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

Abstract

Two new coordination polymers constituted by gallium trichloride and 1,2‐bis(4‐pyridyl)ethylene (bpe) were synthesized. Reactions by the solvent‐free melt‐synthesis approach lead to the unusual formation of multiple cationic coordination polymers containing one‐dimensional chains 1∞[GaCl2(bpe)3]+ and two‐dimensional networks 2∞[Ga2Cl4(bpe)5]2+ in one compound of the formula 2∞[Ga2Cl4(bpe)5]1∞[GaCl2(bpe)3]2[GaCl4]4·3bpe. Reactions under solvothermal conditions in benzene lead to the formation of a neutral one‐dimensional coordination polymer 1∞[GaCl3(bpe)]. Both coordination polymers were characterized by SCXRD, PXRD, simultaneous DTA/TG, elemental analysis, and IR spectroscopy.

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

“…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 [28–38] . Although being less frequent than carboxylate based MOFs and CPs, [39–46] 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 ), [31–33,37,38] 1,2‐di(4‐pyridyl)ethylene ( bpe ) [29,35] and 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine ( tpt ) [30,36] . Stability analysis of the bulk materials, such as simultaneous DTA/TG of phase pure CPs and MOFs were only rarely reported, for example for 1 ∞ [GaCl 3 ( bpe )], 2 ∞ [Ga 2 Cl 4 ( bpe ) 5 ] 1 ∞ [GaCl 2 ( bpe ) 3 ] 2 [GaCl 4 ] 4 ⋅ 3 bpe and 1 ∞ [MX 3 ( tpt )] (MX 3 =AlBr 3 , GaCl 3 , GaBr 3 and InI 3 ) [35,36] . A recent work reported on the single‐crystal syntheses of the aluminum and gallium based CPs 2 ∞ [M 2 Cl 4 ( bpe ) 5 ] 1 ∞ [MCl 2 ( bpe ) 3 ] 2 [MCl 4 ] 4 ⋅ 3 bpe , the AlBr 3 based one‐dimensional CP 1 ∞ [Al 3 Br 8 ( bpe ) 3 ][AlBr 4 ] and the two‐dimensional CP 2 ∞ [Al 2 Br 4 ( bpe ) 5 ][AlBr 4 ] 2 ⋅bpe [29,35] .…”

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. [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 ].…”

“…[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.…”