Structural variety of aluminium and gallium coordination polymers based on bis-pyridylethylene: from molecular complexes to ionic networks

Abstract

Diverse molecular (0D and 1D) as well as ionic (0D, 1D, 2D, mixed 1D–2D) crystal structures of complexes of aluminium and gallium trihalides with bis(4-pyridylethylene) were obtained by solvent-free melt reactions.

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

“…The shortest I⋅⋅⋅H contacts were determined as 318.0(3)–327.4(1) pm (I − ‐ bpe ) and 309.82(7) pm ({AlI 2 N 4 } + ‐ tol ) for 1 , 332.49(9) pm ([AlI 4 ] − ‐ bpa ) for 2 and 330.6(1) pm (I 3 − ‐ bpe ) for 3 . These values are in the same range as other intermolecular X⋅⋅⋅H contacts (X=Cl, Br, 290–310 pm) reported for group 13 metal halide and N‐donor based CPs [29] …”

“…Compared to chemically related structures reported in the literature, the (6,3)‐net topology, originating from octahedral coordinated M 3+ serving as 3‐c node, is, next to the (4,4)‐topology, a common structural motif for group 13 metal halide based coordination polymers. It has previously been reported for the compounds 2 ∞ [M 2 X 4 ( bpe ) 2 ] 1 ∞ [MX 2 ( bpe ) 3 ] 2 [MX 4 ] 4 ⋅ 3 bpe (M=Ga, Al, X=Cl), which contain neutral, one‐dimensional chains and cationic nets as well as for CP 2 ∞ [(AlBr 2 ) 2 ( bpe ) 5 ][AlBr 4 ] 2 ⋅ bpe [29,35] …”

“…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.…”

“…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] . In this this work, we present eight two‐dimensional MOFs with and without interpenetration, which were investigated by SCXRD, PXRD, DTA/TG, IR‐spectroscopy, elemental analysis as well as iodine chemisorption.…”

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.…”