Silver(I)−Organic Networks Assembled with Propargyl-Functionalized Di- and Trihydroxybenzenes

Abstract

A series of four new ligands bearing terminal ethynide moieties attached via pendant arms to a benzene skeleton have been used in the syntheses of four silver(I) complexes: [(Ag2L1)2·(AgCF3CO2)10·(CH3CN)2·(H2O)4·(μ2-H2O)2]·(AgBF4) (1), [(Ag2L2)·(AgCF3CO2)7·(CH3CN)·(H2O)] (2), {[(Ag2L3)·(AgCF3CO2)10·(CH3CN)6·(H2O)2·(OH)2]·(H2O)} (3), and [(Ag3L4)2·(AgCF3CO2)13·(CH3CN)5·(H2O)] (4) (H2L1 = 1,2-bis(prop-2-ynyloxy)benzene, H2L2 = 1,3-bis(prop-2-ynyloxy)benzene, H2L3 = 1,4-bis(prop-2-ynyloxy)benzene, H3L4 = 1,2,3-tris(prop-2-ynyloxy)benzene). In these compounds, the invariable appearance of the μ4- and μ5-ligation modes of the ethynide moiety affirms the general utility of the silver−ethynide supramolecular synthon Ag n ⊂CCCH2OC6H4OCH2CC⊃Ag n (n = 4, 5) in coordination network assembly. Additionally, several conventional and unconventional silver−ethynyl, argentophilic, hydrogen-bonding, silver−aromatic, and π−π interactions play an important role in stabilizing their framework structures. In 1, Ag15 aggregates are fused together by argentophilic interaction to yield thick silver rods, which are further linked through interchain hydrogen bonds into a 2D network. In 2, butterfly-shaped Ag4 baskets are fused into silver(I) columns, which are further associated by external Ag(CF3COO)2 units and argentophilic interactions to give a metal−organic sheet; adjacent layers are then linked into a 3D metal−organic framework through face-to-face aromatic π−π interactions. In 3, Ag6−phenyl ring−Ag6 structural units are interconnected by a pair of μ4-η2,η2 trifluoroacetate groups to yield silver columns, which are further united by hydrogen bonds to give a 3D metal−organic network. Two kinds of silver rods in parallel orientation are bridged by three μ3-η1,η2 and one μ4-η2,η2 trifluoroacetate groups to generate a two-dimensional metal−organic network of 4, in which the trianion exhibits the unprecedented μ20-coordination mode.

Argentophilic Interactions

“…Through corner-, edge-, or face-sharing of the clusters built around the terminal alkynyl anions, multidimensional aggregates are formed, and multidimensionality is also achieved by using multifunctional terminal alkynes as also shown in very recent work. [209,[211][212][213] In several Review articles, the variety of bonding modes has been summarized. [214][215][216][217] It is important to note that alkene and non-terminal alkyne units can become engaged in bonding with silver atoms through h 2 side-on complexation.…”

Functional Molecules for Grafting onto Ionic Surfaces

“…1,2-Bis(prop-2-ynyloxy)benzene, [22] methyl 2-amino-4-bromobutanoate, [18] methyl 4-bromo-2-(tert-butoxycarbonylamino)butanoate, [19] hexyl azide, [23] azidomethyl pivalate, [24] and (6-bromohex-1ynyl)triisopropylsilane [25] were obtained according to the published procedures. HHTP [26] was obtained from hexamethoxytriphenylene (HMTP) [27] according to literature procedure.…”

Crystal structure of poly[(μ3-2-(pyrazin-2-ylthio)acetato-κ3 N:O:S)silver(I)], C6H5AgN2O2S

“…Furthermore Ag(I) has a high affinity for hard donor atoms such as nitrogen, oxygen or sulfur atoms, being a favorable and fashionable building block for MOFs [3][4][5][6][7]. With the aim of constructing unusual coordination architectures, we have engaged in the synthesis of coordination polymer based on 2-(pyrazin-2-ylthio)acetic acid (HL) with silver HL which comprise a pyrazinyl moiety and a carboxylic groups, may show a rich variety of coordination modes with nitrogen, oxygen and sulfur atoms and help to construct novel coordination polymers.…”