3 research outputs found
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 AgÂ(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)ÂbisÂ(1-(pyridin-3-yl)Âmethanimine), <b>L1</b>, and silver salts yield compounds {[AgÂ(<b>L1</b>)Â(MeCN)]Â(CF<sub>3</sub>SO<sub>3</sub><sup>–</sup>)}<sub><i>n</i></sub>, <b>1</b>, {[AgÂ(<b>L1</b>)Â(PF<sub>2</sub>O<sub>2</sub><sup>–</sup>)]·H<sub>2</sub>O}<sub><i>n</i></sub>, <b>2</b>, and {Ag<sub>2</sub>(<b>L1</b>)Â(tosylate)<sub>2</sub>}<sub><i>n</i></sub>, <b>3</b>. The frameworks
of these materials exhibit two distinct net topologies: 3<sup>6</sup>.4<sup>6</sup>.5<sup>3</sup> (<b>1</b> and <b>2</b>)
and 4<sup>4</sup>.6<sup>2</sup> (<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 AgÂ(I)–N
bonds, solvent-based exfoliation of crystals of <b>3</b> was
shown to provide dispersions of large, μm<sup>2</sup>, 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 AgÂ(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)ÂbisÂ(1-(pyridin-3-yl)Âmethanimine), <b>L1</b>, and silver salts yield compounds {[AgÂ(<b>L1</b>)Â(MeCN)]Â(CF<sub>3</sub>SO<sub>3</sub><sup>–</sup>)}<sub><i>n</i></sub>, <b>1</b>, {[AgÂ(<b>L1</b>)Â(PF<sub>2</sub>O<sub>2</sub><sup>–</sup>)]·H<sub>2</sub>O}<sub><i>n</i></sub>, <b>2</b>, and {Ag<sub>2</sub>(<b>L1</b>)Â(tosylate)<sub>2</sub>}<sub><i>n</i></sub>, <b>3</b>. The frameworks
of these materials exhibit two distinct net topologies: 3<sup>6</sup>.4<sup>6</sup>.5<sup>3</sup> (<b>1</b> and <b>2</b>)
and 4<sup>4</sup>.6<sup>2</sup> (<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 AgÂ(I)–N
bonds, solvent-based exfoliation of crystals of <b>3</b> was
shown to provide dispersions of large, μm<sup>2</sup>, 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 AgÂ(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>(-bisÂ(1-pyridin-3-yl)Âmethanimine and AgÂ(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