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Coordination driven axial chirality in a microporous solid assembled from an achiral linker via in situ CN couplingw
Prakash Kanoo,a Ritesh Haldar,b Soumya T. Cyriaca and Tapas Kumar Maji*ab
Downloaded by Cochin University of Science & Technology on 13 September 2011 Published on 09 September 2011 on http://pubs.rsc.org | doi:10.1039/C1CC13877D

Received 29th June 2011, Accepted 25th August 2011 DOI: 10.1039/c1cc13877d Metal mediated in situ CN coupling between 4,4 0 -azobipyridine and disodium-trans-glutaconate at room temperature has formed a new multifunctional linker Z-dhpe which subsequently self-assembles with Zn(II) or Cd(II) resulting in a chiral or an achiral metalorganic framework, respectively, depending on its dierent coordination modes. Metal mediated in situ coupling between two organic components for generating new ligands and their subsequent coordination with metal ions is an elegant method for fabrication of novel coordination compounds which are otherwise inaccessible in direct preparation from the components.1 In situ ligand synthesis, being very important in the context of organic chemistry, has also become an important approach in the crystal engineering of metalorganic frameworks2 (MOFs) exhibiting interesting properties like porosity, photoluminescence, magnetism, sensing etc.3 The hydro(solvo)-thermal method has been found to be very promising for many in situ metal/organic reactions towards the construction of MOFs of dierent dimensionalities.1b,4 Recently, Feller et al. have reported dimerization of L-aspartic acid involving in situ CN coupling to imminodisuccinic acid via a postulated fumaric acid intermediate, precisely coupling between an NH2 and a reactive alkene group, which leads to the formation of a coordination polymer at high temperature.3e Here we report an interesting observation of in situ CN coupling between two organic components, azpy and Na2tga, that leads to the formation of a new linker Z-dhpe (Z-dhpe = (Z)-2-(1,2-(dipyridin-4-yl)hydrazinyl)pent-2-enedioate) in a H2O/ EtOH medium at room temperature. On many occasions, spatial arrangement of in situ generated ligands becomes decisive in dictating the fate of nal structure. Chirality is one such property which may arise in solids because of the asymmetric arrangement of linkers in space.5 Instead of high temperature we preferred metal based coupling at RT which is well known
a

in synthetic organic chemistry. In the course of our study, we have found that Z-dhpe is capable of generating both a chiral and an achiral solid depending on its dierent coordination mode with d10-metal ions Zn(II) and Cd(II), respectively. Self-assembly of Z-dhpe with Zn(II) results in a chiral MOF, {Zn(Z-dhpe)3H2OEtOH}n (1) while with Cd(II) an achiral MOF {Cd2(Z-dhpe)25H2O2EtOH}n (2) at RT. The type of chirality found here is axial and the chiral axis passes through the newly formed CN bond as shown in Scheme 1 and Fig. S1, ESI.w These compounds represent the rst examples in MOFs where tga has been used as a component to assemble framework structures. Despite having a bulky structure of Z-dhpe, its unique distorted tetrahedral geometry allows to grow the polymeric structure in three crystallographic directions upon coordination with Zn(II) resulting in a porous chiral 3D framework structure. The compound has a BET surface area of 870 m2 g1 and shows excellent selective adsorption of CO2 over other gases (H2, N2, Ar, O2) at 195 K. To the best of our knowledge, synthesis of a porous MOF by metal mediated in situ ligand synthesis via CN bond formation under ambient conditions is yet to be accounted. Table S1 lists some of the reported in situ reactions in MOFs and their properties along with the one observed in this work. Single crystal X-ray diraction analysis suggests that compound 1 crystallizes in a chiral space group P212121.z The asymmetric unit of 1 comprises of one Z-dhpe, one Zn(II) atom with a distorted tetrahedral geometry, three water and one ethanol guest molecules. Single crystal structure of compound 1 clearly indicates the presence of a CN bond (C2N2 distance, 1.45 A)

Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientic Research, Jakkur, Bangalore 560 064, India. E-mail: tmaji@jncasr.ac.in; Fax: +91 80 2208 2766; Tel: +91 80 2208 2826 b New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientic Research, Jakkur, Bangalore 560064, India w Electronic supplementary information (ESI) available: Experimental details of synthesis, crystallography and physical measurements. Extensive gures, tables, TGA and PXRD plots. CCDC 830358 and 830359. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c1cc13877d

Scheme 1 Coordination driven self-assembly towards a chiral and an achiral MOF from an in situ generated organic linker (Z-dhpe) via the metal mediated CN coupling reaction.

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in Z-dhpe. The ligand has been further characterized by IR, 1H NMR, 13C NMR and mass spectra to establish the presence of a CN bond (Fig. S2S5, ESIw). Strong evidence comes up from 1H NMR spectra which suggest absence of the ethylene proton peak in Z-dhpe at the point where CN coupling has occurred (Fig. S3, ESIw). Moreover, a medium intensity peak at 1114 cm1 in the IR spectrum corroborates to the presence of a CN bond in 1. A blank reaction was carried out between Na2tga and azpy under similar conditions in the absence of Zn(II)/Cd(II). No reaction occurred between the two organic components up to 90 days which conrms the critical role of Zn(II)/Cd(II) in the formation of Z-dhpe. A proposed mechanism for the formation of the ligand is given in the ESIw (Scheme S1). Four Z-dhpe coordinate to a tetrahedral Zn(II) centre via two oxygen atoms (O1 and O4) from two dierent carboxylate groups and two nitrogen atoms (N1 and N4) from two pyridyl groups (Fig. S6, ESIw). The loss of molecular symmetry of azpy because of the change in hybridization of two nitrogen atoms N2 and N3 from sp2 to sp3 via CN coupling provides the sucient angle (B86.51) to the pyridyl rings to bend away from each other, which gives rise to a distorted tetrahedral geometry in the Z-dhpe linker (Fig. S1, ESIw). This nonlinear spatial disposition of pyridyl groups of Z-dhpe in its Z-conguration helps to grow the polymeric structure along crystallographic b and c axes while the alkyl bicarboxylate chain part allows to extend along the a direction resulting in a 3D framework structure (Fig. 1 and Fig. S7, ESIw). The chiral axis in 1 passes through the newly formed CN bond as shown in Scheme 1 and Fig. S1, ESI.w Single crystal of 1 is homochiral as suggested by Flack parameter obtained from X-ray crystallographic data (Table S2, ESIw). Successively, we collected single crystal data of four dierent crystals from dierent reaction batches and found all are homochiral but have mixed handedness. As a consequence, the bulk sample was found to be heterochiral.

Fig. 1 View of the 3D framework of 1 along the a direction. The channels are occupied by guest water (green balls) and ethanol (pink color) molecules.

Chirality in the present structure is completely coordination driven and very unique too as the assembly of the same ligand with Cd(II) (Fig. S6, ESIw) results in an achiral solid which crystallizes in the C2/c space group (Scheme 1). Unlike 1, the geometry around Cd(II) in 2 is octahedral (Fig. S6, ESIw) and the presence of an inversion centre in the structure renders the compound achiral. Further account about compound 2 will be detailed elsewhere. The most probable explanation for occurrence of chirality in 1 is the presence of a tetrahedral Zn(II) centre with four dierent ligand groups that resembles an asymmetric carbon. Three water and one ethanol guest molecules reside in the 1D channels of 1 extending along the crystallographic a axis decorated with pendant oxygen atoms of the carboxylate group. The approximate dimension of the dumble shaped channel is 12.5 5.25 A2 (Fig. 1, top). 6 Calculation using PLATON shows that the framework 1 possesses B50% void space to the total crystal volume after removing the guest molecules. Topological analysis with TOPOS 4.07 software suggests a 4-connected uninodal net in line with the observed geometry of Z-dhpe with the Schlai symbol {42.63.8} (Fig. S8, ESIw). To analyze the stability and integrity of compound 1 thermogravimetric analysis was carried out under a nitrogen atmosphere (Fig. S9, ESIw). There is a rapid weight loss (expt, 19%; calcd, 21%) in the temperature range of 35120 1C corresponding to the presence of guest water and ethanol molecules in the framework. Slight discrepancy in the weight loss is due to the release of some guest molecules at RT itself. Afterwards, a plateau was observed up to 200 1C and then an abrupt weight loss occurs which suggests collapse of the framework structure. The PXRD pattern of the desolvated compound, 1 0 [Zn(Z-dhpe)], shows negligible shift in peak positions suggesting integrity of the framework structure (Fig. S10, ESIw). However, broadening of some low angle peaks indicates loss of single crystallinity upon desolvation. To establish permanent porosity of 1 0 , N2 adsorption experiment was carried out at 77 K. Before isotherm measurement, as-synthesized compound 1 was evacuated under vacuum at 100 1C for B16 h to remove water and ethanol guest molecules to produce 1 0 . The isotherm shows a typical type-I prole with an uptake volume of 190 mL g1 suggesting the microporous nature of the framework (Fig. S11, ESIw). Calculation using the measured isotherm suggests that framework 1 0 has a BET surface area of B870 m2 g1 which draws comparison with some of the popular zeolitic MOFs, ZIF-95 (1050 m2 g1) and ZIF-100 (595 m2 g1) bearing tetrahedral Zn(II) nodes.8 After the permanent porosity of the framework has been established from the N2 adsorption study, we tested the compound for its uptake capacity for other gases. The CO2 adsorptiondesorption prole of 1 0 measured at 195 K also exhibits a type-I curve similar to the N2 isotherm. The framework shows an appreciable uptake of B42 weight% CO2 (9.96 mmol g1 at STP) without saturation in the measurement pressure range (Fig. 2). Analysis of the isotherm with the DubininRadushkevich9 (DR) equation suggests the value of isosteric heat of adsorption, (qst,f), to be 32 kJ mol1. At 298 K and 1 atm pressure the framework captures B9 weight% of CO2 (1.96 mmol g1) which is very close to the value reported for MOF-5 (2.1 mmol g1) and much higher than activated carbon-MAXSORB (0.5 mmol g1) and
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Notes and references

z Crystal data of 1: formula, C17H24ZnN4O8: Mr = 477.74, orthorhombic, space group P212121 (No. 19), a = 8.741(5), b = 14.796(5), c = 19.340(5) A, V = 2501.3(2) A3, Z = 4, T = 100 K, l (Mo-Ka) = 0.71073, rcalcd = 1.253 g cm3, m = 1.024 mm1, ymax = 31.97, total data = 15 504, unique reections = 8008, reections with I 4 2s(I) = 3074, Rint = 0.077, R = 0.086, wR2 = 0.2689 for all data, GOF = 0.92. Crystal data of 2: formula, C34H44Cd2N8O17, Mr = 1065.51, monoclinic, space group C2/c (No. 15), a = 25.4628(7), b = 9.8868(3), c = 20.2318(6) A, V = 4223.8(3) A3, Z = 4, T = 100 K, l (Mo-Ka) = 0.71073, rcalcd = 1.654 g cm3, m = 1.087 mm1, ymax = 22.1, total data = 21 220, unique reections = 2633, reections with I 4 2s(I) = 2342, Rint = 0.053, R = 0.0385, wR2 = 0.098 for all data, GOF = 1.1. CCDC 830358 (1) and 830359 (2). 1 (a) X.-M. Chen and M.-L. Tong, Acc. Chem. Res., 2007, 40, 162; (b) E. C. Constable, Metals and Ligand Reactivity, VCH, Weinheim, 1996, p. 245; (c) J. Burgess and C. D. Hubbard, Ligand substitution reactions, Adv. Inorg. Chem., 2003, 54, 71. 2 (a) S. Kitagawa, R. Kitaura and S. Noro, Angew. Chem., Int. Ed., 2004, 43, 2334; (b) C. Janiak, Dalton Trans., 2003, 2781; (c) T. K. Maji and S. Kitagawa, Pure Appl. Chem., 2007, 79, 2155; (d) G. Ferey, Chem. Soc. Rev., 2008, 37, 191; (e) J. C. Tan and A. K. Cheetham, Chem. Soc. Rev., 2011, 40, 1059; (f) K.-L. Zhang, H.-Y. Gao, N. Qiao, F. Zhou and G.-W. Diao, Inorg. Chim. Acta, 2008, 361, 153; (g) M. K. Bhunia, S. K. Das, M. M. Seikh, K. V. Domasevitch and A. Bhaumik, Polyhedron, 2011, 30, 2218; (h) Y.-N. Zhang, Y.-Y. Wang, L. Hou, P. Liu, J.-Q. Liu and Q.-Z. Shi, CrystEngComm, 2010, 12, 3840; (i) B. Gil-Hernandez, H. A. Hoppe, J. K. Vieth, J. Sanchiz and C. Janiak, Chem. Commun., 2010, 46, 8270; (j) P. Kanoo, R. Matsuda, M. Higuchi, S. Kitagawa and T. K. Maji, Chem. Mater., 2009, 21, 5860. 3 (a) O. R. Evans and W.-B. Lin, Acc. Chem. Res., 2002, 35, 511; (b) J. Y. Lu, Coord. Chem. Rev., 2003, 246, 327; (c) X.-M. Zhang, Coord. Chem. Rev., 2005, 249, 1201; (d) J.-P. Zhang and X.-M. Chen, Chem. Commun., 2006, 1689; (e) R. K. Feller, P. M. Forster, F. Wudl and A. K. Cheetham, Inorg. Chem., 2007, 46, 8717. 4 (a) R. G. Xiong, X. Xue, H. Zhao, X. Z. You, B. F. Abrahams and Z. L. Xue, Angew. Chem., Int. Ed., 2002, 41, 3800; (b) D. S. Liu, X. H. Huang, C. C. Huang, G. S. Huang and J. Z. Chen, J. Solid State Chem., 2009, 182, 1899; (c) G. B. Li, J. M. Liu, Z. Q. Yu, W. Wang and C. Y. Su, Inorg. Chem., 2009, 48, 8659; (d) S. T. Zheng, M. H. Wang and G. Y. Yang, Inorg. Chem., 2007, 46, 9503; (e) J. Wang, S. L. Zheng, S. Hu, Y. H. Zhang and M. L. Tong, Inorg. Chem., 2007, 46, 795. 5 R. E. Morris and X. Bu, Nat. Chem., 2010, 2, 353. 6 A. L. Spek, J. Appl. Crystallogr., 2003, 36, 7. 7 (a) V. A. Blatov, L. Carlucci, G. Ciani and D. M. Proserpio, CrystEngComm, 2004, 6, 378; (b) V. A. Blatov, A. P. Shevchenko and V. N. Serezhkin, J. Appl. Crystallogr., 2000, 33, 1193. 8 B. Wang, A. P. Cote, H. Furukawa, M. OKeee and O. M. Yaghi, Nature, 2008, 453, 207. 9 M. M. Dubinin, Chem. Rev., 1960, 60, 235. 10 A. R. Millward and O. M. Yaghi, J. Am. Chem. Soc., 2005, 127, 17998. 11 K. B. Lee, M. G. Beaver, H. S. Caram and S. Sircar, Ind. Eng. Chem. Res., 2008, 47, 8048. 12 (a) R. Vaidhyanathan, S. S. Iremonger, G. K. H. Shimizu, P. G. Boyd, S. Alavi and T. K. Woo, Science, 2010, 330, 650; (b) L. Pan, K. M. Adams, H. E. Hernandez, X. Wang, C. Zheng, Y. Hattori and K. Kaneko, J. Am. Chem. Soc., 2003, 125, 3062; (c) A. Comotti, S. Bracco, P. Sozzani, S. Horike, R. Matsuda, J. Chen, M. Takata, Y. Kubota and S. Kitagawa, J. Am. Chem. Soc., 2008, 130, 13664; (d) J. An, S. J. Geib and N. L. Rosi, J. Am. Chem. Soc., 2010, 132, 38; (e) P. Kanoo, G. Mostafa, R. Matsuda, S. Kitagawa and T. K. Maji, Chem. Commun., 2011, 47, 8106; (f) P. Kanoo and T. K. Maji, Eur. J. Inorg. Chem., 2010, 3762.

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Fig. 2 Selective CO2 gas adsorption over H2, N2, O2 and Ar by 1 0 at 195 K.

BPL carbon (0.4 mmol g1) (Fig. S12, ESIw).10,11 Measurement of adsorption isotherms at 195 K for other gases, such as H2, N2, O2 and Ar, shows negligible uptake suggesting the framework is highly selective towards CO2 gas. This type of selective adsorption phenomena is unique in MOFs.12 Abrupt decrease in N2 uptake from 77 K to 195 K could be accounted for higher thermal energy of the inert gas molecules which signicantly decreases interaction with the pore surfaces. Moreover, the structural analysis suggests that pore surfaces in 1 are decorated with free pendant oxygen atoms from the carboxylate groups as well as Zn(II) sites that makes the pore wall polar in nature. Since the CO2 molecule has a large quadrupole moment (1.4 1039 C m2) compared to other gas molecules, it interacts with the pore surface strongly resulting in high uptake at 195 K. In conclusion, we have shown that Zn(II)/Cd(II) mediate the in situ CN coupling reaction during construction of MOFs. The unusual distorted tetrahedral geometry of the newly in situ formed ligand, with a Z-conguration, and its asymmetric coordination with Zn(II) directs the structure in all the three crystallographic axes to generate a chiral 3D framework structure. The chirality in compound 1 is of axial type and is completely coordination driven. The microporous nature of the framework has been established by gas adsorption studies. More interestingly, the compound shows selective adsorption of CO2 gas over H2, N2, O2 and Ar at 195 K. Current eorts are underway in our laboratory for the synthesis of bulk enantiopure/enantiorich 1 via chiral induction or chiral additive eects, which is a prerequisite for its application in chiral recognition and asymmetric catalysis. The authors thank JNCASR and Department of Science and Technology, Government of India for nancial support. PK acknowledges CSIR, Government of India, for a senior research fellowship. We are thankful to Dr. Sridhar Rajaram of ICMS, JNCASR for helpful discussions.

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