Dinuclear clathrochelate complexes with pendent cyano groups as metalloligands

Abstract

Dinuclear clathrochelate complexes with two, three, four, or five cyano groups in the ligand periphery were prepared following two distinct synthetic strategies: (a) zinc(ii)- or cobalt(ii)-templated polycondensation reactions of CN-functionalized arylboronic acids and phenoldioximes, or (b) postsynthetic cross-coupling reactions of polybrominated zinc(ii) clathrochelates with 4-cyanophenylboronic acid. The new clathrochelate complexes were used as metalloligands for the construction of heterometallic Zn/Ag and Co/Ag coordination polymers (CPs), which were characterized by single crystal X-ray diffraction and FT-IR. A one-dimensional CP was observed for ditopic clathrochelates, whereas two- and three-dimensional CPs were generated from tetra- and pentatopic metalloligands. The three-dimensional network is unique as it displays an unprecedented network topology with the point symbol (8·10)(8·10)(8·10)(8·10). Furthermore, it is a self-catenated net with an extremely high topological density.

New salicylaldoximato-borate ligands resulting from anion hydrolysis and their respective copper and iron complexes

“…Polynuclear transition metal (3d) complexes of salicylaldoxime based ligands, have been studied due to their importance as both biological [1][2][3][4][5] and magnetic materials, [6][7][8][9] extractive hydrometallurgy, 10,11 and building blocks for supramolecular structures, such as metal-organic frameworks (MOFs). [12][13][14][15][16][17] The appeal of salicylaldoxime based ligands arises from the various different coordination modes, and possible complex topologies. The monoanionic form of basic salicylaldoxime where the phenolate hydrogen is solely lost can form various topologies, with the most common being cis/trans mononuclear structures, most commonly used in hydrometallurgy extraction.…”

“…[20][21][22][23][24] A key feature of these topologies is the coordination mode of the oximato group, where the N-O atoms form bridges between metal Since 2016, the use of salicylaldoxime based compounds in in situ ligand formation has rapidly grown due to the rise of boron capped/bridged clathrochelate complexes, as this method easily allows for new boron containing ligands to be generated. [12][13][14][15][16][28][29][30] A clathrochelate complex arises from condensation reactions between di-and tri-oximate species and either boronic acids, boron trifluoride etherates or BF -4 anions. 14,31,32 There are several examples of 3d organometallic complexes in which ions such as fluorine and boron play a significant role in bridging metal ions and capping complexes; these boron species have several applications, such as molecular magnetism, catalysis, and most commonly as building blocks for metallasupramolecular assemblies.…”

“…14,31,32 There are several examples of 3d organometallic complexes in which ions such as fluorine and boron play a significant role in bridging metal ions and capping complexes; these boron species have several applications, such as molecular magnetism, catalysis, and most commonly as building blocks for metallasupramolecular assemblies. [12][13][14][15][16][17][28][29][30]32 Suprisingly this method has been under utilised for ligand formation. There are several different types of boron bridged/capped structures known to date, either forming clathrochelate complexes or complexes utilising central bridges, as demonstrated by Tandon et al, 33 who produced a hexanuclear Cu(II) complex with a central µ 6 -BO 3 -…”

Assembled synthesis of luminescent mono/double‐layered 2D and 3D Zn (II)‐based coordination polymers tuned by flexible bis (pyridyl)propane‐1,2‐diamines and diverse organic dicarboxylates

“…Coordination polymers (CPs) have emerged as a promising class of solid materials, and have acquired significant interest over the recent two decades, which is attributed to the intriguing nature of structural and topological novelty, as well as potential applications in luminescence, photocatalysis, gas storage and separation, sensors, etc . In pursuit of constructing pre‐designed architectures in general, the metal cation can be considered as one of the controllable types of building blocks.…”

Template Synthesis and X-Ray Structure of the First Cobalt(II) Glyoximate Clathrochelate with Terminal Formyl Groups

“…

Cobalt(II) tris-glyoximate clathrochelate CoGm 3 (B4-CКлючевые слова: Макроциклические соединения, клатрохелаты, темплатная конденсация.Mono-and binuclear clathrochelate complexes with functionalizing apical and ribbed substituents containing terminal donor groups such as pyridine, carboxylic or cyano groups as prospective rigid and robust macrobicyclic ligands towards transition and main groups metal ions are reported in [1][2][3][4][5][6] allowing to obtain a wide range of nanosized heterometallic clathrochelate-based metallomacrocycles, coordination polymers and cages. On the other hand, the formyl-terminated clathrochelates seems to be suitable ligand synthones or monomers for the design and synthesis of the imine coordination cages and coordination polymers and their amine derivatives as well.

…”