboa (UTL) on 26/09/2013 15:41:18. they also lend highly enhanced catalyst stability. they typically offer substratesize selectivity. 2009. Like other heterogeneous catalysts.

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