amine Ligand - American Chemical Society

Article pubs.acs.org/crystal

Diverse Structures of Metal−Organic Frameworks Based on a New Star-Like Tri(4-pyridylphenyl)amine Ligand Ming-Dao Zhang, Chang-Miao Di, Ling Qin, Xiao-Qiang Yao, Yi-Zhi Li, Zi-Jian Guo, and He-Gen Zheng* State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China S Supporting Information *

ABSTRACT: Four new metal−organic frameworks based on a new star-like ligand tri(4pyridylphenyl)amine (TPPA), namely, {[Cd(TPPA)(trans-chdc)]}n (1), {[Co(TPPA)2(Dca)2]·(H2O)}n (2), {[Ni(TPPA)(bdc)(H2O)]·(H2O)4}n (3), {[Ni(TPPA)(trans-chdc)(H2O)]·(H2O)4}n (4), (trans-H2chdc = trans-1,4-cyclohexanedicarboxylic acid, D-H2ca. = Dcamphor acid, H2bdc = benzene-p-dicarboxylic acid), have been synthesized under solvothermal conditions. Compound 1 represents the first example of a 4-fold interpenetrating 3D metal−organic polyrotaxane framework, with {42.65.83}{42.6} AFUQOH topology. In 2, each D-ca2− anion links adjacent Co2+ atoms to a 2D framework, and only one N atom from each TPPA ligand is involved in coordination, which should be partly attributed to the weak flexibility of the TPPA ligand. Both 3 and 4 reveal 3-fold interpenetrating 3D frameworks bridged by TPPA ligands and bdc2− (or trans-chdc2−) anions, with {4.62}{43.67} crs topology. In addition, photophysical properties of 1 and the TPPA ligand in the solid state have also been studied.

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INTRODUCTION Metal−organic frameworks (MOFs) have attracted great attention not only for their potential applications in the fields of photochemical areas,1 gas adsorption and separation,2 molecular magnetism,3 heterogeneous catalysis,4 and nonlinear optics (NLO)5 but also for their aesthetic topologies.6 However, it is still a challenge to exactly predict the structure of MOFs.6 The self-assembly processes of MOFs are influenced by many factors, such as organic ligands,7 solvent systems,8 metal ions,9 and counterions.10 Among these factors, the coordination geometry of metal ions or clusters and the structural characteristics of polydentate organic ligands play an important role.6,7,9 Systematic studies of diverse ligands and metal ions, leading to different structures in the formation of coordination polymers, are thus important and of intense interest.6 Owing to their natural characteristics, the tripodal rigid multidentate ligands are prominent for constructing porous MOFs with aesthetic topological structure.11,12 Compared with benzene- and triazine-centered triangular ligands, the N-centered triangular ligands more easily meet the geometric requirement of metal ions.12g Recently, a triangular N-centered ligand, namely, tris(4-(1H-imidazol-1-yl)phenyl)amine (TIPA, Scheme 1), has been investigated intensely in the fields of coordination polymers.12 Dozens of coordination polymers, with porosity, chirality, and aesthetic topology structures, have been reported.12 The most impressive example is a 54 interpenetrating network with 103-srs topology constructed by Ag+ and TIPA ligand.12e In addition, our group has reported an unprecedented 3D cluster polymer, based on Mo(W)/Cu/S and TIPA, exhibiting strong third-order nonlinear optical properties.12i A prominent characteristic of TIPA ligand is that three nitrogen coordination © 2012 American Chemical Society

Scheme 1. Carboxylate Ligands and N-Containing Ligands

atoms can adjust coordination orientation when imidazole groups rotate along the C−N bonds connecting phenyl and imidazolyl.12f When three imidazolyl groups of TIPA were replaced by three pyridyl groups (TPPA ligand, Scheme 1), the conformational and geometrical flexibility weakened because nitrogen coordination atoms were on the axes of phenyl-pyridyl arms. How will TPPA ligand behave when it takes part in the construction of MOFs with different metal ions and carboxylic acids? Received: March 23, 2012 Revised: June 15, 2012 Published: July 10, 2012 3957

dx.doi.org/10.1021/cg300386p | Cryst. Growth Des. 2012, 12, 3957−3963

Crystal Growth & Design

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Table 1. Crystallographic Data and Structure Refinement Details for Compounds 1−4

a

frameworks

1

2

3

4

formula formula weight crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) Z V (Å3) Dcalcd (g cm−3) μ(Mo Kα) (mm−1) F(000) temperature (K) theta min,max (deg) tot., uniq. data R(int) observed data [I > 2σ(I)] Nref, Npar R1,wR2 (all data)a S min and max resd dens (e·Å−3)

CdC41H34N4O4 759.12 monoclinic C2/c 16.867(3) 17.127(3) 11.970(2) 90.00 93.268(3) 90.00 4 3452.3(10) 1.461 0.681 1552 293(2) 2.927, 27.483 11384, 3975 0.0431 3700 3975, 229 0.0304, 0.0758 1.038 −0.627, 0.945

Co2C86H78N8O9 1485.42 triclinic P1̅ 13.0956(15) 13.3473(15) 21.610(2) 103.591(2) 100.939(2) 91.078(2) 2 3596.8(7) 1.372 0.529 1552 293(2) 1.64, 26.00 19173, 13730 0.0290 9815 13730, 415 0.0595, 0.1197 1.067 −0.535, 0.314

NiC41H30N4O5 717.40 monoclinic P21/n 17.7338(19) 9.9058(10) 22.944(3) 90.00 91.794(2) 90.00 4 4028.6(7) 1.183 0.526 1488 296(2) 1.43, 25.00 21832, 7080 0.0636 4040 7080, 455 0.0633, 0.1542 1.091 −0.375, 0.597

NiC41H36N4O5 723.45 monoclinic P21/n 17.005(2) 10.5930(13) 24.0013(19) 90.00 91.215(3) 90.00 4 4022.5(8) 1.112 0.491 1512 291(2) 1.45, 26.00 25240, 8483 0.0441 6170 8483, 460 0.0529, 0.1026 1.038 −0.284, 0.294

R1 = Σ||Fo| − |Fc||/|Σ|Fo|. wR2 = {Σ[w(Fo2 − Fc2)2]/Σ[w(Fo2)2]}1/2; where w = 1/[σ2(Fo2) + (aP)2 + bP] and P = (Fo2 + 2Fc2)/3. (m), 1595 (s), 1520 (s), 1485 (s), 1404 (s), 1327 (s), 1292 (s), 1269 (s), 1228 (s), 1011 (w), 926 (w), 850 (w), 814 (s), 752 (s), 673 (w), 538 (m), 507 (m), 476 (w). Synthesis of 2. A mixture of Co(NO3)2·6H2O (29.1 mg, 0.1 mmol), TPPA (47.6 mg, 0.1 mmol), and D-camphor acid (20.0 mg, 0.1 mmol) was dissolved in 15 mL of DMF/H2O (1/2). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (25 mL) under autogenous pressure and heated at 120 °C for 3 days. Purple crystals of 2 were collected in 57% yield (based on TPPA ligand). Calcd for Co2C86H78N8O9: C, 69.54%; H, 5.29%; N, 7.54%. Found: C, 69.49%; H, 5.34%; N, 7.57%. IR(KBr, cm−1): 3419 (s), 3047 (m), 2964 (m), 2887 (w), 2397 (m), 1600 (s), 1495 (m), 1402 (m), 1327 (m), 1288 (m), 1228 (w), 1180 (w), 1120 (m), 817 (s), 756 (m). Synthesis of 3. A mixture of Ni(NO3)2·6H2O (30.0 mg, 0.1 mmol), TPPA (47.6 mg, 0.1 mmol), and benzene-p-dicarboxylic acid (16.6 mg, 0.1 mmol) was dissolved in 15 mL of DMF/H2O (1/1). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (25 mL) under autogenous pressure and heated at 90 °C for 3 days. Green crystals of 3 were collected in 47% yield (based on TPPA ligand). Calcd for NiC41H38N4O9: C, 62.38%; H, 4.85%; N, 7.10%. Found: C, 62.50%; H, 4.86%; N, 7.19%. IR(KBr, cm−1): 3418 (s), 3401 (m), 2234 (w), 1670 (s), 1593 (s), 1487 (s), 1382 (s), 1283 (m), 1226 (m), 1079 (m), 1008 (m), 806 (s), 748 (s), 518 (s). Synthesis of 4. A mixture of Ni(NO3)2·6H2O (30.0 mg, 0.1 mmol), TPPA (47.6 mg, 0.1 mmol), and trans-1,4-cyclohexanedicarboxylic acid (17.2 mg, 0.1 mmol) was dissolved in 15 mL of DMF/MeCN/H2O (1/ 1/2). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (25 mL) under autogenous pressure and heated at 95 °C for 3 days. Green crystals of 4 were collected in 52% yield (based on TPPA ligand). Calcd for NiC41H44N4O9: C, 61.90%; H, 5.58%; N, 7.04%. Found: C, 61.81%; H, 5.53%; N, 7.01%. IR(KBr, cm−1): 3411 (s), 2926 (w), 1667 (m), 1603 (s), 1487 (s), 1412 (m), 1323(m), 1226(m), 1007 (w), 910 (w), 818 (m), 752 (m), 522 (m). X-ray Crystallography. X-ray crystallographic data of 1 and 2 were collected at room temperature using epoxy-coated crystals mounted on glass fiber. X-ray crystallographic data of 3 and 4 were collected at room temperature by way of sealing the better single crystals in a quartz tube with mother liquor. X-ray crystallographic data of these compounds

Herein, three carboxylate ligands with different rigidity, namely, trans-1,4-cyclohexanedicarboxylic acid (transH2chdc),13 D-camphor acid (D-H2ca),14 and benzene-p-dicarboxylic acid (H2bdc)15 (Scheme 1), were used as coligands to react with the TPPA ligand and different bivalent metal salts. Then, four new compounds were obtained under solvothermal conditions, namely, {[Cd(TPPA)(trans-chdc)]}n (1), {[Co(TPPA) 2 (D-ca) 2 ]·(H 2 O)} n (2), {[Ni(TPPA)(bdc)(H 2 O)]·(H 2 O) 4 } n (3), and {[Ni(TPPA)(trans-chdc)(H2O)]·(H2O)4}n (4). All compounds were characterized by elemental analysis, IR spectra, X-ray powder diffraction experiment, and X-ray crystallography. The crystal structures and topological analyses of these compounds are presented. Further, the luminescent properties of TPPA ligand and compound 1 have also been studied.

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EXPERIMENTAL SECTION

Materials and Measurements. Reagents and solvents employed were commercially available. The synthetic route and preparation details of TPPA ligand are presented in the Supporting Information. IR absorption spectra of the compounds were recorded in the range of 400−4000 cm−1 on a Nicolet (Impact 410) spectrometer with KBr pellets. C, H, and N analyses were carried out with a Perkin-Elmer 240C elemental analyzer. Powder X-ray diffraction (PXRD) measurements were performed on a Bruker D8 Advance X-ray diffractometer using Mo−Kα radiation (λ = 0.71073 Å) in which the X-ray tube was operated at 40 kV and 40 mA. Luminescent spectra were recorded on a PerkinElmer LS55 fluorescence spectrophotometer at room temperature. Synthesis of 1. A mixture of Cd(NO3)2·6H2O (30.1 mg, 0.1 mmol), TPPA (47.6 mg, 0.1 mmol), and trans-1,4-cyclohexanedicarboxylic acid (17.2 mg, 0.1 mmol) was dissolved in 15 mL of DMF/MeCN/H2O (1/ 1/2). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (25 mL) under autogenous pressure and heated at 95 °C for 3d. Pale yellow crystals of 1 were collected in 60% yield (based on TPPA ligand). Calcd for CdC41H34N4O4: C, 64.87%; H, 4.51%; N, 7.38%. Found: C, 64.81%; H, 4.53%; N, 7.35%. IR(KBr, cm−1): 3405 (s), 2848 3958



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were collected on a Bruker Apex Smart CCD diffractometer with graphite-monochromated Mo−Kα radiation (λ = 0.71073 Å). Structure solutions were solved by direct methods, and the non-hydrogen atoms were located from the trial structures and then refined anisotropically with SHELXTL using full-matrix least-squares procedures based on F2 values.16 The hydrogen atom positions were fixed geometrically at calculated distances and allowed to ride on the parent atoms. The disordered C atoms in compound 2 (C73, C83) and the disordered C atoms and N atoms in 3 (N3, C37, C38, C39, C40, and C41) were refined using C or N atoms split over two sites with a total occupancy of 1. The distributions of peaks in the channels of 3 and 4 were chemically featureless to refine using conventional discrete atom models. To resolve these issues, the contribution of the electron density by the remaining water molecule was removed by the SQUEEZE routine in PLATON.17 Numbers of solvent water molecules in 3 and 4 were obtained by element analyses. The relevant crystallographic data are presented in Table 1, while the selected bond lengths and angles are given in the Supporting Information (Table S1). A semiempirical absorption correction was applied using SADABS.18 The topological analysis and some diagrams were produced using the TOPOS program.19

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RESULTS AND DISCUSSION Crystal Structure of {[Cd(TPPA)(trans-chdc)]}n (1). The crystal structure determination reveals that compound 1 crystallizes in monoclinic crystal system of C2/c. The asymmetric unit contains one Cd2+ atom, one TPPA ligand, and one deprotonated trans-1,4-cyclohexanedicarboxylic acid. The local coordination geometry around the Cd2+ atom is depicted in Figure 1a. The Cd1 atom coordinates to four oxygen atoms from two distinct trans-chdc2− anions and three N atoms from three different TIPA ligands; thus, the Cd2+ atoms can be considered as 5-connecting nodes. Each TPPA ligand links three Cd atoms, acting as a 3-connecting node to form a 1D ladder-like chain (Figure 1b). In structure 1, adjacent two parallel chains are joined by two trans-chdc2− ligands. Meanwhile, both trans-chdc2− ligands are joined by one Cd2+ atom. Besides, another 1D ladder-like chain is joined with above Cd2+ atom. Finally, a single 3D framework is created by repeating these joints (Figure 1c). There exist rectangular channels (Figure 1d) with a cross-section of approximately 18 × 20 Å (excluding Vander Waals radii) in the single 3D framework, which is almost twice the area of the analogous channels in the previously reported polymers.12g So the channel is large enough to accommodate three other equivalent ones (Figure 1e), giving rise to a 4-fold interpenetrating framework. Upon interpenetration, compound 1 contains a small solvent accessible void space of 2.9% of the total crystal volume calculated by PLATON. The Schläfli symbol for this binodal net is {42.65.83}{42.6}, and the topology type of this net is AFUQOH (Figure 1f). The ladder-like chains (Figure 1b) and deprotonated trans1,4-cyclohexanedicarboxylic acids can be considered as successions of loops and rods, indicating that compound 1 possess the highly rare fascinating polyrotaxane characters. As far as we know, there is only one example of interpenetrating (2-fold) 3D metal−organic framework with polyrotaxane features reported.12b Therefore, compound 1 represents the first example of a 4-fold interpenetrating 3D framework with polyrotaxane features. Crystal Structure of {[Co(TPPA)2(D-ca)2]·(H2O)}n (2). The crystal structure determination reveals that compound 2 crystallizes in the triclinic crystal system of P1̅. The asymmetric unit contains two Co2+ atoms, two TPPA ligands, two D-ca2− ligands, and one free water molecule (Figure 2a). As shown in

Figure 1. (a) Coordination environment of the Cd2+ atoms in 1. The hydrogen atoms are omitted for clarity (30% ellipsoid probability). Symmetry codes: #1 = −1.5 + x, 1.5 − y, −0.5 + z; #2 = 2 − x, y, 1.5 − z; #3 = 2.5 − x, 1.5 − y, 2 − z. (b) View of the ladder-like chain. (c) Perspective view of the 3D framework of 1 (the TPPA ligand is simplified to a 3-connecting node for clarity). (d) Top view of the rectangular channels in 1; the approximate width and height unit are marked. (e) View of 4-fold interpenetrating 3D architecture of 1. (f) Schematic view of the AFUQOH topology of structure 1.

Figure 2a, both Co1 and Co2 are six-coordinated by one nitrogen atom from one TPPA ligand and five carboxylate oxygen atoms from four D-ca2− ligands. For each TPPA ligand, there is only one nitrogen atom from one pyridyl group coordinating to Co2+ atom, which should be partly attributed to the weak flexibility of the TPPA ligand. The coordination modes of the two D-ca2− ligands in asymmetric unit were different (Figure 2b). The two carboxylate groups (O1, O2, O3, and O4) of one D-ca2− ligand take the μ3chelating-bridging tridentate mode, while the two carboxylate groups (O5, O6, O7, and O8) of another D-ca2− ligand adopt chelating in a bidentate mode. Each D-ca2− anion acts as a bidentate ligand to link adjacent Co2+ atoms to a 2D framework (Figure 2c), while only one N atom from each TPPA ligand coordinated to each Co2+ atom (Figure 2d), which may be attributed to the rigidity of TPPA ligand. Crystal Structure of {[Ni(TPPA)(bdc)(H2O)]·(H2O)4}n (3). The crystal structure determination reveals that compound 3 crystallizes in the monoclinic crystal system of P21/n. The asymmetric unit contains one Ni2+ atom, one TPPA ligand, one 3959



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Figure 2. (a) Coordination environment of the Co2+ atoms in 2. The hydrogen atoms and free water molecules are omitted for clarity (30% ellipsoid probability). Symmetry codes: #1 = 2 − x, 3 − y, 1 − z; #2 = x, 1 + y, z; #3 = 2 − x, 2 − y, 1 − z; #4 = 1 − x, 2 − y, 1 − z. (b) Different coordination modes of the two D-ca2− ligands in each asymmetric unit. (c) Views of the 2D network along with the c axis (the TPPA ligands are omitted). (d) Packing drawing of 2.

channel with a cross-section of approximately 10 × 24 Å in the single network (Figure 3d). The channel is so large that the two other 3D frameworks can be accommodated in this channel (Figure 3f). According to a calculation performed using PLATON, compound 3 contains a solvent accessible void space of 19.8% of the total crystal volume. The Schläfli symbol for this binodal net is {4.62}{43.67}, and the topology type of this net is crs (Figure 3f). Crystal Structure of {[Ni(TPPA)(trans-chdc)(H2O)]·(H2O)4}n (4). Although the coligands of 3 and 4 are different, X-ray analysis reveals that compounds 3 and 4 are isostructural from the topological point. There is no obvious difference of the coordination modes of Ni2+ in 3 and 4 (Figure S3, Supporting Information). Schematic representation of a 63 layer of 4 is shown in Figure S4, Supporting Information. Perspective views of the single 3D framework of 4 along the c and a axes are shown in Figures S5 and S6, Supporting Information (simplified picture). Distances of adjacent N4 and Ni atoms (10.538 to 10.630 Å) in 4 are close to that in 3 (10.609 to 10.651 Å). However, distances of adjacent Ni2+ atoms connected by trans-chdc2− (10.962, 11.156 Å) in 4 are smaller than that (11.280, 11.361 Å) in 3, which may lead to a slight difference in the size of the channel (Figure 4a). Similarly to 3, the Ni2+ atoms

bdc2− ligand, one coordinated water molecule, and lattice solvent molecules. Each Ni2+ atom is coordinated by three pyridine nitrogen atoms from three different TPPA ligands, one oxygen atom from one coordinated water molecule, and two oxygen atoms from two different bdc2− ligands (Figure 3a). The coordination environment at Ni2+ can be described as a {NiN3O3} distorted octahedron, with the axial positions occupied by one N donor atom from one TPPA ligand and one oxygen atoms from one bdc2− ligand (Figure 3a). The equatorial plane consists of two N donor atoms from another two TPPA ligands, one oxygen atom from another one bdc2− ligand, and one oxygen atom from one coordinated water molecule. TPPA ligands are coordinated to the Ni2+ atom to form 2D hexagonal grid planar layers (Figure 3b). Such layers are further connected by bdc2− ligands (Figure 3c), leading to the formation of a 3D framework. Better insight into the 3D frameworks can be accessed by the topological method. The Ni2+ atom can be regarded as a fiveconnected node, the TPPA ligand can be considered as a threeconnected node (distances of N4 and Ni: 10.609 to 10.651 Å), and each bdc2− ligand can be considered as a linear linker (distances of corresponding Ni−Ni: 11.280, 11.361 Å), thus forming a (3,5)-connected network (Figure 3e). There is also a 3960



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Figure 3. (a) Coordination environment of the Ni2+ ions in 3. The hydrogen atoms and lattice water molecules are omitted for clarity (30% ellipsoid probability). (b) Schematic representation of a 63 layer of compound 3. (c) Perspective view of single 3D framework of 3 along the c axis, showing that adjacent equivalent layers are linked by bdc2− to form a 3D framework. (d) Top view of the rectangular channel in 3; the approximate width and height unit are marked. (e) Perspective view of the single 3D framework of 3 (TPPA ligand and bdc ligand were simplified to 3-connecting and 2-connecting nodes, respectively, for clarity). (f) Schematic view of the crs topology of structure 3.

and the TPPA ligand can be regarded as five- and threeconnected nodes, respectively (Figure 4b). Photophysical Properties. Luminescent compounds are of great interest due to their various appliatoms in chemical sensor, photochemistry, and light-emitting diodes (LEDs).20 Compound 1 is insoluble in common organic solvents, hence its photoluminescence property was investigated in the solid state at

room temperature. Photoluminescence property of free TPPA ligand was studied in solution state (1 mM in CHCl3). As shown in Figure 5, the free TPPA ligand exhibits an intense emission

Figure 5. Excitation (black curves) and emission (blue curves) spectra of free TPPA ligand (1 mM in CHCl3) and 1 (solid state) at room temperature.

between 480 and 600 nm (λmax = 525 nm upon excitation at 420 nm), which is red-shifted by 120 nm compared to TIPA12b (λmax = 405 nm upon excitation at 388 nm). The emissions of 1 and TPPA ligand have similar profiles. Compound 1 exhibits slightly blue-shifted emission (λmax = 519 nm upon excitation at 420 nm) in comparison with the free TPPA ligand, which can be ascribed

Figure 4. (a) Top view of the rectangular channel in 4; the approximate width and height unit are marked. (b) Schematic view of the crs topology of structure 4. 3961



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to the weak π*−π transitions of the TPPA ligands upon metal coordination. Furthermore, the emission decay lifetimes of 1 and free TPPA ligand were monitored. The luminescent decay curves can be fitted with a double-exponential decay function:21 τ1 = 2.90 ns (100%) for free TPPA ligand (Figure S11, Supporting Information), and τ1 = 2.34 ns (65.15%) and τ2 = 11.05 ns (34.85%) for 1 (Figure S12, Supporting Information). The luminescent lifetimes of 1 and free TPPA ligand do not match well with each other, indicating that the emission of compound 1 is probably not only attributed to the π*−π transitions of the TPPA ligands upon metal coordination but also attributed to the other interactions, such as ligand-to-metal charge-transfer (LMCT) transitions.22 PXRD Results. To confirm whether the crystal structure is truly representative of the bulk materials, a PXRD experiment was carried out for compounds 1−4. The PXRD experimental and computer-simulated patterns of the compounds 1−4 are shown in the Supporting Information, Figures S7−S10, and they show that the bulk synthesized materials and the measured single crystal for 1−4 are the same.

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CONCLUSIONS In this work, four new metal−organic frameworks have been successfully synthesized by the self-assembly of the TPPA ligand, carboxylate ligands (trans-H2chdc, D-H2ca, or H2bdc), and various metal ions under solvothermal conditions. Compound 1 represents the first example of a 4-fold interpenetrating 3D metal−organic framework with polyrotaxane features. In 2, each 2− D-ca anion links to two adjacent Co2+ ions to generate a 2D framework. Compounds 3 and 4 reveal 3-fold interpenetrating 3D frameworks. In addition, photophysical properties of 1 and the TPPA ligand were also studied. Further study about this starlike tri(4-pyridylphenyl)amine ligand is in progress.

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ASSOCIATED CONTENT

S Supporting Information *

Selected bond lengths and angles, synthesis of TPPA, complementary drawings for crystal structures, simulated and experimental X-ray powder diffraction patterns, emission decay curves, and X-ray crystallographic files in cif format for 1−4. This material is available free of charge via the Internet at http://pubs. acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Fax: 86-25-83314502. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by grants from the Natural Science Foundation of China (20971065, 91022011, and 21021062) and National Basic Research Program of China (2010CB923303).

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REFERENCES

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amine Ligand - American Chemical Society

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