DOI: 10.1021/cg1005242
Silver Coordination Polymers Based on Neutral Trinitrile Ligand: Topology and the Role of Anion
2010, Vol. 10 3964–3976
Jia Ni,† Kai-Ju Wei,*,† Yangzhong Liu,*,† Xiao-Chun Huang,‡ and Dan Li‡ †
Department of Chemistry, University of Science & Technology of China, Hefei 230026, P. R. China, and ‡Department of Chemistry, Shantou University, Guangdong 515063, P. R. China Received April 20, 2010; Revised Manuscript Received August 5, 2010
ABSTRACT: One flexible star-shaped bridging molecule tris-(4-cyanophenyl)amine (TCPA) is synthesized from tris-(4iodophenyl)amine by treatment with CuCN in hexamethylphosphorotriamide (HMPA) as a catalyst in high yield. Aniontemplate-controlled reactions of TCPA and silver salts give a series of coordination polymers (CPs) with various topological patterns. The complex [Ag(TCPA)(ClO4)]n 3 nC6H6 (1) forms an undulating 4.82 network, which displays unusual net entanglement. Two 4.82 nets interweave each other to give rise to 2-fold interpenetrating basic layers, which link together via double μ-Operchlorate bridging interactions. The complex [Ag(TCPA)(CF3SO3)]n 3 2nC6H6 (2) forms noninterpenetrating (6,3) nets. The solid state structure of [Ag3(TCPA)(CF3CO2)3]n 3 nCH2Cl2 (3) also is a (6,3) honeycomb network, differently, including a sphere-type Ag4(CF3CO2)62- cluster-anion in the host frameworks, which is a rare example of the host cationic network containing a guest cluster-anion. The complexes [Ag(TCPA)(BF4) 3 0.5H2O]n 3 1.5nC6H6 (4), [Ag(TCPA)(ClO4) 3 0.5H2O]n 3 nC7H8 3 nH2O (5), and [Ag(TCPA)(CF3SO3) 3 0.5H2O]n 3 1.5nC6H6 (6) exhibit three similar (10,3) networks which form rare net entanglements. Four (10,3) nets interweave to generate a 4-fold interpenetrating assemble, which are closely united together via specific μ2-Owater bridging interactions. The complex [Ag4(TCPA)2(CF3CO2)3(CF3SO3)]n 3 nC6H6 3 nCH2Cl2 (7) is a threedimensional (3D) structure formed via multiple “zigzag” Ag4 chains. In this AgI-TCPA system, the structural diversities and topological differences of these networks result from the flexibilities of the bridging ligand TCPA and the template-effect of anions. The free rotation of three Ph-CN “arms” around the central N moiety results in TCPA adopting different conformation in the self-assembly process by using variational solvent system and/or counterions.
Introduction The design and synthesis of coordination polymers (CPs) or metal-organic frameworks (MOFs) have attracted intensive attention over the past decade, not only because of their novel topologies and intriguing structural diversities,1 but also because of their unique chemical and physical properties2-8 and their potential applications in areas such as molecular sieves,3 gas storage,4 size-selective separation,5 ion exchange,6 and heterogeneous catalysis.7 Although most porous CPs or MOFs are not as durable as conventional inorganic porous materials, such as the molecular sieves and zeolites, these frameworks may possess some specific excellent qualities, such as high porosities and low densities.4,8 The ultimate aim of CPs or MOFs research is to control the structures of the target products and investigate the relationship between the structures and physicochemical properties. However, the rational construction of these structures, to control the pore shape or size of a specific open framework, remains a great challenge for the complexities in predicting the overall metal-organic connectivity or even the local coordination geometry in crystal engineering.2-7 One direct strategy to construct CPs or MOFs is the use of connectors-and-linkers, in which metal ions are as connectors and organic ligands are as linkers. Generally, the structural morphology of CPs or MOFs are greatly dependent on the conformation, size, and donor groups of the organic “linkers” because of the controllable and designable properties of organic molecules.4a,b,9 The pore size of CPs or MOFs is, to a great *To whom correspondence should be addressed. Fax: þ86-551-3600874. E-mail:
[email protected] (K.-J.W.);
[email protected] (Y.L.). pubs.acs.org/crystal
Published on Web 08/17/2010
extent, dominated by the length and shape of the organic ligands. That is, the physical and chemical properties of the CPs or MOFs can also be effectively controlled through ingenious modifications of the organic linkers. On this aspect, the rigid ligands have been most extensively studied for robust CPs or MOFs.10 Flexible ligands, which are inclined to form flexible architectures, still remain a great challenge in the selfassembly.11 Furthermore, the flexibility of frameworks has been recognized as an advantage for molecular recognition, separation, and sensing applications. In contrast to the rigid structures based on rigid building blocks, a flexible structure constructed by using flexible molecules can expand, shrink, and even distort its “soft” networks to fit the guest molecules and greatly enhance the mechanical capacities of nets.11 Evidently, the triphenylamine is a good candidate as the flexible molecule, which not only possesses flexibility of the amino group, but also can be easily functionalized at its three 4-positions and covalently linked to other functional moieties.12 It has been proven that triphenylamine derivatives introduced appropriate functional groups can enhance the possibility of forming flexible CPs or MOFs.13 On the other hand, the nitrile functional group on the aromatic ring is an outstanding candidate for coordination bonding in selfassembly, especially for silver(I) or copper(I) complexes.14 Actually, the multitopic nitrile ligands were widely used to construct CPs or MOFs at the beginning of this field for both topology and functionality, such as bidentate ligands 3,6-dicyano-9-phenylcarbazole,15 4,40 -dicyanobiphenyl,16 bis(3-acetylenylphenyl-(4-cyanophenyl))oxadiazole;17 tridentate ligands 1,3,5-tri(4-cyanophenyl-ethynyl)benzene,16 1,3,5-tri-(4(4ethynylbenzonitrile)phenyl)benzene;18 tetradentate ligands r 2010 American Chemical Society
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Scheme 1. Preparation of the Ligand TCPA
Scheme 2. Schematic Representation of the Assembled Topologic Structures of the Ligand TCPA and Ag(I) Ions
4,40 ,400 ,4000 -tetracyanotetraphenylmethane.14p However, a systemic study based on a flexible polytopic nitrile ligand for constructing a series of CPs or MOFs with various topological patterns is rarely reported. Encouraged by these findings and intrigued by the possibility of using a flexible linker based on triphenylamine as a tripodal linker to achieve flexible CPs or MOFs, we synthesized a star-type molecule tris-(4-cyanophenyl)amine (TCPA) with conformational and geometrical flexibility (Scheme 1). The TCPA molecule is capable, to a certain extent, of adjusting itself sterically, in which there are three cyanophenyl moieties and each moiety is linked by a N-C single bond. As a result, each cyanophenyl group has the virtue of allowing rotation around this single bond. That is, TCPA can adopt variational conformations upon coordination to silver ions. Thus, at least three typical topological structures of the assemblies might reasonably exist: 4.82 nets, (6,3) nets, and (10,3) nets (Scheme 2). Taking advantage of these features, we demonstrated that the assembly of TCPA and silver ions with various counterions aims at expanding TCPA units through “soft” metal Ag(I) ion and exploring the templating effects of anions. The ancillary or minor ligation by different counterions, which sometimes take secondary roles in determining the structure and geometry of CPs or MOFs, such as NO3-, BF4-, ClO4-, CF3SO3-, CF3CO2-, PF6-, SbF6-, could result in a significant structural variation.14,15,19 Our previous studies have shown
that the rigid ligand 3,6-dicyano-9-phenylcarbazole, which has two -CN groups as the terminal coordination sites, preferentially forms coordination polymeric chains with silver(I) ions.15a Herein, we report seven silver-containing CPs, based on the flexible tripodal linker TCPA, with various topological structures. Experimental Section Materials and Methods. AgBF4, AgClO4, AgCF3SO3, AgCF3CO2, and CuCN were of reagent-grade quality, obtained from commercial sources and used without further purification. Bromobenzene and hexamethylphosphorotriamide (HMPA) were freshly distilled. Benzene and toluene were freshly distilled over sodium and benzophenone. Dichloromethane was dried and distilled over P2O5 under a nitrogen atmosphere. DMF was dried and distilled over LiH. 1 H NMR spectra were recorded on a Bruker 300 Ultrashield spectrometer operating at 300 MHz. The FT-IR spectra were recorded in the region 400-4000 cm-1 on a Bruker EQUINOX 55 VECTOR22 spectrophotometer: the samples were prepared using KBr pellets. Elemental analyses were carried out with an Elmentar Vario EL-III analyzer. Fluorescence measurements were made on a JOBIN YVON Analytical Instrument FLUOROLOG-3-TAU at room temperature. Safety Note!. Perchlorate salts of silver complexes with organic ligands are potentially explosive! Only small amounts of materials should be prepared, and these should be handled with great caution. Synthesis of Tris-(4-iodophenyl)amine (TIPA). Tris-(4-iodophenyl)amine was synthesized by procedures reported earlier.20 1H NMR (300 MHz, CDCl3, ppm): δ 7.55-7.52 (d, 6H), 6.82-6.79 (d, 6H).
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Table 1. Crystallographic Data for Ligand TCPA and Complexes 1-3 compound
TCPA
1
CCDC 715183 285827 C27H18AgClN4O4 formula C21H12N4 formula weight 320.35 605.77 crystal system orthorhombic monoclinic space group Pbcn C2/c a/A˚ 8.1449(8) 12.7209(13) b/A˚ 11.5943(11) 15.4365(15) c/A˚ 17.4855(16) 27.097(3) R/deg 90 90 β/deg 90 99.045(2) γ/deg 90 90 1651.2(3) 5254.8(9) V/A˚3 1.289 1.531 Dc/Mg m-3 Z 4 8 F(000) 664 2432 0.079 0.909 μ/mm-1 R1 = 0.0577 final R indices [I > 2σ(I)] R1 = 0.0590 wR2 = 0.1250 wR2= 0.1504 R and Rwa 2 1.100 1.074 GOF on F P P P P a R = |Fo| - |Fc|/ |Fo|; Rw = [ w(Fo2 - Fc2)2/ w(Fo2)2]1/2.
Synthesis of Tris-(4-cyanophenyl)amine (TCPA). A mixture of tris-(4-iodophenyl)amine (1.250 g, 0.002 mol) and CuCN powder (0.770 g, 0.008 mol) in anhydrous HMPA (10 mL) was stirred for 18 h under the protection of dry nitrogen at 160 C. The reaction mixture was cooled to ambient temperature, poured into aqueous NaHCO3 (10%), and extracted with dichloromethane. The aqueous phase was discarded, and the organic layer was washed with distilled water to neutral pH, dried with over MgSO4, and concentrated in vacuo. The residue was filtered to give the desired compound as a primrose yellow solid. Yield: 0.514 g, 80%. IR (KBr, cm-1): 2216(vs), 1595(vs), 1499(vs), 1320(m), 1280(s), 1180(m). 1H NMR (300 MHz, CDCl3, ppm): δ 7.624-7.595 (t, 6H), 7.166-7.1371 (t, 6H). Synthesis of [Ag(TCPA)(ClO4) 3 C6H6]n (1). A solution of AgClO4 (0.0622 g, 0.3 mmol) in benzene (4 mL) was layered onto a solution of TCPA (0.0961 g, 0.3 mmol) in CH2Cl2 (10 mL). The solutions were left at room temperature for about 3 days, and yellowish crystals were obtained. Yield: 0.0981 g, 54%. IR (KBr, cm-1): 2220(vs), 1640(m), 1600(vs), 1500(s), 1480(m), 1300(m), 1240(s), 1180(vs), 816(m), 698(m), 625(m). Anal. Calcd for C27H18AgClN4O4: C, 53.53; H, 2.994; N, 9.249. Found: C, 53.57; H, 3.101; N, 9.241. Synthesis of [Ag(TCPA)(SO3CF3)]n 3 2nC6H6 (2). A solution of AgCF3SO3 (0.0771 g, 0.3 mmol) in benzene (10 mL) was layered onto a solution of TCPA (0.0961 g, 0.3 mmol) in CH2Cl2 (10 mL). The solutions were left at room temperature for about 2 days, and yellow crystals were obtained. Yield: 0.1340 g, 61%. IR (KBr, cm-1): 2220(vs), 1590(vs), 1500(s), 1370(m), 1240(s), 1190(vs), 897(m), 816(m), 698(m), 596(m). Anal. Calcd for C34H24AgF3N4O3S: C, 55.67; H, 3.298; N, 7.639. Found: C, 55.71; H, 3.293; N, 7.627. Synthesis of [Ag3(TCPA)(CF3)CO23 3 CH2Cl2]n (3). A solution of AgCF3CO2 (0.0663 g, 0.3 mmol) in benzene (4 mL) was layered onto a solution of TCPA (0.0321 g, 0.1 mmol) in CH2Cl2 (6 mL). The solutions were left at room temperature for about 2 days, and yellow crystals were obtained. Yield: 0.0748 g, 70%. IR (KBr, cm-1): 2920(m), 2850(w), 2220(vs), 1640(m), 1600(vs), 1500(vs), 1480(s), 1370(m), 1290(vs), 1250(vs), 1170(vs), 1030(s), 895(m), 816(m), 698(m), 642(m). Anal. Calcd for C28H14Ag3Cl2F9N4O6: C, 31.49; H, 1.321; N, 5.247. Found: C, 31.55; H, 1.315; N, 5.258. Synthesis of [Ag(TCPA)(BF4) 3 0.5H2O 3 1.5C6H6]n (4). A mixed solution of AgBF4 (0.0584 g, 0.3 mmol) in benzene (5 mL) was layered onto a solution of TCPA (0.0961 g, 0.3 mmol) in CH2Cl2 (8 mL). The solutions were left at room temperature for about 3 days, and yellowish crystals were obtained. Yield: 0.0904 g, 47%. IR (KBr, cm-1): 2250 (vs), 1590(s), 1500(s), 1480(m), 1370(m), 1300(m), 1240(s), 1190(m), 1110(vs), 775(m), 698(m), 594(m). Anal. Calcd for C30H22AgBF4N4O0.5: C, 56.20; H, 3.458; N, 8.738. Found: C, 56.29; H, 3.465; N, 8.691. Synthesis of [Ag(TCPA)(ClO4) 3 1.5H2O 3 C7H8]n (5). A solution of AgClO4 (0.0622 g, 0.3 mmol) in toluene (5 mL) was layered onto a solution of TCPA (0.0961 g, 0.3 mmol) in CH2Cl2 (8 mL). The solutions were left at room temperature for about 3 days, and yellow
2
3
285828 C34H24AgF3N4O3S 733.50 triclinic P1 10.6963(7) 11.5687(7) 13.6314(9) 74.4470(10) 77.4280(10) 87.1810(10) 1585.98(18) 1.536 2 740 0.760 R1 = 0.0633 wR2 = 0.1686 1.073
715181 C28H14Ag3Cl2F9N4O6 1067.94 triclinic P1 11.5437(8) 12.2903(9) 13.5429(10) 76.7510(10) 72.6150(10) 79.0900(10) 1769.7(2) 2.004 2 1028 1.888 R1 = 0.0571 wR2 = 0.1280 1.013
crystals were obtained. Yield: 0.0970 g, 50%. IR (KBr, cm-1): 2220 (vs), 1600(s), 1500(s), 1480(m), 1320(s), 1280(s), 1180(m), 1090(vs), 839(m), 627(m), 569(m). Anal. Calcd for C28H23AgClN4O5.5: C, 51.99; H, 3.584; N, 8.662. Found: C, 52.03; H, 3.590; N, 8.656. Synthesis of [Ag(TCPA)(CF3SO3) 3 0.5H2O 3 1.5C6H6]n (6). A mixed solution of AgCF3SO3 (0.0771 g, 0.3 mmol) in benzene (5 mL) and two drops of water was layered onto a solution of TCPA (0.0963 g, 0.3 mmol) in CH2Cl2 (8 mL). The solutions were left at room temperature for about 3 days, and yellow crystals were obtained. Yield: 0.0120 g, 57%. IR (KBr, cm-1): 2220 (vs), 1600(vs), 1320(m), 1280(m), 1180(m), 1080(s), 839(m), 569(m). Anal. Calcd for C31H22AgF3N4O3.5S: C, 52.93; H, 3.152; N, 7.965. Found: C, 52.86; H, 3.157; N, 7.971. Synthesis of [Ag4(TCPA)2(CF3CO2)3(CF3SO3) 3 C6H6 3 CH2Cl2]n (7). A solution of AgCF3SO3 (0.0257 g, 0.1 mmol) and AgCF3CO2 (0.0663 g, 0.3 mmol) in benzene (10 mL) was layered onto a solution of TCPA (0.0642 g, 0.2 mmol) in CH2Cl2 (10 mL). The solutions were left at room temperature for about 3 days, and yellow crystals were obtained. Yield: 0.1090 g, 63%. IR (KBr, cm-1): 2220 (vs), 1690 (s), 1500 (m), 1290 (m), 1210(vs), 1140 (s), 816 (m), 698 (m), 596 (m). Anal. Calcd for C56H32Ag4Cl2F12N8O9S: C, 39.03; H, 1.871; N, 6.502. Found: C, 39.12; H, 1.877; N, 6.515. X-ray Crystallography. Suitable crystals were mounted with glue at the end of a glass fiber. Diffraction data were collected at 293(2) K with a Bruker-AXS SMART CCD area detector diffractometer using ω rotation scans with a scan width of 0.3 and Mo KR radiation (λ = 0.71073 A˚). Empirical absorption corrections were carried out utilizing SADABS routine. The structure were solved by the direct methods and refined by full-matrix least-squares refinements based on F2. All non-hydrogen atoms were refined with anisotropic thermal parameters, and all hydrogen atoms were included in calculated positions and refined with isotropic thermal parameters riding on those of the parent atoms. The temperature factors of the disordered atoms were restrained to be approximately isotropic. Structure solutions and refinements were performed with the SHELXL-97 package.21 Crystal data and experimental details for the crystals of ligand TCPA and complexes 1-7 are given in Tables 1 and 2.
Results and Discussion Syntheses and Characterization. One of the important issues in determining the dimensions of porous CPs or MOFs is the scale and shape of the organic ligands.22 To achieve frameworks with larger-sized cavities, we synthesized the ligand TCPA, which has a star-shaped flexible backbone involving three symmetric PhCN spacers. The methodologies employed to synthesize TCPA involved either multiple reaction steps23 or specialized reagents based on the coupling
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Table 2. Crystallographic Data for Complexes 4-7 compound
4
5
CCDC 715178 715179 C28H23AgClN4O5.5 formula C30H22AgBF4N4O0.5 formula weight 641.20 646.84 crystal system orthorhombic orthorhombic space group Pnc2 Pnc2 a/A˚ 9.549(4) 9.8704(6) b/A˚ 26.717(10) 26.3900(16) c/A˚ 12.141(5) 12.1381(7) R/deg 90 90 β/deg 90 90 γ/deg 90 90 3097(2) 3161.7(3) V/A˚3 1.375 1.340 Dc/Mg m-3 Z 4 4 F(000) 1288 1288 0.701 0.761 μ/mm-1 R1 = 0.0736 final R indices [I > 2σ(I)] R1 = 0.0738 a wR2 = 0.1808 wR2 = 0.1933 R and Rw 1.047 1.029 GOF on F2 P P P P a R = |Fo| - |Fc|/ |Fo|; Rw = [ w(Fo2 - Fc2)2/ w(Fo2)2]1/2.
of 4-bromocyanobenzene or 4-fluorocyanobenzene with 4-cyanoaniline in moderate yield.24 Herein, TCPA is synthesized in good yield depicted in Scheme 1, in which tris-(4iodophenyl)amine20 reacts with CuCN in the presence of HMPA catalyst under an inert atmosphere. TCPA is easily soluble in common polar organic solvents, such as CH2Cl2 and CHCl3, which potentially facilitates the solution reaction between the ligand and inorganic silver salts. Our synthetic strategy for operating the three equivalent arms of TCPA is the use of the template of solvent and/or anions, which is schematically depicted in Scheme 2. The silver ion is trigonal coordinated by three nitrogen donors from three TCPA ligands, and each TCPA molecule is coordinated to three silver ions. In the coordination of cyanophenyl moieties, the silver ion is generally bridged by three ligands to form a triangle Ag(PhCN)3, which is frequently observed in the Ag-PhCN system.16,18 Since three cyanophenyl moieties of TCPA are connected by N-C single bonds, the resultant [Ag1.5(TCPA)] coordination framework is polymeric. Nevertheless, the overall predictable structures of complexes are different in the network topologies, interpenetration numbers, and pore size. On the basis of the coordinative properties of tritopic ligands and AgI ions, there are three types of basic motifs that can be constructed from TCPA module connecting, which causes the three Ph-CN groups to form a different arrangement around the nitrogen atom of triphenylamine: type I: 4.82 nets; type II: (6,3) nets; type III: (10,3) nets. Evidently, the angle between Ph-CN groups of ligand TCPA influences the shapes of the architectures due to the conformational freedom of the three PhCN groups. The slow diffusion of the organic solution (CH2Cl2, benzene, or CH3CN) of TCPA into a benzene or toluene solution of AgX (X = BF4-, ClO4-, CF3SO3-, and CF3CO2-) afforded the 3:1 ratio of Ag to TCPA for the adduct of CF3CO2- and a 1:1 ratio for five adducts with anion BF4-, ClO4-, and CF3SO3-. This difference maybe results from the different coordinating properties and the subtle templating effect of the anions and/or solvent molecules. Complexes 1-7 are stable in air at room temperature only for a short time (∼several hours). In these Ag-TCPA reactions, the products do not depend on the ligand-to-metal ratio. However, increasing the metal-to-ligand ratio resulted in somewhat
6
7
715180 C31H22AgF3N4O3.5S 703.46 orthorhombic Pnc2 10.0613(8) 26.359(2) 11.9930(9) 90 90 90 3180.6(4) 1.469 4 1416 0.756 R1 = 0.0485 wR2 = 0.1052 1.038
715182 C56H32Ag4Cl2F12N8O9S 1723.34 monoclinic P2(1)/n 10.5230(5) 11.5968(6) 50.242(3) 90 95.6970(10) 90 6100.9(5) 1.876 4 3368 1.486 R1 = 0.0959 wR2 = 0.2457 1.057
Figure 1. ORTEP diagram showing the structure of TCPA with 30% thermal ellipsoids probability and the atom-labeling scheme.
higher yield and higher crystal quality. The structures of these complexes are described below in detail. Crystal Structure of the Ligand TCPA. Crystal structural analysis of tris-(4-cyanophenyl)amine (TCPA) was reported in preliminary form by Radhakrishnanin.24b Herein, we expatiate the structure of ligand TCPA in the next discussion. As shown in Figure 1, TCPA is a tritopical molecule, in which the separation between the central nitrogen atom and terminal N-donor is ∼7.4 A˚. Three benzonitrile moieties are connected via three nitrogen-carbon single bonds to generate a star-shaped spacer, in which three arms can rotate freely around the nitrogen-carbon single bonds. Thus, this flexible TCPA can be very useful in construction of elaborate metal-organic complexes. The central triphenylamine is nonplanar due to the sterically hindered C-H groups. However, the central nitrogen atom N(2) is coplanar with the three carbon atoms to which it bonded C(8), C(5), and its equivalent C(5A) (the sum of bond angles around N(2) is 360). The phenyl ring containing C(8) is non-coplanar with the central NC3 plane with the dihedral angle of 48.69, while the remaining two phenyl rings have the same dihedral angles of 30.02, with the NC3 unit of TCPA, which results in a trifoliate-impeller structure around the central N atom. This phenomenon is also observed in compounds 1-7. Compared with the free ligand TCPA, the corresponding dihedral angles between the NC3
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Figure 3. 2-fold interpenetrated 4.82 topological networks in the complex 1: (a) top views; (b) side views.
Figure 2. The two-dimensional extended frameworks of 1 shown as a space filling model. (Ag purple, C gray, H white, O red, Cl green; solvent molecules and hydrogen atoms are omitted for clarity.)
planes and PhCN planes in 1-7 have different variations and are listed in Table S1, Supporting Information. 4.82 Topological Networks of the Complex [Ag(TCPA)(ClO4)]n 3 nC6H6 (1). Crystallization of TCPA with silver perchlorate in a dry dichloromethane-benzene mixed-solvent system at room temperature afforded 1 as a 2-fold parallel interpenetrated network with 4.82 topology. As shown in Figure 2, each silver(I) atom is coordinated by three nitrogen atoms from three different TCPA ligands. Because of the presence of the flexible center, TCPA can coordinate to the metal ion comfortably to meet the geometric requirement of silver. As a result, the three Ag-N bond lengths are slightly different: Ag(1)-N(1) 2.201(4) A˚; Ag(1)-N(3) 2.183(5) A˚; Ag(1)-N(4) 2.369 (6) A˚. The Ag(I) ion locates within the plane formed by N(1), N(3), and N(4) atoms with deviation less than 0.12 A˚. The N-Ag-N coordination angles range from 93.7(2) to 152.03(18). Each Ag ion is also coordinated by an O atom from ClO4- anion (Ag-O 2.56 A˚). This Ag-O vector is near-perpendicular to this AgN3 plane, in which O-Ag-N angles are 86.1(2), 86.4(2), and 104.1(2), respectively. Each TCPA in turn links three Ag(I) atoms to generate an infinite 2D network, which contains two different metallacycles A and B. In A, four benzonitrile units from two TCPA ligands connect two Ag(I) ions to form a 28-membered ring with a Ag 3 3 3 Ag distance of 13.67 A˚. In B, four TCPA ligands, each ligand uses two of their three benzonitrile units to connect four Ag(I) atoms forming a 56-membered ring with three types of intermetallic separations: Ag(A) 3 3 3 Ag(B) 15.87 A˚, Ag(A) 3 3 3 Ag(C) 17.80 A˚, and Ag(B) 3 3 3 Ag(D) 26.41 A˚, respectively. Each 28-membered ring is surrounded by four 56-membered rings, and each 56-membered ring approaches four 28-membered rings and four 56-membered rings. Thus, the 2D network of 1 can be regarded as a 4.82 topology (Figure 3).25,26 In 1, the 56-membered ring is large enough to include a 28membered ring from another sheet. Two guest benzene molecules are also locked in the vacancy of a 56-membered ring (Figure S2, Supporting Information) and connect to the framework through edge-to-face C-H 3 3 3 π interactions (2.65 A˚). As a result, the corrugation of the 2-D sheets,
caused by the flexible arms of TCPA, is also essential for the parallel interpenetration. Interestingly, the perchlorate anions locate at the “node” and connect to two network through double μ-O bridging interactions. That is, the perchlorate anion plays a double bridging role to link two interpenetrated networks (Figure 4). Although the Ag(1)-O(1)#1 bond distance is somewhat longer (2.947 A˚) than the other Ag-O bond, it is still significantly shorter than the sum of the van der Waals radii for silver and oxygen (1.72 and 1.52 A˚, for Ag and O, respectively).27 This double interpenetrated μ-O bridging interaction potentially increases the stability of networks. Each perchlorate anion acts as a μ-η1 bridging ligand rather than the μ-η2 bridging, terminal, or chelating coordination modes commonly observed in many other Agperchlorate complexes.28,29 Such a μ-η1 coordination perchlorate anion is rare in a silver-perchlorate system.30 This μ-η1 mode results in relatively small O-Ag-O bond angles (83.46), which incline to form the sterically hindered cluster core in the self-assembly process. In contrast to interpenetrating (6,3) topological networks,31 which are frequently observed in coordination polymers, the interpenetrated 4.82 networks are not well-characterized yet.26 In 1, two independent 4.82 networks are linked each other via anions bridging, making an infinite 2D network structure. Flexible TCPA makes its Ag(I) complex 1 possible to interpenetrate each other. Such a feature was not observed in Ag(I) complexes with rigid ligands.32 (6,3) Topological Networks of the Complex [Ag(TCPA)(CFSO3)]n 3 2nC6H6 (2). The bright yellow single crystals of 2 were obtained by slow diffusion of a benzene solution of AgCF3SO3 onto a solution of TCPA ligand in dichloromethane. The X-ray crystallographic analysis reveals that the asymmetric unit of 2 contains one molecule of TCPA, one silver(I) ion, and one molecule of the CF3SO3- anion. As shown in Figure 5, the chelation manner of ligand TCPA is similar to that of 1, although a different anion is present. The Ag-N distances range from 2.217(5) to 2.368(5) A˚, and the coordination angles vary from 106.01(19) to 129.43(18). Additionally, an anionic oxygen also strongly coordinates to the Ag(1) ion with a Ag(1)-O(1) length of 2.478(5) A˚, giving tetrahedral coordination geometry. Each ligand TCPA in turn links again three Ag(I) atoms to generate an infinite 2D sheet based on (6,3) nets as illustrated in Figure 5b. Three Ag(I) atoms and three TCPA ligands (each TCPA using two of the three arms connects two silver
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Figure 4. Top view of two-dimensional double-layer networks of 1 stacked together via double μ-O bridging interactions; benzene molecules and hydrogen atoms have been omitted for clarity. Symmetry transformations used to generate equivalent atoms: #1 -x, y, -z þ 1/2; #2 -x, y - 1, -z þ 1/2; #3 x, -y þ 1, z þ 1/2.
Figure 5. (a) The single honeycomb-shaped cavity in 2. Solvent molecules are shown as space-filling models. Ag purple, N blue, O red, S yellow, F green, C6H6 orange (*symmetrically generated); (b) the 2D extended networks of 2 shown as a space filling model with solvent molecules removed. Ag purple, N blue, O red, S yellow, F green, C6H6 orange.
atoms) form a 42-membered macrocyclic ring through the Ag-N coordination bonds. In this macrometallacycle, the lengths of the sides of a hexagon are almost equivalent (∼9 A˚), and the intermetallic separation of Ag 3 3 3 Ag is about 15.4 A˚. The topological packing diagram of 2 is shown in Figure 6. It can be seen clearly that the 2D layers repeat in an 3 3 3 ABAB 3 3 3 stacking sequence with big cavities occupied by benzene molecules. These 2D layers stack in the ab plane via strong face-to-face π 3 3 3 π stacking interactions between the lateral PhCN planes with an interplane distance of 3.33 A˚. The guest benzene molecules are included into the hostmacrometallacycle by the multiple hydrogen-bond interactions (see Supporting Information). Generally, the (6,3) net is one of the most common topologies in 2D coordination polymers, which are inclined to interpenetrate when a large six-membered ring is formed and the network shows undulating features.31,33 Herein, the nearly planar non-interpenetrating nets of 2 are likely to result from the stuffing effect of guest-benzene molecules on host-networks. In 2, silver(I) ions serve as trigonal nodes, and the formation of networks with (6,3) topology is enhanced by using star-shaped TCPA molecule enclosing an angle of about 120. A (6,3) topology has previously been reported in a
Figure 6. The topological (6,3) networks in 2, showing 3 3 3 ABAB 3 3 3 packing mode.
silver(I) complex [Ag(TCB)](CF3SO3) with a planar and rigid ligand 1,3,5-tricyanobenzene (TCB).32 In contrast to TCB, the ligand TCPA can have various conformations depending on the dihedral angles between the PhCN planes and the
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Figure 7. (a) The 2D cationic networks of complex 3 shown as a space filling model, solvent molecules and Ag4(CF3CO2)62- cluster anions removed; (b) top view of the single honeycomb-shaped cavities in 3; (c) the side view of double layers honeycomb-shaped cavities in 3. [Ag4(CF3CO2)6]2- cluster anion and solvent molecules are shown as space-filling models in the cavities. Ag: purple, N: blue, CH2Cl2: orange, [Ag4(CF3CO2)6]2- cluster: light blue.
central NC3 plane. In each 2D layer of 2, the PhCN planes deviate from the NC3 planes with nearly equivalent dihedral angles of 37.43, 37.57, and 38.91 in each TCPA, respectively. That is, host-networks have not been mightily affected by guest-benene molecules, although the weak hydrogen bonding interactions exist in 2. (6,3) Topological Nets of the Complex [Ag3(TCPA)(CF3CO2)3]n 3 nCH2Cl2, (3), Containing a Rare Ag4(CF3CO2)62Cluster-Anion. In order to further evaluate the influence of the counterions on the structure of the complexes, the more strongly coordinating anion CF3CO2- was used in the reaction with TCPA, in order to compare the structure with the weakly coordinating ClO4- and CF3SO3- anions. Yellowish crystals of [Ag3(TCPA)(CF3CO2)3 3 CH2Cl2]n (3) were successfully isolated. Single-crystal analysis reveals that there are three independent silver(I) centers in 3 (Figure S6, Supporting Information). Although the anion is different from that of 2, the chelation by the TCPA ligand in a similar manner is observed again in 3. The silver(1) is coordinated by three nitrogen atoms from three TCPA molecules with normal Ag-N bond lengths in three bent fashions (N-Ag-N = 110.9(2), 113.3(2), and 129.7(2), respectively). Similar to 2, each TCPA in turn links three Ag(1) atoms to generate an infinite planar (6,3) honeycomb network in 3 (Figure 7). Three Ag(1) ions and three TCPA ligands (each TCPA using two of the three arms connects two silver atoms in each macrocyclic unit) form again a 42-membered macrocyclic ring. In this macrometallacycle, the length of the side is almost equivalent (∼9 A˚), and the intermetallic separations of Ag 3 3 3 Ag are ∼15 A˚, which is shorter than that of 2. The dichloromethane solvent molecules are located in the center of macrocyclic cavities. These planar networks still repeat in an 3 3 3 ABAB 3 3 3 stacking sequence in 3. Different from 2, the hexagonal cavities are almost fully occupied by guest-units CH2Cl2 and [Ag4(CF3CO2)6]2- cluster, as shown in Figure 7b,c. In this discrete tetranuclear Ag-cluster (Figure 8), each silver(I) atom is triangular coordinated by three oxygen atom from the three CF3CO2- anions with Ag-O distances ranging from 2.201(5) to 2.345(5) A˚. In each Ag4O12 core, the four silver(I) atoms are linked by six μ2-CF3CO2- anions to complete
Figure 8. Tetranuclear [Ag4(CF3CO2)6]2- cluster anion showing four Ag-Ag interactions. Ag: purple, N: blue, O: red, F: green (*symmetrically generated).
a Ag4-plane, in which carboxylate groups bridge metal centers in a head-to-head style, rather than the alternate mode commonly found in other complexes.34 The Ag-Ag distances range from 2.956 to 3.072 A˚, which are significantly longer than the sum of van der Waals radii of two silver atoms, 3.44 A˚ and are comparable to those found in other structurally characterized Ag-CF3CO2 complexes.15,34b,35 Obviously, the cluster-anion [Ag4(CF3CO2)6]2- is one of the excellent examples suitable for the study of metallophilic attractions with ligand supported in closed shell AgI systems. The attractive interactions between closed d10 shells in various M(I) clusters are subjects of special attention because the arrangement of metal centers and the number of those in close proximity can affect the photophysical behavior of the resulting polynuclear systems.36 Therefore, the controlled formation of small metal-clusters and the study of their structure-property correlations are of great importance in designing functional materials. In this regard, polynuclear silver(I) carboxylate exhibiting rich luminescent properties and a remarkable structural diversity has recently attracted researchers’ attention. A number of various silver clusters35-38
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Figure 10. The diagram showing the five-metals macrocyclic unit in complexes 4-6 and the unique unit of the (10,3) topological view.
Figure 9. Top view of two-dimensional double-layer metal-organic frameworks of complex 3 (Ag: purple, N: blue, O: red).
with different coordination patterns have been reported based on Ag-CF3CO2, such as linear,39 trianglar,40 and hexagonal41 structures; however, the quadrangular structure is rarely observed.34b Herein, tetrameric cluster is composed of four silver(I) ions and six trifluoroacetate anions, in which four silver(I) ions are bridged by carboxylate groups alternately above and below the Ag4-plane. And the tetrasilver clusters directly link the host framework via coordination interactions to form a polymeric network. This stems from the great electron-withdrawing properties of trifluoroacetate groups that enhance the electrophilicity of the silver(I) centers and enforce additional intermolecular silver-oxygen or silvernitrogen interactions between the Ag4-units and host {[Ag(TCPA)]þ}n frameworks. Thus, fluorination of carboxylate ligands holding a specific polynuclear silver(I) core together can be an important structure-controlling factor that allows switching on and off of the intermolecular forces between clusters and frameworks. This effect can be used to manipulate supramolecular assembly processes in the solid state. Besides hydrogen bonding interactions (Figure S7, Supporting Information), the big guest [Ag4(CF3CO2)6]2- anion is fixed in the cavities of the host-networks for complex 3 through quadruple coordinative inteactions, which forms a hexanuclear silver cluster [Ag6(CF3CO2)6]. As shown in Figure 9, the simple-sheet nets of 3 are linked into a 2D doublelayer via interpolymer Ag-N and Ag-O coordinative interactions. The coordination system involves Ag(1) and N(3) atoms of the cationic networks, and O(1) on the CF3CO2ancillary ligand of the [Ag4(CF3CO2)6]2- cluster as well as Ag(2) atom. The Ag(1)-O(1) and Ag(2)-N(3) bond lengths are 2.91 and 3.20 A˚, respectively. As a result, three PhCN planes in the TCPA deviate from the NC3 planes with different dihedral angles of 19.52, 35.40, and 54.98, respectively, although 3 has a (6,3) topological structure similar to 2. Evidently, this severe twist results from the strong coordinative interactions of guest cluster-anions to host-networks, which is a rare example of the host cationic networks containing guest cluster-anions. (10,3) Topological Networks of the Complexes [Ag(TCPA)(BF4) 3 0.5H2O]n 3 1.5nC6H6 (4), [Ag(TCPA)(ClO4) 3 0.5H2O]n 3 n5H2O 3 nC7H8 (5), and [Ag(TCPA)(CF3SO3) 3 0.5H2O]n 3 1.5nC6H6 (6). Consider that three benzonitrile moieties of
TCPA cannot be coplanar, but reside at a changing dihedral angle. Theoretically, the (10,3) net has the highest symmetry among all three-connected topologies and is easy to form based on [Ag(PhCN)3].42 The [Ag(PhCN)3] secondary building unit (SBU) and the rotation angle of TCPA fully match the geometry requirement of (10,3) topology. On the basis of this consideration, we have obtained three (10,3) networks of [Ag(PhCN)3] through changing the reaction condition. Template-controlled supramolecular structures have been established for these metal triphenylnitriles. The structural properties of these compounds are greatly influenced by the framework flexibility, which are further monitored by single-crystal diffraction studies. The reaction of TCPA with three Ag(I) salts containing different anions generated three 3D MOFs with similar (10,3) toplogical structures: [Ag(TCPA)(BF4) 3 0.5H2O]n 3 1.5nC6H6 (4), [Ag(TCPA)(ClO4) 3 0.5H2O]n 3 n5H2O 3 nC7H8 (5), and [Ag(TCPA)(CF3SO3) 3 0.5H2O]n 3 1.5nC6H6 (6). In these complexes, each Ag(I) ion is coordinated by three terminal benzonitrile nitrogen donors from three different TCPAs. The basic unit is similar to the penta-metal macrocyclic structure [Ag5(TCPA)5], in which five AgI ions are noncoplanar (Figure 10). The interlaced connection of metal ions and two PhCN arms of TCPA constructs a 70-membered macrocyclic unit. Although the anions are different in the three complexes (BF4- for 4; ClO4- for 5 and CF3SO3- for 6), the dimension of macrocyclic units varies very little with the change of anions. The distances of Ag-N are comparable in 4-6 (2.184(9)-2.243(9) A˚ for 4; 2.213(10)-2.247(8) A˚ for 5; 2.213(5)-2.265(4) A˚ for 6). The lengths of sides are almost equivalent in each macrocyclic ring, and the adjacent intermetallic separations of Ag 3 3 3 Ag (or node-to-node distance) range from 15.11 to 15.65 A˚ for complexes 4-6, which is comparable to those of 1-3. Each TCPA in turn links three silver atoms to generate the infinite 3D frameworks based on (10,3) topology (Figure 11a). Large honeycomb channels can be observed in complexes 4-6 by viewing down the ab plane directions. (Figure 11b). These channels are partially filled by three other interpenetrated symmetry-equivalent frameworks, leading to a rare 4-fold interpenetrated structure (Figure 12). However, in the view of host properties, these frameworks do not provide high opportunity since channels have only a limited cavity due to the interpenetration. Guest-water molecules are located in the cavities of frameworks and connect two single (10,3) networks via μ-Owater bridging interactions. That is, each water molecule plays a
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Figure 11. (a) The topological (10,3) networks in complexes 4-6; (b) space-filling diagram of single topological (10,3) nets in complexes 4-6 viewed down the ab plane.
Figure 12. 4-fold interpenetrated (10,3) coordination networks of complexes 4-6.
bridging role to link two adjacent interpenetrated frameworks. The Ag-Owater bond distances are significantly short (2.489(10), 2.474(9), and 2.445(3) A˚ for 4, 5, and 6, respectively), which indicates strong interactions between water and silver ions. This bridging mode results in relatively large Ag-O-Ag bond angles (112.37, 115.86, and 124.63 for 4, 5, and 6, respectively). Such an arrangement certainly reinforces the stability of the host framewoks. Evidently, the remarkable feature of 4-6 is that the single (10,3) nets are linked to each other by the water molecules to form three 4-fold interpenetrated frameworks. Such adamantoid constructions of 4-6 have rarely been observed in MOFs.42,43 In the cases of 4-6, the 4-fold interpenetration of the frameworks generate reduced infinite irregular honeycomb channels along the c axis (Figure 13), in which the anions and solvent molecules fill in cavities as guest molecules. It can be concluded from the architectures of three MOFs that the water molecules play key roles in determining the topological structures of complexes 4-6, rather than counterions (nonpolar BF4- for 4 and ClO4- for 5 as well as polar CF3SO3for 6). Crystal Structure of the Complex [Ag4(TCPA)2(CF3CO2)3(CF3SO3)]n 3 nC6H6 3 nCH2Cl2 (7) with “Zigzag” Ag4 Chain. There are four unique Ag(I) ions, three CF3CO2- anions, one CF3SO3- anion, and two TCPA ligands in the asymmetric unit of complex [Ag4(TCPA)2(CF3CO2)3(CF3SO3)]n 3 nC6H6 3 nCH2Cl2 (7) (Figure 14). In this unique unit, two types of inorganic units, the Ag2O4 cluster (Ag(1) 3 3 3 Ag(2) 3.026 A˚) and the Ag2O3 dimer (Ag(3) 3 3 3 Ag(4) 3.230 A˚), are connected via double μ-O (Ag(3)-O(4) 2.789 A˚ and Ag(2)O(5) 2.426(8) A˚) bridges into a Ag4 cluster. The distance of
Figure 13. 4-fold interpenetration of complexes 4, 5, and 6, showing the channels of frameworks filled with guest molecules (yellow rings: benzene for 4 and 6; toluene for 5). Frameworks are shown as space-filling models, and four sets of (10,3) nets are shown as different colors.
Ag(2) 3 3 3 Ag(3) is 3.67 A˚. Each TCPA acts as a μ3 bridge to link three silver atoms to expand the structure. In particular, N(1) donor adopts μ-N mode and coordinates to two silver(I) ions (Ag(1)-N(1) 2.303(11) A˚; Ag(4)*-N(1) 2.840 A˚; — Ag(1)-N(1)-Ag(4)* 96.77). Thus, Ag4 clusters are further joined into a 1-D silver chain via the linkage on N(1) atoms (Figure 15), which are further extended by the TCPA spacers into 3D networks with special cavities containing guest molecules (benzene and dichloromethane) (Figures S15 and 16). In the structure of 7, the trifluoromethanesulfonate anion acts as a μ-η1 bridging mode44 rather than the μ-η2 bridging, terminal, or chelating mode commonly observed in many other Ag-CF3SO3 complexes.14,44 Three trifluoroacetate anions have two linking types: two of them act as a μ-η3 bridging ligand and the third one plays a μ-η2 chelating coordination mode commonly observed in many other silvertrifluoroacetate complexes.38-41 Herein, we have demonstrated that flexible three “arms” ligand TCPA, with intermolecular bonding capacity, can be used as a “flexible building block” to prepare flexible CPs or MOFs. The various topological nets are constructed by using different templates to manipulate three equivalent flexible “arms”. The three benzonitrile moieties are equivalent in free ligand TCPA; however, upon bonding to silver ions, their conformation varies to a greatly degree for accommodating coordination requirements. In 4.82 topological networks 1, anion perchlorate acts as a μ-η1 bridging ligand to link two
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Figure 14. Crystal structure of complex 7 with partial atom numbering scheme.
Figure 15. One dimensional silver chain in complex 7, showing a rare μ-N bridging and Ag-π interaction (Ag(2)*-C(3) 3.272 A˚; Ag(2)*-C(4) 3.172 A˚). *Symmetrically generated.
interpenetrated networks, which results in three PhCN arms of TCPA highly twisting. In (6,3) nets 2, SO3CF3- anion only acts as a terminal ligand to coordinate the silver ion, and the PhCN planes deviate from the NC3 planes with nearly equivalent dihedral angles in each TCPA. Although compound 3 forms also a (6,3) topological net similar to 2, the anion CF3CO2- has stronger coordination and forms a big guest [Ag4(CF3CO2)6]2- anion cluster, which is fixed in the cavities of the host-networks through strong coordinative interactions. Thus, host-networks of 3 are slightly twisted compared with 2. In 4-6, the rotation of three PhCN arms is nearly comparative, resulting in three similar (10,3) topological networks, although anions are different (BF4- for 4; ClO4- for 5; CF3SO3- for 6). This remarkable feature stems from the solvent water molecules to strongly coordinate to silver ions, which links the single (10,3) nets to construct 4-fold interpenetrated frameworks. That is, the water molecules have a greater effect than that of anions in (10,3) topological nets 4-6. Luminescent Properties. For potential applications as luminescent materials, fluorescence properties have been investigated on metal-organic coordination polymers. Because of the ability to affect the emission wavelength of organic materials, syntheses of inorganic-organic coordination polymers have employed the ingenious design of organic ligands and judicious choice of proper metal ions in order to obtain new types of luminescent materials, especially for d10 metal systems.45 Recently, we have explored the luminescent properties of the rigid ligand 3,6-dicyano-9-phenylcarbazole and its Ag(I) coordination polymer.15a Results indicated that emission color of organic spacers was remarkably affected by Ag coordination compounds. Herein, the luminescent properties of flexible ligand TCPA and its silver complexes 1-7 were investigated.
Figure 16. Emission spectra in the solid state of the free ligand TCPA and its silver compounds 1-3 at room temperature (excitation at 400 nm).
The emission bands of eight compounds in the solid state are different (Figures 16 and 17). A strong emission of the free ligand TCPA with wavelength from 425 to 500 nm (λmax = 450 nm) upon excitation at 400 nm is observed, which is elaborated by Radhakrishnanin.24b Blue/green luminescence is observed with the coordination to silver ions. In the solid state, complexes 1-3 show broad emission bands at 450 nm (1), 459 nm (2), and 447 nm (3), respectively, upon 400 nm excitation. Complexes 4-5 also have broad emission bands with λmax at 428 nm (4) and 443 nm (5), respectively, upon 400 nm excitation, whereas complex 6 has very broad emission bands (bandwidth at half-height > 100 nm) with λmax at 456 nm. Complex 7 has a broad emission bands with λmax at
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counterions. The conformational flexibility of the bridging ligand permits the conformational change of the architecture. Acknowledgment. This work was supported by the National Natural Science Foundation of China (Nos. 20873135; 50903081), the China Postdoctoral Science Foundation (No. 20070420724), the Cultivation Fund of the Key Scientific and Technical Innovation Project, Ministry of Education of China (No. 707036) and the Natural Science Foundation of Jiangsu Province (No. BK2008579). Supporting Information Available: Some figures and tables, as well as crystallographic data. This material is available free of charge via the Internet at http://pubs.acs.org.
References
Figure 17. Emission spectra in the solid state of the free ligand TCPA and its silver compounds 4-7 at room temperature (excitation at 400 nm).
441 nm. All these complexes exhibited relatively weak emissions, which may be a result of the heavy-atom effect of silver.46 It is clear that different emissions in 1-7 are due to the variation of anions and coordination environments of metal centers, because photoluminescence behaviors closely associate with the local environments around silver ions.47 In 1, the anion BF4- induces the 4.82 net pattern. Although 2 and 3 display similar (6,3) nets, the coordination anion-units (moieties for 2 and clusters for 3) are different. The complexes 4-6 show similar topological (10,3) nets and metal coordinaton modes, in which silver centers provide similar coordination geometries, but distinct emission spectra are observed, which is likely to result from the different dissociative anions and guest solvent molecules in MOFs. These guest units entangle with the host MOFs via various H-bonding interactions and/or π-stacking. Conclusions The present work demonstrates that a star-shaped molecule module TCPA can be pertinently assembled to produce various kinds of desired MOFs by a building-block methodology of the molecular arms. The TCPA module is so flexible that it can vary the shape and the dimensionality of the assemblies by changes of the dihedral angles and the conformation via exterior factors. Consequently, the building blocks afford surprising diversities of the assembled structures (Scheme 2); (1) 4.82 nets in 1; (2) (6,3) nets in 2 and 3; (3) (10,3) nets in 4-6. Thus, the control of these features is one of the key factors to develop a pertinent synthesis strategy for the desired architectures from a flexible building block with starshaped arms. The silver ion mediates the tuning of the structures of the motifs and the conformation of three arms because of the properties of three trigonal nodes of the silver ion. Besides silver ions, the structures of the motifs can be described as the result of reading molecular information stored in the TCPA molecule by the anions and solvent molecules (or templates). In this Ag-TCPA system, the synthesis using the TCPA provides a series of novel coordination polymers, which exhibits a variety of topological patterns based on the flexible frameworks responding to specific guest molecules or
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