Utilising Metal Melts of Low‐Melting Metals as a Novel Approach for MOF Synthesis: The 3D‐Imidazolate ³_∞[Ga₂(Im)₆ImH] from Gallium and Imidazole 

Abstract

Metals with low melting points like gallium (mp. 30°C) prove a new approach for the synthesis of MOFs. As the melting point of gallium is even lower than of the linker ligand imidazole, formation of the MOF 3 ∞ [Ga 2 (Im) 6 ImH], Im -= imidazolate anion, ImH = imidazole, can be achieved by reaction of a melt of the referring metal with a melt of the ligand. Gallium is oxidised in the reaction, and hydrogen gas and the imidazolate amide as colourless single crystalline product are formed. At the melting point of imidazole (mp. 88-90°C) two liquid phases are observed. Phase separation lasts until the reaction, * Prof. Dr. Klaus Müller-Buschbaum

2D‐Coordination Polymers Constituted from Indium Halides and Dipyridyl N‐Donor Ligands

“…[21][22][23][24][25] To date, only a limited number of examples are known for CPs and MOFs constituted from group 13 metal halides together with N-donor ligands. [26][27][28][29][30][31][32][33][34][35][36][37][38] The vast majority is constructed from d-block elements as inorganic building blocks and carboxylates as organic linkers. Group 13 metal trihalides act as strong Lewis acids, forming stable donor acceptor complexes in combination with N-donor ligands.…”

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 . Especially, for the tridentate 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine (tpt), which is employed in combination with transition metals 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 ∞ [InCl 3 ) 3 (tpt) 2 ] …”

“…[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 ]. [21] However, tpt is a tridentate linker and despite the reported compounds seems to be a promising candidate for establishing coordination polymers especially in combination with group 13 metal halides.…”

Gallium Species Incorporated into MOF Structure: Insight into the Formation of a 3D Polycrystalline Gallium–Imidazole Framework

“…In this work, we have synthesized a porous gallium–imidazole {Ga­(Im) 6 } framework following a procedure described in the literature . This {Ga­(Im) 6 } MOF system was described as fully crystalline, and it was implied that the crystallization of the 3D framework was achieved using particular conditions .…”