Novel Metal−Organic Frameworks with Specific Topology Formed

Novel Metal-Organic Frameworks with Specific Topology Formed through Noncovalent Br‚‚‚Br Interactions in the Solid State Jian Fan,† Wei-Yin Sun,*,† Taka-aki Okamura,‡ Yue-Qing Zheng,§ Bin Sui,† Wen-Xia Tang,† and Norikazu Ueyama‡

CRYSTAL GROWTH & DESIGN 2004 VOL. 4, NO. 3 579-584

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China, Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, and Municipal Key Laboratory of Inorganic Materials Chemistry, Institute for Solid State Chemistry, Ningbo University, Ningbo 315211, P. R. China Received October 16, 2003;

Revised Manuscript Received March 1, 2004

ABSTRACT: Two coordination polymers [Ag(bib)]NO3‚H2O (1) and [Ag(bib)]ClO4 (2) with one-dimensional (1D) chain structure were synthesized by reactions of ditopic ligand containing imidazole donors, namely, 1-bromo-3,5bis(imidazol-1-ylmethyl)benzene (bib), with corresponding silver salts. While the bib ligand reacted with ditopic diacetato-zinc(II) acceptors, M2L2-type metallocyclic ring-like complex [Zn2(bib)2(OAc)4]‚2H2O (OAc ) acetate anion) (3) was obtained, which was further connected by Br‚‚‚Br interactions to lead to the formation of 1D pseudopolyrotaxane. When ligand bib reacted with Zn(NO3)2‚6H2O and Mn(NO3)2, two complexes [Zn(bib)2(H2O)2](NO3)2‚ 2H2O (4) and [Mn(bib)2(H2O)2](NO3)2‚2H2O (5) with 2D network structure were obtained in which the metal atoms had octahedral coordination geometry. The structures of these coordination complexes were determined by X-ray crystallography, and the results revealed that the coordination geometry of metal atoms have a great impact on the structure of the supramolecular architectures. Furthermore, the nitrate anions located in the voids between the 2D cationic layers in 4 can be exchanged by nitrite anions, which means that complex 4 with 2D network structure has anion exchange properties. Introduction In recent years, there has been great interest in construction of coordination architectures with novel structures and topologies due to their possible chemical and physical properties.1,2 The control of structure and topology of assemblies is one of the major goals in supramolecular chemistry. Many efforts have been devoted to the rational design of specific frameworks including one- (1D), two- (2D), and three-dimensional (3D) structures.3,4 In fact, the formation of metal-organic frameworks is influenced by factors such as solvent system, template, counterions, geometric requirements of metal ions, and sometimes the ratio between the metal salt and the ligand.5 For example, by the reactions of flexible bridging ligand 1,4-bis(imidazol-1-ylmethyl)benzene (bix) with silver nitrate and zinc nitrate hexahydrate, infinite 2D polyrotaxane networks were generated, while the reaction of bix with manganese(II) nitrite gave an infinite 1D structure.6 It is clear that the bridging ligand plays an important role in the formation of these architectures. In our previous studies, we reported the syntheses and structures of metal complexes with imidazole-containing ligands, for example, [Mn(bimb)3](ClO4)2‚2H2O [bimb ) 4,4′-bis(imidazol-1-ylmethyl)biphenyl] and [Cd(dimb)2(MeOH)2](ClO4)2 [dimb ) 1,3-bis(imidazol-1-ylmethyl)-5-methylbenzene] (Scheme 1).7 The results showed that these * Corresponding author: Dr. Wei-Yin Sun. Coordination Chemistry Institute, Nanjing University, Nanjing 210093, China; telephone: +8625-83593485; fax: +86-25-83314502 or +86-25-83317761; e-mail: [email protected]. † Nanjing University. ‡ Osaka University. § Ningbo University.

Scheme 1. Schematic Drawing of Imidazole-Containing Ligands bix, bimb, dimb, and bib

complexes have different structures and topologies due to the different ligands of bimb and dimb, and both Mn(II) and Cd(II) are six-coordinated with octahedral coordination geometry. To expand our system, at the same time, to further investigate the influence of the bridging ligand on formation of supramolecular architectures, we designed and prepared a new imidazolcontaining ligand: 1-bromo-3,5-bis(imidazol-1-ylmethyl)benzene (bib). Compared with the ligand dimb, ligand bib has a bromo group instead of methyl group attached to the benzene ring, and weak interactions involving the bromo group can be expected in the some specific complexes, which may result in complexes with novel structure and topology. In this paper, we report the synthesis, structure, and property of complexes [Ag(bib)]NO3‚H2O (1), [Ag(bib)]ClO4 (2), [Zn2(bib)2(OAc)4]‚2H2O (3), [Zn(bib)2(H2O)2](NO3)2‚2H2O (4), and [Mn(bib)2(H2O)2](NO3)2‚2H2O (5) obtained by reactions of ligand bib with the corresponding metal salts. To the best of

10.1021/cg034190b CCC: $27.50 © 2004 American Chemical Society Published on Web 03/31/2004

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Table 1. Crystallographic Data for Compounds 1-5 chemical formula formula wt crystal system space group a, Å b, Å c, Å β, deg V, Å3 Z λ, Å Dcalcd, g cm-3 µ (Mo KR), cm-1 T, K unique reflns Rint obsd reflns Ra/wRb a

1

2

3

4

5

C14H15AgBrN5O4 505.09 monoclinic P21/c 11.8932(3) 20.1658(4) 14.0997(3) 99.4465(6) 3335.76(13) 8 0.7107 2.011 36.35 200 7645 0.0541 5460 0.0362/0.0739

C14H13AgBrClN4O4 524.51 orthorhombic Pnma 8.3819(12) 12.6782(18) 16.162(2)

C36H42Br2N8O10Zn2 1037.34 monoclinic C2/m 15.9690(10) 17.0710(10) 8.2972(4) 113.836(2) 2068.9(2) 2 0.7107 1.665 31.55 200 2448 0.0951 1522 0.0415/0.0559

C28H34Br2N10O10Zn 895.84 monoclinic P21/n 13.022(12) 8.860(6) 15.910(13) 108.86(7) 1737(2) 2 0.7107 1.713 30.77 200 3968 0.0559 3130 0.0326/0.0832

C28H34Br2MnN10O10 885.41 monoclinic P21/n 13.1127(16) 8.9291(11) 16.0213(19) 109.383(2) 1769.5(4) 2 0.71073 1.662 27.00 293 3890 0.1271 2544 0.0548/0.1445

1717.5(4) 4 0.71073 2.028 36.83 293 2052 0.0930 948 0.0464/0.0729

R ) ∑||Fo| - |Fc||/∑|Fo|. b wR ) |∑w(|Fo|2 - |Fc|2)|/∑|w(Fo)2|1/2, where w ) 1/[σ2(Fo2) + (aP)2 + bP]. P ) (Fo2 + 2Fc2)/3.

our knowledge, complex 3 is the first example of 1D pseudo-polyrotaxane formed by Br‚‚‚Br interactions. Experimental Section General Methods. All commercially available chemicals were of reagent grade and used as received without further purification. Solvents such as acetonitrile and methanol were dried and purified by distillation before use. C, H, and N analyses were made on a Perkin-Elmer 240C elemental analyzer at the analysis center of Nanjing University. 1H NMR spectral measurements were performed on a Bruker DRX-500 NMR spectrometer. Infrared (IR) spectra were recorded on a Bruker Vector22 FT-IR spectrophotometer by using KBr disks. Powder X-ray diffraction patterns were recorded on a Rigaku D/max-RA rotating anode X-ray diffractometer with graphitemonochromatic Cu-KR (λ ) 1.542 Å) radiation at room temperature. The ligand bib was prepared in two steps with total 46% yield. 1-Bromo-3,5-dimethylbenzene reacted with N-bromosuccinimide (NBS) in CCl4 to give 1-bromo-3,5-bis(bromomethyl)benzene, which was then treated with imidazole in alkaline DMSO solution to provide ligand bib. 1H NMR (CDCl3, 25 °C): δ ) 5.09 (s, 4H), 6.82 (s, 1H), 6.89 (s, 2H), 7.14 (s, 2H), 7.24 (s, 2H), 7.55 (s, 2H). Anal. Calcd for C14H13BrN4 (317.19): C 53.01, H 4.13, N 17.66; Found C 52.98, H 4.15, N 17.63. Preparation of the Complexes. All procedures, for example, synthesis and measurements, for silver(I) complexes were carried out in the dark. Caution. Perchlorate salts of metal complexes with organic ligands are potentially explosive and should be handled with care. [Ag(bib)]NO3‚H2O (1). The compound was prepared by a layering method. A buffer layer of a solution (10 mL) of methanol and water (3:1) was carefully layered over an aqueous solution (3 mL) of AgNO3 (17.0 mg, 0.1 mmol). Then a solution of bib (31.7 mg, 0.1 mmol) in methanol (5 mL) was layered over the buffer layer. Crystals (31.3 mg, 62%) were collected after two weeks. Anal. Calcd for C14H15AgBrN5O4 (505.08): C 33.29, H 2.99, N 13.87; Found C 33.13, H 3.08, N 13.86. [Ag(bib)]ClO4 (2). The complex 2 was obtained by similar procedures to complex 1 using AgClO4‚H2O (22.5 mg, 0.1 mmol) instead of AgNO3 to react with bib (31.7 mg, 0.1 mmol) by the layering method. Crystals (26.7 mg, 51%) were obtained after about three weeks. Anal. Calcd for C14H13AgBrClN4O4 (524.51): C 32.06, H 2.50, N 10.68; Found C 32.03, H 2.63, N 10.66. [Zn2(bib)2(OAc)4]‚2H2O (3). An aqueous mixture (10 mL) of Zn(OAc)2‚2H2O (10.9 mg, 0.05 mmol) and bib (16.0 mg, 0.05 mmol) was sealed in a stainless steel vessel and heated to 130

°C for 1 day, and then cooled to room temperature and filtered to give the title complex (13.0 mg, 48%). Anal. Calcd for C18H21BrN4O5Zn (518.67): C 41.68, H 4.08, N 10.80; Found: C 41.66, H 4.14, N 10.76. [Zn(bib)2(H2O)2](NO3)2‚2H2O (4). An aqueous solution (5 mL) of Zn(NO3)2‚6H2O (14.9 mg, 0.05 mmol) was added slowly with constant stirring to a solution of bib (32.7 mg, 0.1 mmol) in acetonitrile (15 mL) to give a clear solution. The reaction mixture was left to stand at room temperature for three weeks. Colorless crystalline product was obtained (35.0 mg, 78%). Anal. Calcd for C28H34Br2N10O10Zn (895.84): C 37.54, H 3.82, N 15.64; Found C 37.44, H 3.84, N 15.75. [Mn(bib)2(H2O)2](NO3)2‚2H2O (5). The title complex was prepared by the same procedures to complex 4 using Mn(NO3)2 (0.05 M, 2 mL) instead of Zn(NO3)2‚6H2O to react with bib (31.7 mg, 0.1 mmol). Colorless crystalline product was obtained (32.3 mg, 73%). Anal. Calcd for C28H34Br2N10O10Mn (885.41): C 37.98, H 3.87, N 15.82; Found C 38.02, H 3.97, N 15.77. Crystallography. The intensity data were collected at 200 K for 1, 3, and 4 on a Rigaku RAXIS-RAPID imaging plate diffractometer. The structures were solved by direct methods using SIR928 and expanded using Fourier techniques.9 All nonhydrogen atoms were refined anisotropically by the full-matrix least-squares method. The hydrogen atoms except for those of water molecules were generated geometrically. Two nitrate anions and two water molecules in complex 1 are disordered: the atoms N1, O11, O12, O13 of one nitrate anion and O201 of one water molecule have two positions each with the site occupancy factors of 0.50, while the atoms N3, O31, O32, O33 of another anion and O203 of another water molecule have two positions with the site occupancy factors of 0.526(4) and 0.474(4), respectively. All calculations were carried out on an SGI workstation using the teXsan crystallographic software package.10 The data collection for complexes 2 and 5 was made on a Bruker Smart Apex CCD with graphite monochromated MoKR radiation (λ ) 0.71073 Å) at 293 K. The structures were solved by direct methods using SHELX-9711 and refined by full-matrix least-squares method anisotropically for nonhydrogen atoms. Calculations were performed on a personal computer with the Siemens SHELXTL program package.12 The crystal parameters, data collection and refinement results for the compounds are summarized in Table 1. Selected bond length and angles are listed in Table 2. Further details are provided in Supporting Information.

Results and Discussion Crystal Structure Description. As shown in Figure 1a, the ligand bib has a trans conformation in 1 and connects two silver(I) atoms. The Ag-N bond distances

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Table 2. Selected Bond Distances (Å) and Angles (deg) for Complexes 1-5a Ag(1)-N(112) Ag(2)-N(132) N(112)-Ag(1)N(12)

Ag(1)-N(1)

[Ag(bib)]NO3‚H2O 1 2.102(3) Ag(1)-N(12) 2.110(3) Ag(2)-N(32) 175.29(11) N(132)-Ag(2)-N(32)

[Ag(bib)]ClO4 2 2.086(4) N(1)-Ag(1)-N(1)#1

2.103(3) 2.111(3) 168.78(11)

180.00

[Zn2(bib)2(OAc)4]‚2H2O 3 Zn(1)-O(1) 1.983(2) Zn(1)-N(12) 2.004(2) O(1)-Zn(1)-N(12) 106.21(9) O(1)-Zn(1)-O(1)#2 95.16(12) O(1)#2-Zn(1)116.62(9) N(12)-Zn(1)114.77(14) N(12) N(12)#2 [Zn(bib)2(H2O)2](NO3)2‚2H2O 4 Zn(1)-N(12) 2.129(2) Zn(1)-N(32) Zn(1)-O(1) 2.175(3) N(32)-Zn(1)-O(1) N(12)-Zn(1)86.50(8) N(12)-Zn(1)-O(1) N(32) N(12)-Zn(1) 93.50(8) N(32)#3-Zn(1)-O(1) -N(32)#3 N(12)#3-Zn(1)- 89.99(10) O(1) [Mn(bib)2(H2O)2](NO3)2‚2H2O 5 Mn(1)-O(1) 2.207(3) Mn(1)-N(12) Mn(1)-N(32) 2.263(3) O(1)-Mn(1)-N(12) O(1)#4-Mn(1) 90.83(11) O(1)-Mn(1)-N(32) -N(12) O(1)#4-Mn(1) 89.89(11) N(12)#4-Mn(1) -N(32) -N(32) N(12)-Mn(1)-N(32) 94.19(10)

2.171(2) 89.86(9) 90.01(10) 90.14(9)

2.232(3) 89.17(11) 90.11(11) 85.81(10)

a Symmetry transformations used to generate equivalent atoms: #1 1 - x, -y, 1 - z; #2 - x, y, -z; #3 2 - x, 1 - y, 1 - z; #4 1 - x, 2 - y, -z.

Figure 1. (a) 1D chain structure of 1. (b) Perspective view of 2D network structure of 1 linked by Ag‚‚‚Br interactions indicated by dashed lines. Hydrogen atoms, anions, and solvent molecules were omitted for clarity.

range from 2.102(3) to 2.111(3) Å, and the N-Ag-N coordination angles are 175.3(1) and 168.8(1)° (Table 2), respectively. The combination of linear metal center (ca. 180° bond angle) and trans conformation of bib ligand results in the formation of an infinite 1D chain. It is interesting that the 1D chains of 1 are linked together through weak Ag‚‚‚Br interactions to produce an infinite 2D network structure as exhibited in Figure 1b. The distance of 3.55 Å between the Br atom of one

Figure 2. (a) Crystal structure of complex 2 with atom numbering scheme; weak Ag‚‚‚O interactions were indicated by dashed lines. (b) Space-filling view of square-wave-like 1D chain of 2.

chain and the Ag atom from another chain indicates the presence of weak noncovalent Ag‚‚‚Br interactions. The disordered nitrate anions and water molecules locate at the border of the 2D network and connect the neighboring layer through C-H- - -O hydrogen bonds to generate a 3D framework (Figure S1). To evaluate the effect of anion during the construction of the supramolecular architectures, AgClO4‚H2O, instead of AgNO3, was employed to react with bib ligand to give 2. Complex 2 has the same metal/ligand ratio as that in 1. The silver atom in complex 2 sits on the inversion center and each Ag is coordinated by two N atoms from two different bib ligands with the N-Ag-N coordination angle of 180° (Figure 2a). A distance of 3.04 Å between the O1 and Ag1 atoms implies the presence of weak interactions between the silver atom and the O atom of perchlorate anion. It is noteworthy that the bib ligand has a cis conformation in complex 2 which is different from that in 1 and as a result a square-wavelike 1D chain structure was generated (Figure 2b). The different shapes of the 1D chains in complexes 1 and 2 are attributed to the different coordination preferences and geometric shapes of perchlorate and nitrate anions, and the different conformations of the ditopic bib linker appeared in complexes 1 and 2. The 1D chains of 2 are further joined together by weak Ag‚‚‚Br interactions with a Ag‚‚‚Br distance of 3.36 Å and a C3-H3‚‚‚O3(1 - x, -1/2 + y, 1 - z) hydrogen bond with a distance of 3.448(6) Å between C3 and O3(1 - x, -1/2 + y, 1 - z) to form the 3D frameworks (Figure S2).

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Figure 3. (a) M2L2 metallocyclic structure of 3, the thermal ellipsoids were drawn at 50% probability. (b) 1D pseudopolyrotaxane constructed via Br‚‚‚Br interactions indicated by yellow bonds; acetate anions and hydrogen atoms were omitted for clarity.

In complexes 1 and 2, the coordination angles around the metal atom are about 180°, while in 3 with the tetrahedral zinc(II) atom, the coordination angle is about 109°. The use of the acetate anions as ancillary ligands and of the diacetato-zinc(II) as a ditopic acceptor with ∼109° bond angle is inspired by the cage-like structure in the previously reported complex [Zn3(tib)2(OAc)6]‚4H2O [tib ) 1,3,5-tris(imidazol-1-ylmethyl)benzene], in which the acetate anions coordinated to the Zn(II) center in a monodentate fashion.13 Crystallographic analysis provides direct evidence of M2L2 metallocyclic ring-like structure of complex 3. The complex has space group imposed 2/m symmetry, and the 24-numbered M2L2 metallocyclic ring was achieved by two diacetato-zinc(II) units and two bib ligands. As shown in Figure 3a, two bib ligands that are both in cis conformations adopt a face-to-face orientation and are held together by two zinc(II) atoms. The Zn-N bond distance is 2.004(2) Å, and the N-Zn-N angle is 114.77(14)° (Table 2), respectively. The intermetallic distance between the two zinc(II) atoms (i.e., Zn1‚‚‚Zn1A) is 9.42 Å and the two benzene ring planes are strictly parallel each other with a separation of 10.14 Å, which are comparable with those in the complex [Zn3(tib)2(OAc)6]‚ 4H2O.13 Two benzene rings in one M2L2 metallocycle are in a gauche conformation, which was also observed in the previously reported complexes [Ag2(bitmb)2](PF6)2‚ 2CH3CN [bitmb ) 1,3-bis(imidazol-1-ylmethyl)-2,4,6trimethylbenzene],14 and [Zn2H-2L]Br2(H2O)2 [L ) 3,6,9,17,20,23-hexazatri-cyclo[23.3.1.1.11,15]triconta-1(29),11(30),12,14,25,27-hex-aene-6,20-bis(2-hydroxyethyl)].15 The ligand bib in cis conformation has a preference of forming a M2L2 metallocycle over forming an extended chain by using a ditopic acceptor with the bonding angle about 109°. In addition to the flexibility of linkers, thermodynamics is an important factor in determining the size of macrocycles, and it has been suggested that small cycles are favored over larger ones.16

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A remarkable feature of the complex 3 is that there are Br‚‚‚Br interactions involved in the stabilization of crystal lattice. The Br-Br distance within the range of 3.3-3.9 Å is considered to have Br‚‚‚Br interactions.17,18 The distance between two Br atoms from two alternately M2L2 metallocycles is 3.58 Å, which is comparable with that observed in crystal packing of compound 3,5dibromo-2,4,6-trimethylbenzoic acid (dBr‚‚‚Br ) 3.72 Å).17 Directional interactions formed between the halogens are polarization-induced and have been used intensively in systematic crystal engineering.18 In the compound 3, the M2L2 metallocyclic rings are joined together by such Br‚‚‚Br interactions to lead to the formation of an infinite 1D chain. Strikingly, two of these 1D chains interpenetrate each other, with each ring section of one chain penetrated by a Br‚‚‚Br “bond” of the other chain, to form an 1D pseudo-polyrotaxane as schematically illustrated in Figure 3b. The Br‚‚‚Br interactions are encouraged by the gauche conformations of the M2L2 metallocycles. To the best of our knowledge, complex 3 is the first example of 1D polyrotaxane formed by Br‚ ‚‚Br interactions. The results show that the coordination geometric requirements of metal centers have a remarkable influence on the structure and topology of the assembly products. In complex 3, the zinc(II) atom has a tetrahedral coordination environment and is coordinated by two N atoms from two different bib ligands and two acetate anions served as ancillary ligands. While the reactions between bib and metal salts with anions having a weak or noncoordination ability, e.g., nitrate anion, were carried out, complexes 4 and 5 were isolated. As listed in Table 1, similar cell parameters of complexes 4 and 5 indicate that they have an analogous structure. Therefore, only the structure of 4, as a typical example, is described here in detail. X-ray crystallographic analysis shows that the zinc(II) atom in complex 4 is sixcoordinated, rather than four-coordinated as that in 3, with an octahedral coordination environment. The equatorial plane is completed by four N atoms from four bib ligands and the apical positions were occupied by two O atoms of two water molecules. In complex 4, ligand bib has trans conformation, and four bib ligands and four metal ions form a macrocyclic ring, which is further linked by Zn-N bonds to give a 2D network structure as illustrated in Figure 4b. The packing arrangement of the pleated cationic 2D sheets is shown in Figure S3, and the vacancy formed between the two adjacent cationic 2D layers were occupied by the nitrate anions and water molecules. There are three kinds of hydrogen bonds between the nitrate anions and the cationic layers. The bromo group is not involved in the formation of hydrogen bonds or halogen‚‚‚halogen interactions in complexes 4 and 5. While the Ag‚‚‚Br and Br‚‚‚Br interactions were found in complexes 1, 2, and 3. Anion Exchange Properties of Complex 4. Recently, anion exchange properties of cage-like frameworks and cationic-layered architectures have been investigated in our lab.7,19 As revealed by the crystal structure analysis of [Zn(bib)2(H2O)2](NO3)2‚2H2O 4, the nitrate anions are only loosely bound to the framework through the hydrogen bonds. To investigate whether these loosely bound nitrate anions can be exchanged by

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Figure 5. FT-IR spectra of (a) complex 4; (b) complex 4 treated with aqueous solution of NaNO2.

Figure 4. (a) Crystal structure of 4, the thermal ellipsoids were drawn at 50% probability. (b) Infinite 2D network of complex 4.

other anions, an anion exchange reaction was carried out for complex 4. A well-powdered sample of [Zn(bib)2(H2O)2](NO3)2‚2H2O (4) (50 mg, 0.056 mmol) was suspended in an aqueous solution (20 mL) of NaNO2 (2.0 g) with stirring for 1 day at room temperature, then filtered, washed with water several times, and dried to give a white powder. It can be seen clearly that the intense bands from 1270 to 1223 cm-1 originating from the NO2- anion appeared, while the intense band at 1384 cm-1 of the NO3- anion disappeared in the FT-IR spectrum of exchanged solid (Figure 5). Furthermore, the results of elemental analysis of the anion exchanged product (C 38.80, H 3.92, N 16.01) also indicated a complete anion exchange, that is, [Zn(bib)2(H2O)2](NO2)2‚ 2H2O [C28H34Br2N10O8Zn (863.83) calcd. C 38.93, H 3.97, N 16.22]. To investigate the stability of the framework of complex 4 during the ion-exchange process, we recorded X-ray powder diffraction (XRPD) and the results were shown in Figure S4. The exchanged products gave a sharp XRPD pattern, which is similar to that of complex 4, which indicates that the crystal structure has been maintained after the exchange of NO3- by NO2-.20 However, the complex 4 was exchanged with NaClO4 by same procedures as mentioned above; the FT-IR spectrum of exchanged solid was the same with that of original complex 4, which indicated that the NO3- anions in 4 could not be exchanged by

Figure 6. Schematic drawing for reactions between the bib ligand and Ag(I) or Zn(II)/Mn(II) salts; Ag(I) and Zn(II)/Mn(II) centers are represented by the red and green balls, respectively, and the bib ligands are represented by the blue sticks.

ClO4- anions. Namely, the anions in the framework of 4 could be exchanged selectively, which may be attributed to the different size and geometry between the ClO4- and NO3- anions. The anion exchanges described here are considered to occur in a solid-state, rather than a solvent-mediated process,19 since complex 4 is insoluble in water, and the negative result of exchange obtained with the perchlorate anion is a good counterproof. Conclusion We have shown that when the ligand bib reacted with ditopic acceptor Ag(I) (∼180° bond angle) salts and zinc(II) (∼109° bond angle) salt, three kinds of structures are generated as schematically shown in Figure 6. The formation of the M2L2 metallocyclic ring in 3 is favored by the coordination angle of the zinc(II) atom. While the bib reacted with Zn(NO3)2‚6H2O and Mn(NO3)2, in which both metal ions have the preference for octahedral coordination geometry, two 2D networks having (4, 4) topology with selective anion exchange property were obtained, and the ligands in these two complexes are

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in trans conformation. The results show that the nature of organic ligand and geometric needs of metal atoms have a great influence on the structure of metal-organic frameworks. Furthermore, the introduction of the halogen atom to the ligand may, to a certain extent, affect the resultant structure, which provides opportunities for the construction of architectures with novel structure and topology. Acknowledgment. The authors are grateful to the National Natural Science Foundation of China (Grant No. 20231020) for financial support of this work. Supporting Information Available: X-ray crystallographic file in CIF format, crystal packing diagrams for 1, 2, and 4 (Figures S1-3) and powder XRD for anion exchange of 4 (Figure S4). This material is available free of charge via the Internet at http://pubs.acs.org.

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