含全碳和多炔阴离子配体的银簇化合物的超分子组装及其结构研究

doi:10.7503/cjcu20150601

摘要/Abstract

摘要：

总结了我们在新型炔银簇化合物研究方面的最新进展. 这些化合物分为以下几种类型: (a)1,3,5-己三炔基和1,3,5,7-辛四炔基; (b)1,5-己二炔基; (c)经膦酸配体组装的乙炔基和烷基乙炔基; (d)苯乙炔基、环烷基乙炔基和含氮杂环基乙炔基结构单元的银簇化合物; (e)经不同类型的银-碳配位键连接, 并进一步通过分子内/分子间作用力稳固其配位网络的炔银化合物. 我们还进一步讨论了溶剂、配体的位阻大小和辅助配体类型对于多维配位网络结构的影响.

关键词: 全碳配体, 亲银作用, 多炔配体, 炔基, 银簇网络结构, 超分子合成子

Abstract:

This review summarizes recent advances conducted by our group on related silver complexes of (a) all-carbon ligands $C 6 2 -$ and $C 8 2 -$ , (b) 1,5-hexadiyne-1,6-diide C₆ $H 4 2 -$ , (c) ethynediide $C 2 2 -$ and ethynide R— $C 2 -$ assembled with phosphonic acids, (d) aryl, alicyclic and heteroaromatic ethynides, and (e) ethynides that are stabilized by different types of silver…carbon binding interactions in the crystalline state, which are further consolidated by weak intra/intermolecular forces. The effects of the solvent, bulkiness of ligands and ancillary ligands on the construction of coordination networks are also discussed.

Key words: All-carbon ligand, Argentophilicity, Carbon-rich ligand, Ethynide, Organosilver(I) network, Supramolecular synthon

中图分类号:

TrendMD:

侯俊傑, 胡婷, 譚耀新, 麥松威. 含全碳和多炔阴离子配体的银簇化合物的超分子组装及其结构研究. 高等学校化学学报, 2015, 36(11): 2115.

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. Chem. J. Chinese Universities, 2015, 36(11): 2115.

图/表 29

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.10 Top-down view(A) and side view(B) of the molecular skeleton of {Ag8(dppm)4(tBuPO3)2·(ClO4)(NO3)0.67(H2O)1.33}·(ClO4)2.33·(CH3OH)6.67 cluster

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)

Scheme 1 Structural formulas of ligands H2L13 and H2L14

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)

Scheme 2 Structural formulas of ligands H2L15—H2L19

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)

Scheme 3 Structural formulas of ligands H2L20—H2L24

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)

Scheme 4 Isomeric pairs of diethynyl-functionalized stilbenes synthesized for the assembly of organosilver(I) frameworks

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 5 A series of ligands based on aromatic skeletons bearing terminal ethynyl and ethenyl groups on separate pendent arms

Fig.21 Perspective view of crystal packing in AgL36·6AgCF3CO2·H2O(A) and perspective view of crystal packing in AgL37·7AgCF3CO2·4H2O(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

Scheme 7 Classification of different types of silver-ethynide interactions

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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