Anion induced structural transformation in silver-(3,6-dimethoxy-1,2,4,5-tetrazine) coordination polymers under mechanochemical conditions

Abstract

Mechanochemical reactions of 3,6-dimethoxy-s-tetrazine (dmotz) with AgCF3SO3 and AgClO4 afforded the 1D linear polymer [Ag(dmotz)(CF3SO3)]n (1) and the 2D grid polymer {[Ag(dmotz)2](ClO4)}n (2), respectively. Mechanochemical processes convert 1 to 2 in the presence of an equivalent of [ClO4](-) and dmotz; even on using excess [CF3SO3](-), conversion from 2 to 1 was not observed.

Design, Synthesis, and Antibacterial Assessment of Silver(I)-Based Coordination Polymers with Variable Counterions and Unprecedented Structures by the Tuning Spacer Length and Binding Mode of Flexible Bis(imidazole-2-thiones) Ligands

“…In this structure, the Ag atom is coordinated by three sulfur atoms with μ 2 -S coordination mode from three distinctly different L 1‑Me ligands and the anion is bonded to the central atom through only one of its oxygen atoms. As in polymer 3 in the structure of [Ag 2 L 2 1 (CF 3 SO 3 ) 2 ] n [ L 1 = bis­(phenylthio)­methane], the Ag atoms adopt a distorted AgS 2 O 2 tetrahedral coordination geometry and the triflate anion chelates to the Ag in a bidentate fashion …”

“…In the investigation of coordination polymers, it is important to understand the major factors that affect the metal coordination and crystal packing of the final product. For a given metal and ligand set, the factors that play an important role in controlling the structure of coordination polymers include structure and conformation of the ligands, − the coordinating potential of the anions, − oxidation state , and hard/soft properties of the metal ions, − the reaction conditions, − the solvent, − the metal-to-ligand ratio, , and so on. In the structural design of coordination polymers, predicting the topology when using flexible multidentate bridging ligands is more difficult than that of a rigid one because their flexibility and conformational freedom allow them to coordinate to metal centers in unpredictable coordination modes and form unexpected structures with specific properties.…”

Anion‐Templated Self‐Assembly of Silver(I) Frameworks Bridged by μ‐, μ3‐, μ4‐1,2,4,5‐Tetrazine

“…[28][29][30] For this purpose, we reported Ag(I)-3,6-dimethoxy-1,2,4,5-tetrazine (dmotz) coordination polymers, where anion π-interaction between the π-acidic dmotz ring and . 31 As a part of our aim for better understanding the role of anion-π interactions in the formation of coordination polymers, we have synthesized coordination polymers using more concise ligand, ttz, and various AgX (X = BF 4 , PF 6 and OTf) salts. Herein, we report the anion-directed assembly of Ag [THF]) at room temperature leads to the formation of dark-red crystalline products.…”

Dicarboxylate‐Induced Structural Diversity of Luminescent Zn(II)/Cd(II) Metal–Organic Frameworks Based on the 2,5‐Bis(4‐pyridyl)thiazolo[5,4‐d]thiazole Ligand

“…Therefore, the design and synthesis of diverse structural MOFs with smart optical properties are highly demanded. However, it is difficult to control the final structures of MOFs, because they may be influenced by many factors, including metal center, organic ligand, synthetic method, temperature, solvent, reactant ratio, pH value, counterion, auxiliary ligand, etc . Among the various factors, organic ligand is believed to be the most critical one, whose type, shape, rigidity, length, substituent group can lead to diversity of the whole framework …”