Synthesis and Characterization of [M₂(OH)₂(C₄O₄)₂(H₂O)₄]·2H₂O (M = Al or Ga)

Abstract

Two new squarate complexes based on aluminum and gallium, [Al2(OH)2(C4O4)2(H2O)4]·2H2O (1) and [Ga2(OH)2(C4O4)2(H2O)4]·2H2O (2) were hydrothermally synthesized and characterized by infrared spectroscopy and thermogravimetric measurements. The structure of 1 was determined by single‐crystal X‐ray diffraction and the structure of 2 was refined from PXRD data. The dinuclear squarate complexes consist of two MO6 polyhedra (M = Al or Ga) interconnected by two squarate ions in axial and two hydroxyl groups in equatorial position. Two water molecules are coordinating to each central metal atom in equatorial position to complete the coordination spheres. Furthermore, a non‐coordinating water molecule is located between the dinuclear units. Hydrogen bonding leads to the interconnection of the molecular complexes to a three‐dimensional network.

Iodine‐Chemisorption, Interpenetration and Polycatenation: Cationic MOFs and CPs from Group 13 Metal Halides and Di‐Pyridyl‐Linkers

“…[26,27] The incorporation of complex anions in the structures is found for cationic coordination polymers and MOFs including group 13 metal halide based compounds constituted together with N-donor ligands. [28][29][30][31][32][33][34][35][36][37][38] Although being less frequent than carboxylate based MOFs and CPs, [39][40][41][42][43][44][45][46] the research concerning N-donor based coordination polymers with group 13 metals has gained growing interest. Until now, only a limited amount of coordination polymers constituted from group 13 metal halides and N-donor ligands have been reported, for example for the linkers pyrazine (pyz), [28,34] 4,4'-bipyridine (bipy), [31][32][33]37,38] 1,2-di(4-pyridyl)ethylene (bpe) [29,35] and 2,4,6-tri(4-pyridyl)-1,3,5triazine (tpt).…”

Group 13 Metal Halide Based Coordination Polymers of Al, Ga, In and 2,4,6‐Tri(4‐pyridyl)‐1,3,5‐triazine

“…As for most MOFs and CPs, the most common organic linkers for coordination polymers and MOFs based on group 13 metals are carboxylate based . Whereas N‐donor based ligands are not so frequent, most compounds constituting from group 13 metal halides together with pyrazine ( 1 ∞ [GaCl 3 (pyz)]), 4,4'‐bipyridine ( 2 ∞ [(InF 3 )(bipy)]), and 1,2‐bis(4‐pyridyl)ethylene ( 2 ∞ [Ga 2 Cl 4 (bpe) 5 ] 1 ∞ [GaCl 2 (bpe) 3 ] 2 [GaCl 4 ] 4 · 3bpe]) as organic linkers .…”

“…As for most MOFs and CPs, the most common organic linkers for coordination polymers and MOFs based on group 13 metals are carboxylate based. [10][11][12] Whereas N-donor based ligands are not so frequent, most compounds constituting from group 13 metal halides together with pyrazine ( 1 ϱ [GaCl 3 (pyz)]), [13] 4,4'-bipyridine ( 2ϱ [(InF 3 )(bipy)]), [14] and 1,2-bis(4-pyridyl)ethylene ( 2 ϱ [Ga 2 Cl 4 (bpe) 5 ] 1 ϱ [GaCl 2 (bpe) 3 ] 2 [GaCl 4 ] 4 •3bpe]) [15] as organic linkers. [13][14][15][16][17][18][19] Especially, for the tridentate 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt), which is employed in combination with transition metals [20] in a large variety of scientific studies, only one polymeric structure in combination with group 13 metal halides has been reported until now, being 3 ϱ [InCl 3 ) 3 (tpt) 2 ].…”

Gallium Coordination Polymers Based on Bis‐pyridylethylene Containing Neutral and Cationic 1D Chains and 2D Networks

“…While a greater number of coordination polymers (CPs) and metal‐organic frameworks (MOFs) containing transition metals and lanthanides are known, a limited number of group 13 metal based coordination polymers are reported. For instance, the largest range of known CPs and MOFs are carboxylate‐based, whereas, CPs based on N‐donor ligands account for only a small share . In complexes containing group 13 metal halides, different coordination numbers (CN = 4, 5, 6) of the central atom can be found, depending on the complex composition, the type of the metal halide and the Lewis basicity of the used ligand .…”