Syntheses and structures of metal tetrazole coordination polymers

Abstract

Two salts and seven copper(I/II) and silver(I) coordination polymers containing tetrazolyl ligands have been hydro(solvo)thermal synthesized by metal salts, NaN3 and various nitriles generated via [2 + 3] cycloaddition reactions of organonitriles and sodium azide. The study also shows that in some cases the azide can play a dual role in the in situ syntheses of metal tetrazole complexes, namely, starting material for tetrazole ligand and co-ligand in the tetrazole-based coordination complexes. Compounds and are simple salts of ammonium and sodium 5-methyltetrazolate. Compound has a 3-D framework with intersecting channel and unprecedented (4(9).6(6)) topology constructed from mixed-valent Cu8 clusters. Compounds and are isomorphous, and have 3-D organic-inorganic frameworks constructed by [M2(mtta)]+ (Hmtta = 5-methyltetrazole) ribbon and [M2(N3)]+ (M = Cu, Ag) layer two types of structural motifs, which contains an mu(4)-1,1,1,3 azide. Compound is a 3-D four-connected chiral complex with (4(2).8(4))(Cu)(4(2).8(2).10(2))(tta) topology. The structure of consists of 2-D three-connected layers that are linked by ligand-unsupported Ag(I)...Ag(I) interactions to form a 3-D supramolecular array. Compound shows a 3-D chiral framework containing tetrahedrally and linearly coordinated Ag(I) ions and mu3- and mu4-two types of 5-propyltetrazolate. Compound has a 2-D layered structure formed by linkage of [Ag(tetrazolyl)] ribbons via C-C and N-Ag bonds. Magnetic measurement confirmed that there are two Cu(II) ions and six Cu(I) ions per Cu8 unit consistent with a mixed-valent Cu(I,II) complex.

Design and characterization of silver(I) azide coordination polymers based on 1,2-bis(4-pyridyl)ethane and phenazine

“…Although the coordination polymers of transition metal azides have been extensively studied for their great importance in magnetism and other properties [17][18][19][20], silver azide coordination polymers have been only subjected to few investigations [21][22][23]. The present study deals with room temperature preparation of novel supramolecular silver azide polymers containing bipodal spacer ligands.…”

Synthesis, crystal structures and properties of two complexes constructed from in situ-generated new ligands

“…To get designed and predictable frameworks and properties, an enormous amount of researches have been carried out by choosing versatile organic ligands and functional metal ions. Heterocyclic carboxylic acids such as pyridyl-, tetrazole-, piperidine-, imidazole-, and pyrazole-carboxylic acids as building blocks have attracted much attention [16][17][18][19][20][21][22][23][24][25]. Among these, the pyridyl-carboxylic acid is the most typical example, in which the heterocyclic N atom and the carboxyl O atoms can coordinate to the metal center, and the coordination modes of carboxyl groups are very rich.…”

Coordination Architectures of 5-Aminotetrazole-1-Acetic Acid (Hatza) Flexible Ligand and 2,2′-Bipy Rigid Auxiliary Ligand with Mn(II)

“…Therefore, through the choice of organic ligands and metal ions, it is possible to develop a targeted architecture. Among numerous tetrazole-based ligands, 5-methyl-, 5-ethyl-, 5-amino-, 5-(2-pyridyl)-, 5-(3-pyridyl)-, and 5-(4-pyridyl) tetrazolate, 1-methyl-, 1-ethyl-and 1-propyltetrazole, 1,5-diaminotetrazole, 1,4-benzeneditetrazolate, 1,3,5-benzenetristetrazolate, etc., have been widely employed in the construction of coordination polymers with or without the auxiliary ligands [9][10][11][12]. However, tetrazolate-carboxylate ligands have only been the subject of a limited study with metal ions [13][14][15][16][17][18][19].…”