Thermodynamically stable and metastable coordination polymers synthesized from solution and the solid state

Abstract

Different Fe(ii) and Cd(ii) thiocyanate coordination compounds with unusual topology including isomeric modifications were synthesized with 4-picoline and investigated in regard to their thermodynamic relations.

Crystal structure, synthesis and thermal properties of bis(4-benzoylpyridine-κN)bis(isothiocyanato-κN)bis(methanol-κN)iron(II)

“…Following this approach, in most cases compounds are obtained in which the metal cations are octahedrally coordinated by two N-and two S-bonding thiocyanate anions as well as two coligands, all of them in trans-positions, and are linked into chains by pairs of -1,3-bridging anions (Neumann et al, 2019;Rams et al, 2020;Mautner et al, 2018). However, in some cases a cis-cis-trans coordination is observed, which can lead to the formation of linear but also to corrugated chains (Jochim et al, 2018;Neumann et al, 2020). This is the case for e.g.…”

Coordination Polymers in Dicyanamido-Cadmium(II) with Diverse Network Dimensionalities

“…Cadmium(II) ion forms complexes with phosphates, amino acids, peptides, nucleobases, nucleotides, and nucleic acids ( [1] (a,b)). The most common coordination geometry in cadmium(II) complexes is octahedral, but tetrahedral and five-coordinate geometries were also formed, depending on the steric coordination environment [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. The interaction of small pseudo halides (N 3 − , NCS − , and NCO − ) and the longer dicyanamide, dca (dca = N(CN) 2 − ) with the divalent metal(II) ions and co-ligands, are considered to be the most studied pseudohalide compounds.…”

“…The interaction of small pseudo halides (N 3 − , NCS − , and NCO − ) and the longer dicyanamide, dca (dca = N(CN) 2 − ) with the divalent metal(II) ions and co-ligands, are considered to be the most studied pseudohalide compounds. These anions have the capability of assembling metal ions, leading to the formation of bridged dinuclear and polynuclear, as well as coordination polymers (CPs) with various architecture topologies [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] and interesting potential applications [17][18][19][20][21][22][23]. One of the most obvious reasons for the formation of these compounds is their wide range of coordination bonding modes.…”

Synthesis, Structures, Thermal and Luminescence Properties of Zn and Cd Halide Coordination Polymers with 2‐Cyanopyrazine

“…[11] Because the ligands are irreversibly removed, the new compounds are ob-tained in quantitative yields and, depending on the reaction conditions, also metastable polymorphic or isomeric modifications can be obtained. [12][13][14][15][16] In several cases, compounds that cannot be obtained from solution or that can only be obtained as mixtures of different compounds, are accessible, if the synthesis is performed in the solid state. [17,18] In general, this approach can be used for the synthesis of a wide range of compounds including not only transition metal thio-and selenocyanates but also transition metal halide coordination compounds with Cu I , Zn II , Cd II and other 3d cations.…”

“…Therefore, such reactions enforces the formation of new compounds with condensed networks of different dimensionality . Because the ligands are irreversibly removed, the new compounds are obtained in quantitative yields and, depending on the reaction conditions, also metastable polymorphic or isomeric modifications can be obtained . In several cases, compounds that cannot be obtained from solution or that can only be obtained as mixtures of different compounds, are accessible, if the synthesis is performed in the solid state , …”