Silver(I) Arylsulfonates:  A Systematic Study of “Softer” Hybrid Inorganic−Organic Solids

Abstract

The present study represents the first systematic examination of the effects on the layered structure of simple silver aryl-monosulfonates as the breadth of the pendant aryl group is increased beyond that where a simple "phosphonate-like" motif is sustainable. Five new silver arenesulfonates are reported. On the basis of comparison with Ag benzenesulfonate, a threshold of approximately 6.4 A is proposed and confirmed as the critical breadth of an aryl group for a simple layered motif to be observed in silver sulfonates. Ag 1,1'-biphenyl-4-sulfonate (1) and Ag 2-naphthalenesulfonate (2) are below this threshold and so form simple layered networks, termed type 1 solids. When the pendant group is broadened to a 1-naphthyl group, the layer incorporates coordinated water to maintain a layered structure giving Ag 1-naphthalenesulfonate hemihydrate (3a). This more diffuse structure is termed a type 2 solid. For anhydrous Ag 1-naphthalenesulfonate (3) and Ag 1-pyrenesulfonate (4), the additional breadth is compensated for by the formation of Ag-pi interactions and the formation of type 3 solids. Interactions between the pendant groups are observed to play a significant role in the packing of the solid. All frameworks are characterized by single crystal and powder X-ray diffraction, IR, DSC-TGA, and elemental analysis. The significance of this adaptable framework is discussed along with implications for design of stacked arene arrays.

Benzoquinolateplatinum(ii) complexes as building blocks in the synthesis of Pt–Ag extended structures

“…17,23 These η 1 -Ag-C interactions are important and, along with the Pt-Ag bonds contribute to fulfilling the electronic requirements of the acidic silver centre and the formation of the infinite chain. We note that the affinity of silver for some aromatic π-donor systems is well known, 33,[72][73][74][75][76][77] the η 1 and η 2 coordination modes being the most usual ones. Also, the Ag-C lines are usually almost perpendicular to the plane of the aromatic rings, which is almost accomplished in complex 2 taking into consideration the additional constraints caused by the existence of the Pt-Ag bonds.…”

Luminescent Pt–Ag Clusters Based on Neutral Benzoquinolate Cyclometalated Platinum Complexes

“…[32] These η 1 -Ag-C interactions are important and, along the Pt→Ag bonds, contribute to fulfil the electron density requirements of the acidic silver centre. The affinity of this metal for some π-donor systems is well known, [33,[69][70][71][72][81][82][83][84][85][86][87][88][89] being the most usual the η 1 and η 2 coordination modes. Ag-C lines are usually perpendicular to the aromatic planar ring system, which is more or less observed also in 7, 9 and 10, given the geometric limitations imposed by the Pt-Ag bonds.…”

Structural Constraints in the Design of Silver Sulfonate Coordination Networks: Three New Polysulfonate Open Frameworks

“…It has been shown by our group, and others, that sulfonate groups, which are generally regarded as weakly coordinating, can adopt a range of different bridging modes with metal centers, particularly with silver(I). , Structurally, silver(I) sulfonates are related to the well-studied metal phosphonate family, adopting the classic layered motif of hybrid inorganic−organic solids. For metal phosphonates, the interlayer region may be made porous by alternating pillaring groups with nonpillaring monophosphonate or phosphate groups …”