Influencing the outcome: Diorganotin(IV) ladder to macrocycle conversion through solvent selection

Formation of Metal-Based 21- and 22-Membered Macrocycles from Dinuclear Organotin Tectons and Ditopic Organic Ligands Carrying Carboxylate or Dithiocarbamate Groups

“…The opportunities related to assemblies based on the combination of metal ions and organic ligands are exponentially increasing as seen from the number of publications in this field. − This can be attributed to the large number of metals in the periodic table of the elements with varying properties such as coordination number and geometry, oxidation state, color, magnetic moments, etc., which, in combination with organic ligands, give an almost infinite number of zero-, one-, two-, and three-dimensional (0D, 1D, 2D, and 3D) aggregates. − …”

“…At the beginning of the 21st century, organotin compounds started to receive attention in the field of metal-coordination driven self-assembly, and since then, the number of reports on macrocyclic, cage-type, and infinite 1D, 2D, and 3D coordination polymers is increasing. When compared to constructs derived from non-organometallic metal complexes, assemblies carrying organic groups attached by covalent binding to the metal atom are appealing due to the opportunity of structural and functional modification.…”

“…The possibility of modifying the chemical composition of the substituents attached to the metal enables one to vary the electronic and steric properties around the metal atom and to functionalize the interior and periphery of the resulting molecules, which is important for potential applications such as adsorption, molecular recognition, supramolecular catalysis, etc . Organotin compounds exhibit relatively inert metal–carbon bonds with aliphatic and aromatic substituents and can be frequently manipulated under non-inert conditions. − Moreover, the coordination chemistry of organotin compounds is quite predictable, in particular when bidentate ligands such as carboxylates or dithiocarbamates are used. Diorganotin dicarboxylates and bis-dithiocarbamates, i.e., R 2 Sn­(OOCR) 2 and R 2 Sn­(dtc) 2 , are generally six-coordinate complexes with skewed-trapezoidal bipyramidal coordination environments, while the triorganotin analogues are essentially four-coordinate with distorted tetrahedral geometry, i.e., R 3 Sn­(OOCR) and R 3 Sn­(dtc). , …”

Dinuclear Organotin Building Blocks and their Conversion into a Tetranuclear Macrocycle Containing Sn−O−Sn Linkages

“…In the context of metalla-macrocyclic and supramolecular chemistry involving the element tin, generally mononuclear organotin compounds are combined with di-or oligotopic inorganic or organic ligands. [43][44][45][46][47][48][49][50][51] Although diverse di-and oligonuclear organotin specimens are known for more than 80 years (!) and easily accessible, [52] their employment for the assembly of macrocyclic and cage-type molecular architectures remains still underdeveloped.…”