Spontaneous Resolution upon Crystallization of 3D, Chiral Inorganic

Subscriber access provided by YORK UNIV

Article

Spontaneous resolution upon crystallization of 3D, chiral inorganic networks assembled from achiral, polyoxometallate units and metal ions. Amanpreet Kaur, Geeta Hundal, and Maninder S. Hundal Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg4007197 • Publication Date (Web): 22 Jul 2013 Downloaded from http://pubs.acs.org on July 23, 2013

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Spontaneous resolution upon crystallization of 3D, chiral inorganic networks assembled from achiral, polyoxometallate units and metal ions. AmanpreetKaur, Geeta Hundal and Maninder Singh Hundal* Department of Chemistry, Guru Nanak Dev University, Amritsar-143005, Punjab, India. [email protected]; [email protected]; [email protected]

Abstract: Two enantiomerically pure 3D chiral POM-based compounds 1a and 1b having formula (H3O+)2[K2(SiW12O40)(H2O)4].H2O have been isolated during crystallization. Singlecrystal X-ray diffraction analysis revealed that 1a and 1b are enantiomers, crystallizing in chiral space group P6222and P6422, respectively. The compounds are optically active and their UV spectra show cotton effects in the opposite direction. Compounds 1a and 1b represent the examples of 3D chiral frameworks of POM based inorganic skeletons, obtained by spontaneous resolution upon crystallization from achiral precursors. The crystal structures represent open framework with water molecules in the chiral, nanotubular channels.

Key words- Spontaneous resolution, POM based inorganic network, optically active, cotton effect, chiral channels, guest water molecules

Introduction Polyoxometalates1 (POMs) are compounds which constitute a unique class of metal oxide clusters with interesting properties, finding applications in medicine2, biology3, magnetism4, materials science5 and catalysis6 as well as act as precursors for synthesis of organometallic derivatives.7 The assembly of purely inorganic POM-based frameworks occupies high potentiality for the synthesis of new porous materials which combine the thermodynamic stability of zeolites and mesoporous silicas8. Assembly of chiral POM based compounds incorporates the functionality from both POMs and chiral materials and is an active research field in recent years.9 Two main approaches have been developed for the formation of chiral POM-based frameworks. The first method is based on the use of chiral species (chiral organic linkers or chiral metal 1 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 16

complexes) as structure-directing agents.10 The second approach is based on the use of achiral ligands with spontaneous resolution without any chiral auxiliaries, which yields a conglomerate.11 Industrially, such a mechanical mixture of chiral crystals can be separated by entrainment.12-14 Manufacturing a racemic mixture, followed by chiral separation of the two enantiomers, is always preferred over the more expensive stereo-selective synthesis, which may not provide sufficient purity.15 Spontaneous resolution16 which is known as the segregation of enantiomers upon crystallization, was discovered as early as 1846 by Louis Pasteur, but it is still a rare phenomenon that cannot be predicted earlier because the laws of physics determining the processes are not yet fully understood.17 Nonetheless, this crystallization-induced dynamic resolution (CIDR) has proven to be a very practical and efficient asymmetric transformation, in which labile substrates are transformed by a dynamic resolution followed by selective crystallization into optically pure compounds.18 There are many examples of chiral MOFs 10,19, 20 and also of their spontaneous resolution

16, 21, 22

with both chiral and achiral precursors, but

design and construction of chiral POM-based compounds is more difficult,18,23, 24 and more so is the spontaneous resolution of achiral inorganic components. Therefore, a rational synthesis of chiral, high-dimensional open frameworks constructed from POM units, is a great challenge. Here we report, potassium metal ion and POM based inorganic frameworks 1a-1b, which are resolved by spontaneous resolution upon crystallization, in the absence of any chiral source into 3D, chiral open frame networks. Single-crystal X-ray diffraction analyses reveal that compounds 1a and 1b are enantiomers. In addition, 1a-1b have been characterized further by IR, XRD powder pattern, EDS and thermo gravimetric analyses (TGAs). The optical activity of the enantiomers has been proven by optical rotation measurements and the CD spectroscopy. The successful isolation of these species not only produces interesting examples of enantiomerically pure architectures but may also provide a strategy for synthesis of chiral POM-based inorganic frameworks used here i.e. by opting crystallization in the presence of some non-reactive foreign materials.

Experimental Section Materials and physical measurements: All the reagents were commercially available and used as received. The melting points were determined with an electrically heated apparatus. The IR spectra of compounds were recorded on 2 ACS Paragon Plus Environment

Page 3 of 16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Perkin ELMER FTIR spectrometer in the range 4000-400cm-1. Thermogravimetric analysis (TGA) data were collected on a NetzschTG-209 instrument with a heating rate of 10⁰ C min-1. The X-ray powder diffraction (XRPD) measurements were recorded on a Rigaku miniflex X-ray diffractometer with Cu Kα radiation. UV spectra were recorded on a Shimadzu 1700 spectrophotometer in water. The CD measurements were performed on JASCO-815 spectrophotometer interfaced with an IBM PC compatible computer, calibrated with D-camphor sulfonic acid. CD spectra were collected in water as an average of four multiple scans between the ranges of 250-350 nm at the scanning rate of 100 nm min-1 using quartz cells of 10 mm path length with volume capacity of 1 ml. Data were collected in terms of milli degrees versus wavelength. Optical rotation was measured on JASCO DIP-360 digital polarimeter in water at 20 °C. The morphology and elemental (EDX) analysis were performed on scanning electron microscope (JEOL JSM-6610LV) using voltage of 15 KV. Syntheses of 1a and 1b A mixture of sillicotungstic acid (H4SiW12O40) (1.439 g, 0.5 mmol), Mn(NO3)2.6H2O (0.1789 g, 0.1 mmol) (for 1a) or Eu(NO3)3.5H2O (0.428 g, 0.1 mmol) (for 1b), was stirred and heated at 60⁰C for 3 hours. Then 3.0 g KCl is added vigorously and white precipitates were formed immediately. The precipitates were filtered and recrystallized from warm distilled water. Colorless, block-shaped crystals of 1a and 1b were isolated after a few days. For 1a: Yield: 65%, For 1b: Yield: 68%, Anal. Calcd. for K2H16O47SiW12 : K 2.54; Si 0.91; W 71.62. Found : K 2.69; Si 0.85 ;W 72.56% ; IR (KBr, cm-1): 3397 (O-H), 1624 (bending mode of water), 974(WOt), 915 (Si-Oa), 873(W-Ob-W), 730 (W-Oc-W) cm-1 for 1a and 1b (ESI, Fig. S1a-S1b), specific rotation [α]20 = +20.8°(S) for 1a and -20.8° (R) for 1b, CCDC Number 937951 for 1a and 937952 for 1b. The racemic conglomerate 1c of the same compound was prepared by dissolving sillicotungstic acid (1.439 g, 0.5 mmol) and 3.0 g KCl in distilled water with vigorous stirring resulting in the formation of white precipitates. Colorless, block-shaped crystals were isolated by recrystalizing in warm distilled water. IR (KBr, cm-1):3397 (O-H), 1624 (bending mode of water), 915(Si-Oa), 974(W-Ot), 873(W-Ob-W), 730 (W-Oc-W) cm-1, specific rotation [α]20= -1.2 for 1c which means an enantiomeric excess of 5.7% for (R) enantiomer in it.

X-ray crystallography 3 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 16

The crystals were grown by slow evaporation at room temperature from distilled water. X-ray data of all three complexes (1a, 1b and 1c) were collected on a Bruker’s Apex-II CCD diffractometer using Mo Kα (λ=0.71069 Å) at room temperature. The data were processed by SAINT correcting for Lorentz and polarization effects. An empirical absorption correction was applied using SADABS from Bruker. The structures of 1a and 1b were solved in hexagonal chiral, enantiomorphic space groups P6222 (space group number 180), and P6422 (space group number 181), respectively with correct configurations. The solutions were obtained by direct methods, using SIR-9225 and refined by full-matrix least squares refinement methods26 based on F2, using SHELX-97. All calculations were performed using Wingx package.27All non-hydrogen atoms were refined anisotropically except one highly disordered water molecule O2W (see below) which was refined isotropically only. Three crystallographically unique water molecules were located, O1W is at a general position, O3W lying on 2 fold axis and another highly disordered water molecule O2W lying at 222.These were assigned to be oxygen atoms due to their electron densities being close to it. The moiety formula thus have one Keggin POM unit, two K+ ions and seven water molecules out of which former four are coordinating to the two K+ ions and the latter three are lattice waters. No other completely occupied water molecule sites could be located from the residual electron density, which had maxima of 3.49 and 3.7 e/Å3in 1a and 1b, respectively. In both the cases these maxima lie very close (0.67 Å) to the disordered water molecule O2W, a fact suggesting positional disorder. The other residual electron density maxima are ~ 1.8 and 1.4 2 e/Å3 and may represent some partially occupied water oxygen but these could not be satisfactorily resolved and consequently no further attempts were made to identify any more water molecules. Otherwise also the residual electron densities of the order of 3 to 4 e/Å3 is a common feature in the X-ray crystal structures of POMs and their complexes.28 No H-atoms of water molecules in compounds 1a and 1b could be located from the difference Fourier map. The final residuals (R1 = 0.0355 for 1a and R1 = 0.0255 for 1b), are quite small. The crystal and refinement data parameters are given in Table 1. The crystal structures show very large solvent accessible voids in them which are due to packing forces (see discussion below).

Results: The K containing coordination polymers were formed during a reaction of the silicotungstic acid with KCl in the presence of manganese nitrate (for 1a) and europium nitrate 4 ACS Paragon Plus Environment

Page 5 of 16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(for 1b) in the presence of potassium chloride. These new species (1a and 1b) have been obtained during our attempts to make POM based inorganic frameworks of silicotungstic acid with Mn2+ and Eu3+, in the presence of KCl. In both the cases we ended up getting the formation of the coordination complex of silicotungstic acid with the K+ ion (EDS spectra, ESI Fig. S2). Neither of the reactions gave any incorporation of the transition metal ion but in the process a spontaneous resolution of the potassium complex occurred and two pure enantiomers of the K+ ion complex were resolved. It was revealed unambiguously by their single crystal X-ray diffraction analysis that shows that compounds 1a and 1b crystallize in enantiomeric space group P6222 and P6422, respectively. The Flack parameters of 1a and 1b are 0.01(3) and 0.02(3), respectively indicating enantiomeric purity of the single crystals. A direct reaction of KCl with [H4SiW12O40] also resulted in the formation of a similar coordination complex (1c) with K+ but apparently produced a conglomerate, because some of the atoms in the structure could not be refined anisotropically in any of the two enantiomorphic space groups, even on collecting a low temperature data on more than one crystal. Every time either Si or W and the oxygen atoms of the POM became non-positive definite and the refinement was not successful. The powder patterns of all three compounds are similar and match well with the generated one from the crystal structure of 1b (ESI, Fig. S3). As both the compounds have similar structures so the structure of only one of them (1b) is explained here. The single-crystal X-ray diffraction analysis reveals that the asymmetric unit contains 1/4th of the POM with Si lying at 222, a K+ ion and a lattice water molecule O3W lying on 2 fold axis and one, highly disordered lattice water molecule O2W also lying at 222. The moiety formula thus have one Keggin POM unit, two K+ ions and seven water molecules out of which four are coordinating to the two K+ ions and three are lattice waters. Thus there are as many as 12 coordinated water molecules and 9 lattice water molecules in the unit cell. For charge balancing the water molecules O3W lying on the symmetry 2 may be considered as the hydronium ions. Unfortunately in the wake of so many heavy W atoms, none of the hydrogens of any of the water molecules could be located. The [SiW12O40]4- anion exhibits a typical α-Keggin structure which consists of a central SiO44tetrahedron surrounded by 12 WO6, edge and corner sharing octahedrons present as four W3O13 groups (Fig. 1) The forty oxygen atoms are divided according to their different coordination environments into three groups, twelve terminal oxygens Ot (W=O), twenty four edge or corner 5 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 16

sharing bridging oxygens Ob (W-O-W) and four Oc oxygens bridging between Si and W (Si-OW). The Si-O distance 1.622(8) Å and W-Ot, W-Ob and W-Oc distances are 1.707(9) to 1.724(10) Å, 1.870(9) to 1.937(8) and 2.334(8) Å, respectively.

Fig.1. ORTEP of the asymmetric units at 30% probability for 1a and 1b.

Fig.2. Showing the partial structure of the 3D coordination polymer, W purple, K green, Si yellow, O red.

6 ACS Paragon Plus Environment

Page 7 of 16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Each Keggin ion is coordinated to eight K+ ions using the four Ot (O2) and four Ob (O3) atoms at four corners. Each O2 is unsymmetrically bridging between two symmetry related K+ ions but each O3 is coordinating to only one K+ ion. Thus each K+ ionis coordinated to four symmetry related Keggin ions and out of its eight coordinating sites; two are occupied by coordinated water molecules O1W, four by O2, and the remaining two by bridging O3oxygen atoms (Fig.2).The average K-O bond distances are K-O2 2.714(9) and 3.146(10) Å; K1-O3 2.853(8) Å, and K1-O1W as 2.929(14) Å. The coordination around K+ produces helical chains parallel to the [001] direction (Fig. 3).

Fig.3. Showing a right handed (1a) and a left handed (1b) helical axis passing through the coordination polymer, parallel to the c axis.

These helical chains are further linked by the silicotungstic anions to form an open, 3D chiral network with stacking down the c axis (Fig. 4a). This network has 1D nanotubular chiral channels running parallel to the c axis. The terminally bonded O4 and O9 oxygens of the POM are pointing inward within the channels. These channels are bound by six helical chains and are of approximately 14 Å in diameter (distance between two symmetry related terminal oxygens of the POM on opposite corners). Lattice water molecules O3W are partially filling these chiral channels of 1a and 1b. (Fig. 4b), whereas lattice water O2W are lying between the consecutive 7 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 16

POMs parallel to the b axis. The amount of void space available in the channels was calculated by removing occluded O3W water molecules and using CALC SOLV routine from PLATON.29 The volume of SAV calculated was 1320 Å3 (33.4% of the total unit cell volume) and with O3W molecules retained in the structure it came out to be 1122 Å3 (28.4%). The key to the framework assembly is the ability of the potassium ions to connect the particular clusters by selforganizing with (K···K= 4.710(4) Å). The two crystal structures (1a and 1b) are enantiomeric, is evident from Fig. 3 as well as Fig. 5, the latter shows them to be non-super imposable mirror images.

Fig. 4. (1a) shows the expanded view of a small portion of the 3D structure about one helical chain, Si atom: green ball. (1b) A polyhedral representation of packing of the inorganic POM based 3D network with water molecules in chiral channels, shown down the c axis. Si blue, K purple, W cyan and O red.


Page 9 of 16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(1a)

(1b)

Fig. 5. Partial structures of 1a and 1b showing them to be non-super imposable mirror images and chirality at the sillicon.

A search request to ICSD for compounds having K and silicotungstic acid, was returned with three examples of well refined structures, having K and α-Keggin ion [SiW12O40]4- which are isomorphous and isostructural with the present complex. In all of them there are Co(II) and/or Co(III) instead of Si(IV) in the Keggin anion30, 31 and they have been crystallized in hexagonal P6222 space group only. The other enantiomer has not been found in any of them. The central Co-O distance lies in the range 1.836(10) and 1.931(14) Å for Co (III) and Co(II), respectively whereas for the tetraalkylammonium salts of [SiW12O40]4- the central Si-O distance is 1.64(2)32 which is comparable to the Si-O distance in the present complex.

Powder X-ray diffraction studiesThe powder XRD for 1a and 1b are similar to those generated from their crystal structures and have been compared to the racemic mixture 1c as well (Fig. S3, ESI). These XRD patterns show the homogeneity of the samples. To further investigate the stability of the network at high temperature the powder XRD of 1b were recorder after heating it at various temperatures (Fig.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 16

6). On heating at 50 °C there is some slight change in the XRD pattern at 2θ 10.75°, but the rest of the pattern is similar to the one at RT and there is no significant difference further on heating after 100 °C up to 250 °C (upper limit for heating ). The experiment shows that the coordination polymer is quite stable after losing water molecules. The same is also found from the thermogravimetric analysis of the compounds (ESI, Fig. S4) which show that the network is stable even after 600 °C.

Fig. 6. Showing the XRPD for 1b after heating at various temperatures.

UV and CD Spectra-


Page 11 of 16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


The UV-vis spectra of 1a and 1bwere recorded in distilled water. A very broad and strong absorption band was recorded having a λmax. 291 nm (ε= 9860 M-1cm-1) for both 1a and 1b enantiomers. The band is obviously a composite band of a number of very close energy transitions which could not be resolved on our machine. These transitions may be assigned to pπ(O)-dπ* (W) transitions in the W=O bonds and dπ–pπ–dπ transitions between the energetic levels of the W–O–W tricentric bonds, respectively33 which fall in this range. We used these absorption bands to confirm the optical activity of the two enantiomers by recording CD spectra at these wavelengths. The results of CD measurements confirm the chiral nature of 1a and 1b enantiomers. As shown in Fig. 7, the crystals of 1a in distilled water show positive and negative Cotton effects, while the crystals of 1b in distilled water show opposite Cotton effects in the region of same wavelengths, which confirms spontaneous resolution during the course of the crystallization. There is no significant CD signal for the racemic mixture 1c.

Fig. 7. (a) UV spectra of two enantiomers (b) CD spectra of 1a and 1b showing opposite Cotton effects while no circular dichroism is shown by 1c.

ConclusionCrystallization induced simultaneous resolution has been shown to produce enantiomerically pure, POM-based coordination polymers with potassium ion. These compounds represent 3D 11 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 16

chiral frameworks of POM based, purely inorganic and robust networks which have been obtained from achiral precursors. Their crystal structures represent open framework with water molecules in the homochiral, nanotubular channels. The generation of homochirality from achiral precursors is still an unpredictable and unexplained phenomenon and most of the time two enantiomers are obtained in the form of a conglomerate from the same bulk material, during crystallization by spontaneous resolution (later on being separated manually, exploiting their physical attributes) and characterized using X-ray diffraction. In the present case the two enantiomeric homochiral crystals are being isolated from achiral precursors, during different crystallization experiments, i.e. in the presence of either europium nitrate or manganous nitrate which, to the best of our knowledge, is unprecedented, at least in chiral MOFs.

Supporting Information. EDS spectra of 1a and 1b; IR spectra of complexes 1a and 1b; XRPD and TGA of 1a and 1b. This material is available free of charge via the Internet at http://pubs.acs.org.

Acknowledgements- AK thanks DST for INSPIRE fellowship. GH thanks UGC for research grant under UPE (University with potential for excellence) scheme for GNDU. The authors are thankful to Prof. (Dr.) S.S. Chimni (Department of Chemistry, Guru Nanak Dev University) for the optical rotation measurements, Prof. (Dr.) S. Kukreti (Department of Chemistry, University of Delhi) for CD spectral measurements and Dr. Narinder Singh (Department of Chemistry, Indian Institute of Technology, Ropar) for EDS measurements.

References-

(1)(a) Fukaya, K.; Yamase, T. Angew. Chem. 2003, 115, 678-682. (b) Wu, C. D.; Lu, C. Z.; Zhuang, H. H.; Huang, J. S. J. Am. Chem. Soc. 2002, 124, 3836-3837. (c) Burkholder, E.; Zubieta, J. Chem. Commun. 2001, 2056-2057. (d) Bi, L. H.; Chubarova, E. V.; Nsouli, N. H.; Dickman, M. H.; Kortz, U.; Keita, B.; Nadjo, L. Inorg. Chem. 2006, 45, 8575-8583. (e) Sun, C.-Y.; Liu, S.-X.; Liang, D.-D.; Shao, K.-Z.; Ren, Y.-H.; Su, Z.-M. J. Am. Chem. Soc. 2009, 131, 1883-1888. (f) Cheng, J.W.; Zheng, S.T.; Ma, E.; Yang, G.Y. Inorg. Chem. 2007, 46, 10534-10538. 12 ACS Paragon Plus Environment

Page 13 of 16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(2) (a) Ding, N.; Chung, D. Y.; Kanatzidis, M. G. Chem. Commun. 2004, 1170-1171. (b) Wang, X. H.; Liu, J. F.; Pope, M. T. Dalton Trans. 2003, 957-960. (3) Li, J.; Qi, Y.; Wang, E.; Li, J.; Wang, H.; Li, Y.; Lu, Y.; Hao, N.; Xu, L.; Hu, C. J. Coord. Chem.2004, 57, 715-721. (4) (a) Carlucci, L.; Ciani, G.; Proserpio, D. M. Coord. Chem.Rev. 2003,246, 247-289. (b) Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A. O.;Snurr, R. Q.; O’Keeffe, M.; Kim, J.; Yaghi, O. M. Science 2010, 239, 424-428. (5) (a) Long, L. D.; Burkholder, E.; Cronin, L. Chem. Soc. Rev. 2007, 36, 105-121. (b) Sun, Y. Q.; Zhang, J.; Chen, Y. M.; Yang, G. Y. Angew. Chem., Int. Ed. 2005, 44, 5814-5817. (6) (a) Kçgerler, P.; Cronin, L. Angew. Chem. 2005, 117, 866-868. (b) Xu, L.; Lu, M.; Xu, M. M.; Wei, Y. G.; Peng, Z. H.; Powell, D. R. Angew. Chem. 2002, 114, 4303-4306.(c) Abrahams, B.F.; FitzGerald, N.J.; Robson, R. Angew. Chem., Int. Ed. 2012, 49, 2896-2899. (7)(a) Sokolov, M. N.; Adonin, S. A.; Sinkevich, P. L.; Vicent, C.; Mainichev, D. A.; Fedin, V. P.Dalton Trans. 2012, 41, 9889-9892. (b) Zhang, D.; Zhao, J.; Zhang, Y.; Hu, X.; Li, L.; Ma, P.; Wang, J.; Niu, J. Dalton Trans. 2013, 42, 2696-2699 (8) Zeolites and ordered mesoporous materials: Progress and prospects. In Studies in Surface Science; van Bekkum, H., Cejka, J., Eds.; Elsevier: Amsterdam, The Netherlands, 2005, 157. (9) Judd, D. A. J.; Nettles, H.; Nevins, N.; Snyder, J. P.; Liotta, D. C.; Tang, J.; Ermolieff, J.; Schinazi, R. F.; Hill, C. L. J. Am. Chem. Soc. 2001, 123, 886-897. (10) (a) Long, D. L.; Kçgerler, P.; Farrugia, L. J.; Cronin, L. Chem. Asian J. 2006, 1, 352-357. (b) Long, D. L.; Burkholder, E.; Cronin, L. Chem. Soc. Rev. 2007, 36, 105-121. (c) Streb, C.; Long, D. L.; Cronin, L. Chem. Commun. 2007, 471-473. (d) Fang, X. K.; Anderson, T. M.; Hou, Y.; Hill, C. L. Chem. Commun. 2005, 5044-5046. (11) (a) Pérez-García, L.; Amabilino, D. B. Chem. Soc. Rev. 2002, 31, 342-356. (b) PérezGarcía, L.; Amabilino, D. B. Chem. Soc. Rev. 2007, 36, 941-967. (12) Lorenz, H.; Perlberg, A.; Sapoundjiev, D.; Elsner, M. P.; Seidel- Morgenstern, A. Chem. Eng. Process 2006, 45, 863-873. (13) Coquerel, G.; Amabilino, D. B. In Chirality at the Nanoscale; Amabilino, D. B., Ed.; WileyVCH: Weinheim, 2009, 305-348. (14) Coquerel, G. In Novel Optical Resolution Technologies; Sakai, K.; Hirayama, N.; Tamura, R. Eds.; Springer-Verlag: Berlin, 2007, 1-51. 13 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 16

(15) Rekoske, J. E. AIChE J. 2001, 47, 2-5. (16) Jacques, J.; Collet, A.; Wilen, S. H. Enantiomers, Racemates and Resolutions; Krieger Publishing Company: Malabar, FL, 1994. (17) (a) Gao, E. Q.; Yue, Y. F.; Bai, S. Q.; He, Z.; Yan, C. H. J. Am. Chem. Soc. 2004, 126, 1419-1429. (b) He, C.; Zhao, Y. G.; Guo, D.; Lin, Z. H.; Duan, C. Y. Eur. J. Inorg. Chem.2007, 3451-3463. (c) Chen,C. Y.; Cheng, P. Y.; Wu, H. H.; Lee, H. M. Inorg. Chem. 2007, 46, 5691-5699. (18) Anderson, N. G. Org. Process Res. Dev. 2006, 10, 683-696. (19) (a) Li, J-R.; Tao, Y.; Yu, Q.; Bu, X-H.; Sakamoto, H.; Kitagawa, S. Chem. Eur. J. 2008, 14, 2771-2776.(b) An, H-Y.; Wang, E-B.; Xiao, D-R.; Li, Y-G.; Su, Z-M.; Xu, L. Angew. Chem. Int. Ed. 2006, 45, 904-908. (20) Bu, X-H.; Chen, W.; Du, M.; Biradha, K.; Wang, W-Z.; Zhang, R-H. Inorg. Chem. 2002, 41, 437-439. (21) Zheng, X-D.; Zhang, M.; Jiang, L.; Lu, T-B. Dalton Trans. 2012, 41, 1786-1791. (22) Tong, X-L.; Hu, T-L.; Zhao, J-P.; Wang, Y-K.; Zhang, H.; Bu, X-H. Chem. Comm. 2010, 46, 8543-8545. (23) Sharma, M.; Chatterjee, T.; Vindhya, H.; Das, S. K. Dalton Trans. 2012, 41, 1862-1866. (24) Chao Qin, Xin-Long Wang, Ling Yuan, and En-Bo Wang, Cryst. Growth Des. 2008, 8, 2093-2095. (25) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J. Appl. Crystallogr.1993, 26, 343. (26) Sheldrick, G. M. ActaCrystallogr. A. 2008, A64, 112. (27) Farrugia, L. J. J. Appl. Crystallogr.1999, 32, 837. (28) Li, J.; Chen, Y- G.; Zhang, C- J.; Kong, Q- J. J. MolecularStruc. 2009, 921, 233-238. (29) Spek, A. L.; Platon: A Multipurpose Crystallographic Tool; Utrecht University: Utrecht, The Netherlands, 2001. (30) Pastor, N. C.; Romero, P. C.; Jameson, G. B.; Baker, L. C. W. J. Am. Chem. Soc. 1991, 113, 5658-5663. (31) Baker, L. C. W.; McCutcheon, T. P. J. Am. Chem. Soc. 1956, 78, 4503-4510. (32) Fuchs, J.; Thiele, A.; Palm, R. Z. Naturforsch. 1981, 36b, 161-171.


Page 15 of 16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(33) Streb, C.; Ritchie, C.; Long, D-L.; Kögerler, P.; Cronin, L. Angew. Chem. Int. Ed. 2007, 46, 7579-7582.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 16

For graphics

Crystallization induced simultaneous resolution has been shown to produce enantiomerically pure, chiral POM-based coordination polymers with potassium ion, which are optically active. These compounds represent 3D chiral frameworks of POM based, purely inorganic and robust networks which have been obtained from achiral precursors. Their crystal structures represent open framework with water molecules in the chiral, nanotubular channels.

ACS Paragon Plus Environment

Spontaneous Resolution upon Crystallization of 3D, Chiral Inorganic

Recommend Documents