Two-Dimensional Frameworks Based on Ag(I)–N Bond Formation: Single Crystal to Single Molecular Sheet Transformation

A series of new two-dimensional coordination framework materials, based on Ag­(I)–N bond formation, has been synthesized and structurally characterized by single crystal methods. Reactions between the poly-monodentate bridging ligand <i>N</i>,<i>N</i>′-((1r,4r)-cyclohexane-1,4-diyl)­bis­(1-(pyridin-3-yl)­methanimine), <b>L1</b>, and silver salts yield compounds {[Ag­(<b>L1</b>)­(MeCN)]­(CF₃SO₃^–)}_<i>n</i>, <b>1</b>, {[Ag­(<b>L1</b>)­(PF₂O₂^–)]·H₂O}_<i>n</i>, <b>2</b>, and {Ag₂(<b>L1</b>)­(tosylate)₂}_<i>n</i>, <b>3</b>. The frameworks of these materials exhibit two distinct net topologies: 3⁶.4⁶.5³ (<b>1</b> and <b>2</b>) and 4⁴.6² (<b>3</b>). In all cases, <b>L1</b> ligands are found to be fully saturated, in terms of metal ion binding, with both sets of pyridyl and imino N atoms involved, though in <b>1</b> and <b>2</b>, crystallographically independent <b>L1</b> moieties also display pyridyl-only binding. Either solvent (<b>1</b>) or the anion (<b>2</b> and <b>3</b>) acts as a terminal ligand to support interlayer interactions in the solid state. For <b>2</b> and <b>3</b> the molecular sheet orientation lies in the plane of the largest crystal face, indicating that crystal growth is preferentially driven by coordinate bond formation. Despite the relatively labile nature, typical of such Ag­(I)–N bonds, solvent-based exfoliation of crystals of <b>3</b> was shown to provide dispersions of large, μm², flakes which readily deposit on oxide surfaces as single-molecule sheets, as revealed by atomic force microscopy

Two-Dimensional Frameworks Based on Ag(I)–N Bond Formation: Single Crystal to Single Molecular Sheet Transformation

A series of new two-dimensional coordination framework materials, based on Ag­(I)–N bond formation, has been synthesized and structurally characterized by single crystal methods. Reactions between the poly-monodentate bridging ligand <i>N</i>,<i>N</i>′-((1r,4r)-cyclohexane-1,4-diyl)­bis­(1-(pyridin-3-yl)­methanimine), <b>L1</b>, and silver salts yield compounds {[Ag­(<b>L1</b>)­(MeCN)]­(CF₃SO₃^–)}_<i>n</i>, <b>1</b>, {[Ag­(<b>L1</b>)­(PF₂O₂^–)]·H₂O}_<i>n</i>, <b>2</b>, and {Ag₂(<b>L1</b>)­(tosylate)₂}_<i>n</i>, <b>3</b>. The frameworks of these materials exhibit two distinct net topologies: 3⁶.4⁶.5³ (<b>1</b> and <b>2</b>) and 4⁴.6² (<b>3</b>). In all cases, <b>L1</b> ligands are found to be fully saturated, in terms of metal ion binding, with both sets of pyridyl and imino N atoms involved, though in <b>1</b> and <b>2</b>, crystallographically independent <b>L1</b> moieties also display pyridyl-only binding. Either solvent (<b>1</b>) or the anion (<b>2</b> and <b>3</b>) acts as a terminal ligand to support interlayer interactions in the solid state. For <b>2</b> and <b>3</b> the molecular sheet orientation lies in the plane of the largest crystal face, indicating that crystal growth is preferentially driven by coordinate bond formation. Despite the relatively labile nature, typical of such Ag­(I)–N bonds, solvent-based exfoliation of crystals of <b>3</b> was shown to provide dispersions of large, μm², flakes which readily deposit on oxide surfaces as single-molecule sheets, as revealed by atomic force microscopy

Structural Diversity and Argentophilic Interactions in One-Dimensional Silver-Based Coordination Polymers

A series of new one-dimensional coordination polymer materials, based on Ag­(I)–N bond formation, has been synthesized and structurally characterized by single crystal X-ray diffraction. Reactions between the poly-monodentate ligands based on (<i>1E</i>,<i>1</i>′<i>E</i>′)<i>-N</i>,<i>N</i>′<i>-</i>(-bis­(1-pyridin-3-yl)­methanimine and Ag­(I) salts give products that feature simple coordination chains or metallacyclic- and tape-based structures. For the simple chains these are as either isolated units, or assembled in dimeric and tetrameric arrangements through intermetallic, argentophilic interactions. However, crystal packing effects and solvent inclusion are found to readily disrupt this type of bonding. Density functional theory calculations provide an assessment of the bond order and the influence of anion binding on these interactions