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. 2013 Sep 11;135(36):13222-34.
doi: 10.1021/ja308229p. Epub 2013 Aug 28.

Metal-organic frameworks as a tunable platform for designing functional molecular materials

Cheng Wang  1 , Demin Liu, Wenbin Lin
Affiliations

Metal-organic frameworks as a tunable platform for designing functional molecular materials

Cheng Wang et al. J Am Chem Soc. .

Abstract

Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting class of crystalline molecular materials that are synthesized by combining metal-connecting points and bridging ligands. The modular nature of and mild conditions for MOF synthesis have permitted the rational structural design of numerous MOFs and the incorporation of various functionalities via constituent building blocks. The resulting designer MOFs have shown promise for applications in a number of areas, including gas storage/separation, nonlinear optics/ferroelectricity, catalysis, energy conversion/storage, chemical sensing, biomedical imaging, and drug delivery. The structure-property relationships of MOFs can also be readily established by taking advantage of the knowledge of their detailed atomic structures, which enables fine-tuning of their functionalities for desired applications. Through the combination of molecular synthesis and crystal engineering, MOFs thus present an unprecedented opportunity for the rational and precise design of functional materials.

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Figures

Figure 1
Figure 1
Synthesis of functional MOFs for various applications.
Figure 2
Figure 2
Left, calculated methane (red), ethane (blue), ethylene (green) and acetylene (orange) breakthrough curves for an equimolar mixture of the gases at 1 bar flowing through a fixed bed of Fe2(DOBDC) at 318K. Right, schematic representation of the separation of a mixture of methane, ethane, ethylene, and acetylene using three packed beds of Fe2(DOBDC) in a vacuum swing adsorption or temperature swing adsorption process. Reproduced with permission from reference [34]. Copyright: Science Magazine 2012.
Figure 3
Figure 3
a) Construction of MOFs with 3-D diamond structures from a linear pyridinecarboxylate ligand and Zn2+/Cd2+ nodes. b) Structures of linear pyridinecarboxylate ligands. c) Diamondoid structures built from linear pyridinecarboxylate ligands. d) Asymmetric unit of the crystal of Cd-TBP. e) Electric field polarization cycles of Cd-TBP. d) and e) reproduced with permission from reference [39c]. Copyright: American Chemical Society 2006.
Figure 4
Figure 4
a) Chemical structures of BINOL-derived tetracarboxylic acid ligands (BINOL-TC). b) Representation of the BINOL-TC ligand as a blue distorted tetrahedron and the [Cu2(O2CR)4] paddlewheel as a red square, and simplified connectivity scheme of the MOF structure. c) Schematic representation of asymmetric alkyl- and alkynylzinc additions catalyzed by the MOF-based Ti-BINOLate catalyst within large open channels. Reproduced with permission from reference [16f]. Copyright: Nature Publishing Group 2010.
Figure 5
Figure 5
Schematic representation of sequential asymmetric epoxidation and ring-opening reactions catalyzed by the Mn-Salen-based ligand and [Zn4(µ4-O)(CO2)6] SBU, respectively. Reproduced with permission from reference [16g]. Copyright: Royal Society of Chemistry 2011.
Figure 6
Figure 6
Left, electron transport pathway through a continuum of TTF moiety in the crystal structure of Zn2(TTFTB). Middle and right, crystal structure of Zn2(TTFTB) showing porosity and charge transport through parallel channels. Reproduced with permission from reference [12d]. Copyright: American Chemical Society 2012.
Figure 7
Figure 7
a) Schematic showing energy transfer in a MOF crystal (left) and decay transients of Ru(bipy)32+* and Os(bipy)32+* in Os-doped MOFs built from Ru(bipy)32+ derivatives (right). b) Light-harvesting with a MOF microcrystal. The 3MLCT excited states undergo rapid intra-framework energy migration to carry out electron transfer quenching at the MOF/solution interface. c) Chemical structures of the photoactive MOF building blocks and reductive tetramethylbenzidine (TMBD) and oxidative benzoquione (BQ) quenchers. Reproduced with permission from references [19a] (a) and [19b] (b and c). Copyright: American Chemical Society 2009 and 2010.
Figure 8
Figure 8
Luminescent quenching of [Zn2(bpdc)2(bpee)] by vapor of solid explosives DNT and DMNB for explosive detection. Reproduced with permission from reference [15b]. Copyright: Wiley 2009.
Figure 9
Figure 9
a) T1-weighted MR phantom images of suspensions of Gd(BDC)1.5(H2O)2 in water containing 0.1 % xanthan gum as a dispersing agent. b) Luminescence of ethanolic dispersions of Eu- and Tb-doped Gd(BDC)1.5(H2O)2 when irradiated with UV light.
Figure 10
Figure 10
T2 weighted MR images of Wistar rats injected with no particle (a,c,e) or 220 mg/kg MIL-88A (e,d,f). The images were acquired using either gradient echo (a,b,e,f) or spin echo (c,d) sequences. The images show the liver (a–d) or spleen (e,f) regions 30 minutes post-injection. [dm=dorsal muscle, k=kidney, li=liver, s=spleen, st=stomach]. Reproduced with permission from reference [18a]. Copyright: Nature Publishing Group 2010.
Figure 11
Figure 11
Left) SEM image of MIL-101. The inset shows the 42@silica@PEG particles. Right) Confocal microscopy image of H460 cells that have been incubated with MIL-101@SiO2-PEG-AA. Reproduced with permission from reference [18c]. Copyright: American Chemical Society 2009.
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    1. There is currently no consensus on the definitions of coordination polymer vs. metal-organic framework. In this perspective, we use the two terms synonymsly.

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