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Review
. 2009;48(4):650-8.
doi: 10.1002/anie.200803387.

Modular synthesis of functional nanoscale coordination polymers

Wenbin Lin  1 , William J Rieter, Kathryn M L Taylor
Affiliations
Review

Modular synthesis of functional nanoscale coordination polymers

Wenbin Lin et al. Angew Chem Int Ed Engl. 2009.

Abstract

The coordination-directed assembly of metal ions and organic bridging ligands has afforded a variety of bulk-scale hybrid materials with promising characteristics for a number of practical applications, such as gas storage and heterogeneous catalysis. Recently, so-called coordination polymers have emerged as a new class of hybrid nanomaterials. Herein, we highlight advances in the syntheses of both amorphous and crystalline nanoscale coordination polymers. We also illustrate how scaling down these materials to the nano-regime has enabled their use in a broad range of applications including catalysis, spin-crossover, templating, biosensing, biomedical imaging, and anticancer drug delivery. These results underscore the exciting opportunities of developing next-generation functional nanomaterials based on molecular components.

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Figures

Figure 1
Figure 1
a) Scheme illustrating the synthesis of cyanometallate nanoparticles. TEM images of cyanometallate nanoparticles synthesized in Co(AOT)2 water-in-oil microemulsions at (b) W = 30 and (c) W = 10.[7b] Sacle bar = 200 nm. AOT is sodium bis(2-ethylhexyl) sulphosuccinate whereas W is the water to surfactant molar ratio.
Figure 2
Figure 2
a) Scheme for the synthesis of valence-tautomeric nanoparticles. b) SEM and (c) TEM micrographs of valence-tautormeric nanoparticles.[15]
Figure 3
Figure 3
SEM micrographs of Gd2(BDC)3(H2O)4 nanoparticles synthesized using a reverse microemulsion with (a) W = 5 and (b) W = 10. (c–d) SEM micrographs of [Gd(iBTC)(H2O)3]·H2O.[16]
Figure 4
Figure 4
(a) SEM and (b) TEM micrographs of crystalline Mn(BDC)(H2O)2. (c) SEM and (d) TEM micrographs of crystalline Mn3(BTC)2(H2O)6.[17]
Figure 5
Figure 5
(a) SEM and (b) TEM micrographs of Gd2(BHC)(H2O)6. Crystal structures illustrating the (c) Gd coordination environment, (d) linking of BHC to eight different Gd centers, and (e) packing in Gd2(BHC)(H2O)6. Structures were drawn using the cif file for isostructural La2(BHC)(H2O)6.[20]
Figure 6
Figure 6
(a–b) SEM micrographs of [Gd2(BHC)(H2O)8]·2H2O. Crystal structures illustrating the (c) Gd coordination environment, (d) linking of BHC to eight different Gd centers, and (e) packing in Gd2(BHC)(H2O)8]·2H2O.[20]
Figure 7
Figure 7
(a) Scheme for the synthesis of Zn-MS-Zn nanowires and their subsequent transformation into nanocubes. (b–d) SEM micrographs illustrating the transformation of nanowires into nanocubes during the synthesis.[21]
Figure 8
Figure 8
Magnetic thermal hysteresis for [Fe(Htrz)2(trz)](BF4) nanoparticles.[18]
Figure 9
Figure 9
(a and b) TEM images of Gd2(BDC)3(H2O)4 NMOFs with a 2–3 nm silica shell; (c) TEM image of Gd2(BDC)3(H2O)4 NMOFs with an 8–9 nm silica shell; (d) TEM image of 8–9 nm silica nanoshells generated from (c). Scale bars are 50 nm unless otherwise indicated.[22]
Figure 10
Figure 10
(a) T1-weighted MR phantom images of suspensions of Gd2(BDC)3(H2O)4 NMOFs in water containing 0.1 % xanthan gum as a dispersing agent. (b) Luminescence of ethanolic dispersions of Eu- and Tb-doped Gd2(BDC)3(H2O)4 NMOFs when irradiated with UV light.[16] (c) Luminescence of a series of Zn-BMSB-Zn particles in toluene with different ancillary ligands.[12]
Figure 11
Figure 11
(a) Schematic showing luminescence sensing of dipicolinic acid using core-shell nanostructures. (b) Ratiomeric curves obtained by plotting the Tb to Eu luminescence signal intensities exhibited by Tb-EDTA functionalized Gd1.96:Eu0.04(BDC)3(H2O)4 against DPA concentration (red = 544 nm/592 nm, black = 544 nm/615 nm). The inset shows the linear relationship at low DPA concentrations.[22]
Figure 12
Figure 12
Merged confocal images of HT-29 cells that were incubated with (a) no Mn3(BTC)2(H2O)6/silica core-shell nanostructures, (b) non-targeted Mn3(BTC)2(H2O)6/silica core-shell nanostructures, (c) c(RGDfK)-targeted Mn3(BTC)2(H2O)6/silica core-shell nanostructures. The blue color was from DRAQ5 used to stain the cell nuclei while the green color was from rhodamine B.
Figure 13
Figure 13
(a) Schematic showing controlled release of DSCP from the core-shell nanostructure. (b) In vitro cytotoxicity assay curves for HT-29 cells incubated with various Pt-based NCPs.[13]
Figure 13
Figure 13
(a) Schematic showing controlled release of DSCP from the core-shell nanostructure. (b) In vitro cytotoxicity assay curves for HT-29 cells incubated with various Pt-based NCPs.[13]
Scheme 1
Scheme 1
Synthesis of an organometallic nanocatalyst.[10]
Scheme 2
Scheme 2
Synthesis of NCPs based on the M-BMSB building block.[12]
Scheme 3
Scheme 3
Synthesis of NCPs based on the anticancer drug disuccinatocisplatin (DSCP).[13]
Scheme 4
Scheme 4
Examples of various dipyrrin “dimers” used to synthesize NCPs by Maeda et al.[14]
See this image and copyright information in PMC

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