Chem. J. Chinese Universities ›› 2015, Vol. 36 ›› Issue (11): 2115.doi: 10.7503/cjcu20150601
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Sam S. K. HAU1,2, Ting HU1,3, Dennis Y. S. TAM1, Thomas C. W. MAK1,*()
Received:
2015-07-31
Online:
2015-11-10
Published:
2015-10-13
Contact:
Thomas C. W. MAK
E-mail:tcwmak@cuhk.edu.hk
CLC Number:
TrendMD:
Sam S. K. HAU, Ting HU, Dennis Y. S. TAM, Thomas C. W. MAK. Assembly of Organosilver(I) Networks with Multinuclear Supramolecular Synthons Containing All-carbon and Carbon-rich Anionic Ligands[J]. Chem. J. Chinese Universities, 2015, 36(11): 2115.
Fig.1 Coordination chain structure of Ag2C2·4AgCF3CO2·(bipyH)(CF3CO2)·H2O(A), discrete molecular structure of Ag2C2·7AgCF3CO2·(H3O)(CF3CO2)·2(bipyH2)(CF3CO2)2·3H2O(B), coordination chain structure of 2Ag2C2·8AgCF3CO2·6L1(L1=pyrazole)(C) and coordination chain structure of Ag2C2·10AgCF3CO2·2L2[L2=4,5-dihydro-3-(4-pyridinyl)-2H-benz(g)-indazole](D)
Fig.2 Ribbon-like coordination chain along b-axis formed by linkage of (C2)2@Ag15 units by bridging L3 ligands in [(Ag2C2)2(AgCF3COO)11(L3)(μ2-DMSO)3(DMSO)5]·1/4H2O
Fig.3 Discrete molecular structures of [(Ag2C4)(AgCF3CO2)6(L)6](L=2-cyanopyridine)(representative of 0D structure)(A), coordination chain structure of [(Ag2C4)2(AgCF3CO2)9(L)7(H2O)]n(L=3-chloropyridine)(representative of 1D structure)(B), coordination layer structure of [{(Ag2C4)0.5(AgNO3)3(L)}·H2O]n (L=3-chloropyridine)(representative of 2D structure)(C) and three-dimensional coordination network of [{(Ag2C4)(AgCF3CO2)5(L)1.5(H2O)2}·H2O]n(L=2-methylpyrazine)(representative of 3D structure)(D)
Fig.4 Coordination layer structure of Ag2C6·8AgCF3CO2·6H2O along c-axis(A) and ladder-like silver(I) double chain structure of 2.5(Ag2C8)·10AgCF3CO2·10DMSO(B)
Fig.5 Two typical coordination modes of C6H42- dianion (A) Agm?C6H4?Agn, anti “stretched-Z” conformation; (B) C6H4?Agn, gauche “arch-like” conformation.
Fig.6 3D coordination network of Ag2C6H4·2AgNO3·2AgL1 constructed by linking silver layers by pillar-like nitrate groups(A) and Ag2C6H4·4AgNO3·2L5 with coordination layers linked by weak N—H…O hydrogen bonds involving imidazole ligands and nitrate groups to form a 3D supramole-cular framework(B) and 3D supramolecular framework of Ag2C6H4·4AgNO3·2L6 with each coordination layer constructed by cross-linkage of silver chains by nitrate ligands
Fig.7 Infinite-chain structure of Ag2C6H4·5AgCF3CO2·3L5(A), two-dimensional coordination layer in 3Ag2C6H4·10AgCF3CO2·4L1(B) and three-dimensional coordination network of Ag2C6H4·3AgCF3CO2·2AgL7·H2O(C)
Fig.8 Top-down view of centrosymmetric Ag16 cluster in {(NO3)2@Ag16(PhC≡≡C)4[(tBuPO3)4V4O8]2·(DMF)6(NO3)2}(A) and top-down view of the core structure of pseudo-C3 Ag43 cluster in {[(O2)V2O6]3@Ag43(PhC≡≡C)19[(tBuPO3)4V4O8]3(DMF)6} For enhanced visibility, the three independent encapsulated [(O2)V2O6]4- species are represented by gray, turquoise, and blue semi-transparent polyhedra with V atoms included.
Fig.9 Core skeleton of one of the two nearly identical Ag28 clusters in [{Ag5(NO3@Ag18)Ag5}(tBuC≡≡C)16·(tBuPO3)4(H2O)4]·3SiF6·4.5H2O·3.5MeOH(A) and Cl@Ag22 cluster skeleton in[{Ag8(Cl@Ag14)}(tBuC≡≡C)14(tBuPO3)2F2·(H2O)2]BF4·3.5H2O, lying on a crystallographic C2 axis(B)
Fig.11 Layer structure of compound 1 viewed along the a-axis, in which the C2@Ag9 cages are linked by phosphonate groups(A) and three-dimensional architecture of compound 7 generated from the cross-linkage of silver chains by coordination bonding with aqua ligands(B)
Fig.12 Perspective views of argentophilic layer structure in [AgC≡≡CPh·AgNO3](A), silver(I) chain in [2AgC≡≡CPh·5CF3CO2Ag·4DMSO](B) and thick silver coordination column in [10AgC≡≡CPh·2AgOTf·AgNO3·3DMSO](C)
Fig.13 Perspective views of argentophilic silver(I) layer structure in 12[Ag(4-MeC6H4C≡≡C)]·7AgNO3(A) and the silver layer structure in 2[Ag(4-PhC6H4C≡≡C)]·AgNO3(B)
Fig.14 Argentophilic silver(I) structures in complexes generated with halophenylethynide ligands (A, D, G) Cl; (B, E, H) Br; (C, F, I) I; (A, B, C) para position; (D, E, F) meta position; (G, H, I) ortho position.
Fig.15 Different coordination modes of anionic tridentate L8 ligands in Ag11 and Ag12 aggregates(A) and coordination mode of L9 in [(AgL9)·(AgCF3CO2)5·(H2O)3][L9=1-chloro-2-(prop-2-ynyloxy)benzene]
Fig.16 Perspective views of a portion of an infinite silver-organic chain in the crystal packing of AgL11·3AgCF3CO2·3H2O(L11=2-ethynylquinoline)(A) and Ag8 aggregate in [(AgL12)·(AgCF3CO2)3](L12=2-ethynyl-4,6-dimethylpyrimidine)(B)
Fig.17 Coordination modes of independent L13 ligands in double salt(Ag2L13)·9AgCF3CO2·3H2O·3CH3CN(A) and perspective view of the linkage between metallocycles in the infinite-chain structure of (Ag2L13)2·9AgCF3CO2·11H2O(B)
Fig.18 Perspective view of the silver(I) atoms and ethynide groups in (Ag2L15)·8AgCF3CO2·6DMSO(A) and coordination environment of the silver(I) atoms and ethynide groups in (Ag2L19)·5AgCF3CO2·2H2O(B)
Fig.19 Coordination environment of the silver(I) atoms and ethynide groups in complex 11(A) and perspective view of the coordination silver-organic chain with L24 and Ag(I) aggregates in complex 12(B)
Fig.20 Perspective view of coordination geometry in double salt 2(Ag2L25)·7AgCF3CO2·3CH3CN(A) and perspective view of crystal packing in 3(Ag2L30)·14AgCF3CO2·[Ag2(CH3CN)3]·(CF3CO2)2·4H2O·6CH3CN(B)
Scheme 6 A series of ten ligands containing an aromatic core with a rigid/flexible terminal ethynyl group, an internal ethynyl group, and a vinyl substituent at various positions on an aromatic ring
Fig.22 Coordination modes of the anionic ligands in their corresponding silver complexes, in which part (J) illustrates the presence of all the four kinds of silver-carbon binding interactions in AgL44·6AgCF3CO2·H2O·MeOH
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[1] | CHEN Jia-Mei, WU Chuan-Bin, LU Tong-Bu*. Application of Supramolecular Chemistry on Pharmaceutical Cocrystals [J]. Chem. J. Chinese Universities, 2011, 32(9): 1996. |
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