The Power of Heterometalation through Lithium for Helix Chain-Based

Communication Cite This: Cryst. Growth Des. 2017, 17, 5634-5639

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The Power of Heterometalation through Lithium for Helix ChainBased Noncentrosymmetric Metal−Organic Frameworks with Tunable Second-Harmonic Generation Effects Yong-Peng Li, Xing-Xia Wang, Shu-Ni Li, Hua-Ming Sun,* Yu-Cheng Jiang, Man-Cheng Hu, and Quan-Guo Zhai* School of Chemistry & Chemical Engineering, Key Laboratory of Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi’an, Shaanxi, 710062, P. R. China S Supporting Information *

ABSTRACT: We demonstrate herein a general strategy for developing acentric or chiral nonlinear optical MOFs from centrosymmetric ligands by shifting the asymmetrical roles to the metal centers through heterometalation. With 1,3,5-benzenetricarboxylic acid (H3BTC), a very common polyfunctional centric ligand, the Li+/Zn2+, Li+/Co2+, or Li+/Cd2+ heterometallic combinations successfully led to five new noncentrosymmetric metal−organic frameworks, namely, {[Zn(HBTC)(H 2 O)]} n (SNNU-71), {Li4[Cd2(HBTC)(BTC)2]}n (SNNU-72), {CoLi(BTC)(DMA)2}n (SNNU-73), {CdLi2(BTC)4/3(H2O)3}n (SNNU-74), and {Li2[Zn3Li5(BTC)4(MTAZ)(H2O)4]}n (MTAZ = 5-methyl tetrazole, SNNU-75). All these MOFs are acentric or chiral on the base of helical chain building blocks and four colorless members of them show remarkable and tunable SHG effects. Remarkably, more than 1000 metal-BTC frameworks are reported to date and most of them are centrosymmetric due to the C3-symmery of BTC ligands. Clearly, our heterometalation approach greatly increases the possibility for induction of spontaneous resolution, which provides a fresh opportunity for the development of noncentrosymmetric functional MOF materials.

A

needs to be done to understand and explore the spontaneous resolution process of acentric MOFs. We propose here a general strategy for developing acentric or chiral MOFs from centrosymmetric ligands by shifting the asymmetrical roles to the metal centers. In other words, we demonstrated that heterometalation is a powerful method to eliminate the symmetry of organic ligand and therefore produce acentric or chiral MOFs from centrosymmetric ligands. As an important component for the development of inorganic NLO materials such as LiBO3 and LiNbO3,40−43 lithium is first selected in our work. Taking the small radius and generally 4-coordinated tetrahedral geometry of Li+ into account,44−46 we speculate that the heterometalation of Li+ and transition metal ions such as Zn2+, Co2+, and Cd2+ should be an effective combination to eliminate the symmetry of organic ligand through the coordination process. On the other hand, 1,3,5-benzenetricarboxylic acid (H3BTC), a very common polyfunctional centric ligand, was selected in our work to demonstrate the efficiency of our heterometalation method.

s one of the most important nonlinear optical (NLO) behaviors, second-harmonic generation (SHG) has been widely used in the domain of photonics and optoelectronics.1−9 Recently, SHG active metal−organic frameworks (MOFs) have been receiving increasing interest because they combine advantages of both inorganic and organic NLO materials.10−14 Due to the requirement of noncentrosymmetry for NLO materials, the rational design and preparation of noncentrosymmetric MOFs are of great challenge because most crystalline materials are inclined to crystallize in a centric lattice. The general approach to noncentrosymmetric MOFs is using unsymmetrical bridging ligands or employing chiral molecules, which is the simplest method to break the centrosymmetry of a framework.15−25 For example, Lin, Cui, and Luo et al. have demonstrated several series of NLO frameworks by employing acentric or chiral ligands.26−33 Because of the limitation and very often the high cost of the unsymmetrical and chiral pool, it is highly desirable to create NLO materials other ways. In fact, taking advantage of the spontaneous resolution process, acentric or chiral MOFs may also be formed by the assembly of metal ions with centrosymmetric linkers.34,35 However, such formation of acentric MOF materials generally cannot be guaranteed since many factors (composition, templates, solvents, and so on) may affect the ultimate molecular organization in crystals.36−39 Therefore, more work © 2017 American Chemical Society

Received: September 18, 2017 Revised: October 9, 2017 Published: October 13, 2017 5634

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Table 1. Summary of Crystal Data and Refinement Resultsa α/β (deg)

γ (deg)

R (F)

flack parameter

13.767(8)

90

120

0.0573

0.11(2)

17.2692(15)

22.649(2)

90

90

0.0613

0.07(4)

13.2699(3)

13.2699(3)

17.6469(10)

90

90

0.0789

0.02(4)

R3c

31.0217(6)

31.0217(6)

16.2941(7)

90

120

0.0478

−0.02(4)

P3221

23.7899(8)

23.7899(8)

13.1159(10)

90

120

0.0671

0.02(4)

space group

a (Å)

b (Å)

name

formula

SNNU71 SNNU72 SNNU73 SNNU74 SNNU75

{[Zn(HBTC)(H2O)]}n

P61

21.436(8)

21.436(8)

{Li4[Cd2(HBTC)(BTC)2]}n

P212121

16.0672(13)

{CoLi(BTC)(DMA)2}n

P41212

{CdLi2(BTC)4/3(H2O)3}n {Li2[Zn3Li5(BTC)4(MTAZ)(H2O)4]}n

a

c (Å)

H3BTC = 1,3,5-benzenetricarboxylic acid; MTAZ = 5-methyl-1H-tetrazole; DMA = N,N′-dimethylacetamide.

Figure 1. Six types of helical chains observed in this work: SNNU-71 (a), SNNU-72 (b and c), SNNU-73 (d), SNNU-74 (e), and SNNU-75 (f).

Under solvothermal condition, the self-assembly of Li+/Zn2+, Li /Co2+, or Li+/Cd2+ heterometallic combinations with H3BTC led to five new metal−organic frameworks (SNNU71−75), which all crystallize in acentric or chiral space groups. Five noncentrosymmetric MOFs are all constructed from helical chain building blocks and four colorless members show high and tunable SHG effects. Notably, the Li+ ions not only function as templates, but also serve as nodes of dimensional grids to extend the product structure. Clearly, our heterometalation approach demonstrated herein greatly increases the possibility for induction of spontaneous resolution, which provides a fresh opportunity for the development of functional acentric or chiral MOF materials. Acentric MOFs SNNU-71−75 were synthesized under similar solvothermal conditions with the reactions of H3BTC, LiCl·H2O, and corresponding transition-metal nitrates at 100 °C for 4−6 days. Although many factors could have an impact on the formation of MOFs under solvothermal process, the compared experiments show that solvent is a key factor for the MOF crystallization. In fact, five different kinds of solvents were involved: DMF/DMP for SNNU-71, DMF for SNNU-72, DMA for SNNU-73, DMA/1,4-dioxane for SNNU-74, and DMA/methanol for SNNU-75. The change of solvent for any of them all led to unidentified powder or other reported transition metal−BTC MOFs. Also, the presence of Li+ plays a vital role for the formation of these noncentrosymmetric

structures. The compared experiments showed that all these structures cannot be obtained without LiCl·H2O. Overall, a suitable solvent together with the presence of Li+ successfully led to the formation of this series of noncentrosymmetric MOFs (Table 1). The flack parameters are of 0.11(2), 0.07(4), 0.02(4), −0.02(4), and 0.02(4) for SNNU-71−75, which clearly indicate the acentric or chiral structures of these MOFs. The crystal photos, powder XRD and FT-IR spectra of SNNU71−75 have been provided in Figures S1−S3, which clearly confirmed the phase purity of as-synthesized products. Single-crystal X-ray diffraction analyses reveal that SNNU-71 crystallizes in the chiral hexagonal space group P61 and the asymmetric unit consists of one Zn(II), one HBTC2−, and one coordinated water molecule. Zn atom shows a slightly distorted tetrahedral geometry formed by H2O and three carboxylate O atoms (Figure S4). Adjacent Zn atoms were connected by benzenetricarboxylate ligands to form a helical chain with a pitch of 13.767 Å and the Zn···Zn distance is of 8.252 Å (Figure 1a). Helical chains are further extended by residue carboxylate groups to give the 3D chiral framework of SNNU-71 with 1D helix channels along the c-axis direction (Figure 2a). To better elucidate the 3D network, Zn(II) and the BTC ligands can be regarded as independent 3-connected nodes, and the integral structure exhibits a chiral etd binodal topology (Figures 3a, S5, and S6). As stated above, although Li+ does not exist in the structure, which is indispensable for the synthesis of SNNU-71.

+

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Figure 2. 3D polyhedral structures of SNNU-71 (a), SNNU-72 (b), SNNU-73 (c), SNNU-74 (d), and SNNU-75 (e).

Figure 3. Topological representation of five noncentrosymmetric frameworks: (a) 3-connected etd net for SNNU-71, (b) (3,4,5)-connected net with Schläfli symbol of {62.8}2{63}{64.85.10}{65.8} for SNNU-72, (c) 3-connected SrSi2 topological net for SNNU-73, (d) (3,4)-connected ctn net for SNNU-74, (e) (3,6,6)-connected net with Schläfli symbol of {42.6}4{43.810.102}{45.64.86} for SNNU-75.

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asymmetric unit consists of two Zn(II), three Li(I), two BTC3−, and two coordinated water molecules. Two unique Zn atoms are of tetrahedral coordination geometry finished by three carboxylate O atoms and one tetrazolate N atoms for Zn(1), and four carboxylate O atoms for Zn(2). Three unique Li atoms all have similar distorted tetrahedral geometries by four O atoms. The Zn−O and Li−O distances are in the range of 1.913−2.003 Å and 1.880−1.987 Å, and the O−Zn−O and O− Li−O angles are in the range of 95.4−128.1° and 101.0−116.4° (Table S3). As shown in Figure S4, Zn(1) and Li(1) are first bridged by three carboxylate groups to give a three-bladed paddle-wheel [ZnLi(COO)3] binuclear unit. Adjacent binuclear clusters are linked by MTAZ ligand through the imdiazole like fashion to form a [Zn2Li2(COO)6(MTAZ)] motif. On the other hand, one Zn(2), two Li(2), and one Li(3) atom are also jointed by six carboxyl to generate [ZnLi3(COO)6] building block. As shown in Figure 1f, adjacent [ZnLi3(COO)6] clusters are linked via BTC ligands to form a left-handed helix with a pitch distance of 13.328 Å along the crystallographic b-axis direction. Furthermore, the [Zn2Li2(COO)6(MTAZ)] clusters and helical chains are interlinked with each other to give the 3D framework of SNNU-75 (Figure 2e). Two types of tetranulclear clusters both can be regarded as 6-connected nodes and thus this complicated framework can be simplified as novel (3,6,6)-connected net with the Schläfli symbol of {42.6}4{43.810.102}{45.64.86} (Figures 3e, S5 and S6). Overall, on the base of our heterometalation strategy, five new acentric or chiral MOFs were successfully produced, which all are constructed from helical chain-shaped building blocks as stated above. Up to now, more than 1000 metal-BTC frameworks have been reported; however, most of them crystallize in the centrosymmetric space groups due to the C3symmery of BTC ligands. The formation of acentric or chiral MOFs SNNU-71−75 clearly demonstrated that heterometalation can effectively eliminate the C3-symmetry of H3BTC and thus led to noncentrosymmetric frameworks. It should be pointed out that three types of functions have been observed for Li+ cations: structure-directing agent for SNNU-71, chargecompensating species for SNNU-72 and -75, and framework nodes for SNNU-73, -74, and -75. In our opinion, the different sizes and coordinated spheres of Li+ and Zn2+, Co2+, or Cd2+ should play an important role during the crystallization of these acentric MOFs since the angle between the coordinating sites of these compounds is ca. 120° which is inseparable with BTC ligand.47 This synthetic route for noncentrosymmetric metal− organic complexes via the combination of symmetrical ligands and mixed metal centers may be feasibly introduced to other systems in the future. SNNU-71−75 all are of 3D noncentrosymmetric frameworks and their porosity were investigated first. Due to their small pore size, these MOFs show neglectable N2 adsorption but remarkable uptakes of small gas molecules such as H2 and CO2. The low-pressure H2 sorption isotherms are given in Figure S9a. At 77 K and 1 atm, the H2 uptakes (cm3 g−1) are 34.7, 17.1, 46.3, and 102.6 for SNNU-71, -72, -73, and -75. The sorption behaviors of these compounds toward CO2 at 273 and 298 K were also investigated. At 273 K and 1 atm, the CO2 uptakes (cm3 g−1) are 12.64, 7.90, 18.18, and 30.88 for SNNU71, -72, -73, and -75 (Figure S9b and S9c). Although the H2 or CO2 uptakes are not high for SNNU-71−75, these results are comparable to other reported Li-MOFs such as CPM-42 and CPM-46.48,49 Overall, the H2 and CO2 uptake performance of SNNU-75 is better than that of other members, which may be

SNNU-72 crystallizes in the chiral orthorhombic space group P212121 and the asymmetric unit consists of two cadmium atoms, two HBTC2−, and two BTC3− anions. Cd1 centers are hexacoordinated bridged by four monodentate and one bidentate carboxyl groups, while Cd2 centers are heptacoordinated by one monodentate and three bidentate carboxyl groups from BTC linkers (Figure S4). The Cd−O distances are in the range of 2.254−2.592 Å, and O−Cd−O angles are in the range of 53.4−173.3° (Table S3). Two Cd2+ cations are connected by different BTC ligands to give two independent helical chains with pitches of 16.0672 Å (Figure 1b and c). Two types of helical chains interconnected with each other through the residue carboxylate groups to form a 3D anionic structure and Li+ cations help to balance the framework charge (Figure 2b). Two Cd atoms can be simplified as a 4- and 5-connected nodes, which are extended by 3-connected BTC nodes to generate a new (3,4,5)-connected topological network with the Schläfli symbol of {62.8}2{63}{64.85.10}{65.8} (Figures 3b, S5, and S6). SNNU-73 crystallizes in the chiral tetragonal space group P41212 and has crystallographic C2 symmetry. The asymmetric unit consists of one Co(II)/Li(I) mixed metal site one BTC3−, and one coordinated DMA molecule. The occupancy of Co(II)/Li(I) is 0.5/0.5, which is supported by the structural refinements and XPS results (Figure S7). The metal site shows a slightly distorted tetrahedral geometry coordinated by four O atoms from three carboxylate groups and one DMA. The M−O distances are in the range of 1.917−1.984 Å, and the O−M−O angles are in the range of 98.15−120.36° (Table S3). Two crystallographically equivalent metals are bridged together by three carboxylate groups in the bidentate fashion to give a three-bladed paddle-wheel [M2(COO)3] fragment with the M···M distance of 3.151 Å (Figure S4). Based on these connection modes, the M2-based SBUs are connected by BTC ligands to form an infinite helical chains running along the baxis direction with a pitch of 17.647 Å (Figure 1d). Two adjacent helical chains are bridged by sharing BTC ligands and thus lead to a 3D homochiral network of SNNU-73 (Figure 2c). If BTC ligands and dinuclear zinc units are regarded as three-connected nodes, this structure can be simplified as a 3connected network with SrSi2 topology (Figures 3c, S5 and S6). SNNU-74 crystallizes in the trigonal space group R3c and the asymmetric unit consists of one Cd(II), two Li(I), 4/3 BTC3−, and three coordinated water molecules. The existence of Cd(II) and Li(I) could be further supported by XPS analysis (Figure S7). Cd atom has distorted octahedral coordination geometry with six oxygen atoms of BTC3− carboxylate groups. Li(1) shows tetrahedral coordination geometry by three carboxylate oxygen and one oxygen atom from water. Li(2) site has tetrahedral geometry by two carboxylate oxygen and two oxygen atom from coordinated water. The Cd−O and Li−O distances are in the range of 2.151−2.425 Å and 1.802−2.035 Å, respectively (Table S3). One cadmium and two lithium atoms are linked by four bridging carboxylate groups to form a [CdLi2(COO)4] secondary building unit (Figure S4). Adjacent trinuclear units were connected by BTC ligands to form a 1D helical chain along the b-axis direction with a pitch of 16.2941 Å (Figure 1e). Each helical chain links the near six neighbors to generate the 3D structure of SNNU-74 with a (3,4)-connected ctn topology when BTC and [CdLi2(COO)4] units are simplified as nodes (Figure 2d and 3d). Under the similar synthesis condition as SNNU-71, the addition of another bridging ligand MTAZ led to SNNU-75 crystallizing in the chiral trigonal space group P3221. The 5637

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caused by the synergistic effect of open Li sites and appropriate pores. This is also supported by the isosteric heat of adsorption calculated by the virial model (Figures S10 and S11).50 It is well-known that lithium is an important component of inorganic NLO materials.51−56 Considering their noncentrosymmetric frameworks, these Li-introduced MOFs should have good NLO property. SNNU-71, -72, -74, and -75 all are colorless and transparent crystals; thus, their nonlinear optical properties are investigated. According to the method proposed by Kurtz and Perry, the second-harmonic generation (SHG) efficiency can be measured by using a powder technique.57 In this work, the SHG efficiency is measured by using pure microcrystalline samples, and the result is in contrast with KDP. The curves of SHG signal as a function of particle size are shown in Figures S12−S15. The SHG intensity of these complexes increases with increasing particle size, according to the rule proposed by Kurtz and Perry.55 Four MOFs all are phase-matchable at the wavelength of 1064 nm. The intensities of crystal powder of SNNU-71, -72, -74, and -75 are about 5, 0.4, 1.4, and 0.8 times that of a KDP marker in the same particle size of 0.125−0.08 mm, respectively (Figure 4). With the variations of particle size, the relative intensity change accordingly. For example, the intensity of SNNU-75 is about 3

times that of the KDP marker in the particle size of 0.06−0.04 mm. These SHG effects are comparable to those reported NLO MOFs built from chiral or acentric organic ligands, and SNNU71 surpasses most of them.58−62 In our opinion, the different size of metal cations and coordination numbers are two main factors47 for the origin of SHG effects of these MOFs. Importantly, SNNU-71, -72, -74, and -75 all are constructed from the same cheap and common H3BTC centric ligands. Overall, the heterometalation-induced spontaneous resolution for acentric or chiral MOFs and their tunable SHG effects demonstrated in this work are undoubtedly of high significance for the development of novel metal−organic NLO materials. In summary, taking advantage of the spontaneous resolution process, five noncentrosymmetric MOFs have been isolated by the assembly of metal ions with centrosymmetric benzenetricarboxylic acid linkers. Induced by the different coordination geometries between Li+ and Zn2+, Co2+, or Cd2+, six types of helical chains are generated and thus lead to the acentric or chiral frameworks. Except for their remarkable H2 and CO2 uptake performance, four colorless MOF materials show tunable NLO property. Overall, heterometalation is demonstrated to be a powerful strategy for acentric or chiral MOFs from centrosymmetric ligands.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.7b01320. Materials and Methods; Characterization; Crystallographic data (PDF) Accession Codes

CCDC 1550549, 1550551−1550553, and 1551377 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/ data_request/cif, or by emailing [email protected]. uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Shu-Ni Li: 0000-0002-6614-9241 Man-Cheng Hu: 0000-0003-2920-0439 Quan-Guo Zhai: 0000-0003-1117-4017 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is financially supported by the National Natural Science Foundation of China (21671126), the Natural Science Foundation of Shaanxi Province (2014KJXX-50), and the Fundamental Research Funds for the Central Universities (GK201701003).

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Figure 4. Oscilloscope traces of the SHG signals at 1064 nm (a) and plots of SHG intensity vs particle size (b) of SNNU-71, -72, -74, and -75. KDP samples serve as the references.

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DOI: 10.1021/acs.cgd.7b01320 Cryst. Growth Des. 2017, 17, 5634−5639