From gallium to thallium: Group 13 one-dimensional polymers

Samanamú, Christian R.; LoCoco, Peter M.; Richards, Emma

doi:10.1016/j.ica.2007.03.048

Cited by 19 publications

(17 citation statements)

References 33 publications

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“…The obtained results (Table 1) indicate that for pyz complexes the reaction energy is always positive (the non-ionic chain motif is favored by 46-126 kJ mol −1 ), which is in qualitative agreement with the known experimental structures of pyrazine complexes (non-ionic 1D coordination polymers (MX 3 pyz) ∞ (M = Al, Ga; X = Cl, Br) 11,12 or simple monomeric adduct GaI 3 pyz 12 ). In contrast, in the case of 4,4′-bipy, the computed reaction energies are negative (Table 1), indicating the energetic preference of the ionic structure.…”

Section: Computational Studiessupporting

confidence: 85%

“…We have been able to grow single crystals and structurally characterize the following complexes: 1 : 1 composition: AlCl 3 bipy (1), AlBr 3 bipy (2), GaCl 3 •bipy (3), and GaBr 3 bipy (4); 1 : 2 composition: GaCl 3 bipy 2 •2bipy (5); 2 : 1 composition: (AlCl 3 ) 2 bipy (6), (GaCl 3 ) 2 bipy (7), heterobimetallic complex AlGaCl 6 bipy (8), (AlBr 3 ) 2 bipy (9), (GaBr 3 ) 2 bipy (10) and heterobimetallic complex AlGaBr 6 bipy (11). Experimental details on the crystal structure of all complexes are presented in Tables S1-S4 (ESI †).…”

Section: Structural Studiesmentioning

confidence: 99%

“…Known examples include non-ionic 1D coordination polymers which are realized in 1 : 1 stoichiometry complexes (MX 3 pyz) ∞ where Al and Ga atoms possess the coordination number 5 (trigonal bipyramidal environment). 11,12 Interestingly, in the case of In, the complex of other stoichiometry InCl 3 pyz 1.5 is formed, in which additional pyz molecules link -In-pyz-Inchains to complete the octahedral coordination of the In atom. 11 Usage of a longer bridging ligand, such as 4,4′-bipy, may lead to the construction of coordination polymer networks with larger pores, which could potentially serve as hosts for different molecules and new functional materials.…”

Section: Introductionmentioning

confidence: 99%

“…11,12 Interestingly, in the case of In, the complex of other stoichiometry InCl 3 pyz 1.5 is formed, in which additional pyz molecules link -In-pyz-Inchains to complete the octahedral coordination of the In atom. 11 Usage of a longer bridging ligand, such as 4,4′-bipy, may lead to the construction of coordination polymer networks with larger pores, which could potentially serve as hosts for different molecules and new functional materials. Crystal structure analysis of InF 3 bipy 7 revealed a neutral 2D coordination network.…”

Section: Introductionmentioning

confidence: 99%

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Versatile structures of group 13 metal halide complexes with 4,4′-bipy: from 1D coordination polymers to 2D and 3D metal–organic frameworks

et al. 2015

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A systematic structural study of complexes formed by aluminium and gallium trihalides with 4,4'-bipyridine (bipy) in 2 : 1, 1 : 1, and 1 : 2 stoichiometric ratios has been performed. Molecular structures of 11 complexes in the solid state have been determined for the first time. Complexes of 2 : 1 composition are molecular, while complexes of 1 : 1 composition form metal-organic frameworks of different kinds: an ionic 3D network (three interpenetrated lvt nets for AlCl3bipy), an ionic 2D network for AlBr3bipy and GaBr3bipy and a 1D coordination polymer in the case of GaCl3bipy. Thus, the nature of the Lewis acid plays a critical role in the structural type of the complex in the solid state. Incorporation of excess bipy molecules into (GaCl3bipy)∞ (formation of crystallosolvate) leads to an unprecedented change of the molecular structure from a non-ionic 1D coordination polymer to an ionic 2D metal organic framework [GaCl2bipy2](+)[GaCl4](-)·2bipy. As indicated by the temperature-dependent XRD study, removal of bipy by heating in a vacuum restores the non-ionic 1D structure. Quantum chemical computations for simple cluster model systems (up to eight Al and Ga atoms) reveal that ionic forms are slightly favourable, although the energy differences between the ionic and non-ionic structures are not large. These theoretical predictions are in good agreement with experimental findings. Thus, even relatively simple cluster models may be used to indicate the structural preferences in the solid state. Both experimental and computational IR frequency shifts of the in-plane ring bending mode of bipy upon complexation correlate well with the M-N bond distances in the complexes.

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Section: Computational Studiessupporting

confidence: 85%

Section: Structural Studiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Versatile structures of group 13 metal halide complexes with 4,4′-bipy: from 1D coordination polymers to 2D and 3D metal–organic frameworks

et al. 2015

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“…Polymeric structures of GaCl 3 ·pyz and GaBr 3 ·pyz in the solid state were established in 2007 by Richards and co-workers. 11 Previous mass spectrometry and tensimetry studies of the complex formation in the GaCl 3 -pyz system 12 confirmed the existence of the individual molecules (GaCl 3 ) 2 ·pyz and GaCl 3 ·pyz in the gas phase. Both complexes undergo reversibly thermal dissociation in the gas phase; GaCl 3 ·pyz is the dominant form in vapors, while the (GaCl 3 ) 2 ·pyz content is very low (0.2% at 383 K and only 0.05% at 673 K).…”

Section: Introductionmentioning

confidence: 84%

Structural and thermodynamic properties of molecular complexes of aluminum and gallium trihalides with bifunctional donor pyrazine: decisive role of Lewis acidity in 1D polymer formation

et al. 2013

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Solid state structures of group 13 metal halide complexes with pyrazine ( pyz) of 2 : 1 and 1 : 1 composition have been established by X-ray structural analysis. Complexes of 2 : 1 composition adopt molecular structures MX 3 ·pyz·MX 3 with tetrahedral geometry of group 13 metals. Complexes of AlBr 3 and GaCl 3 of 1 : 1 composition are 1D polymers (MX 3 ·pyz) ∞ with trigonal bipyramidal geometry of the group 13 metal, while the weaker Lewis acid GaI 3 forms the monomeric molecular complex GaI 3 ·pyz, which is isostructural to its pyridine analog GaI 3 ·py. Tensimetry studies of vaporization and thermal dissociation of AlBr 3 ·pyz and AlBr 3 ·pyz·AlBr 3 complexes have been carried out using the static method with a glass membrane null-manometer. Thermodynamic characteristics of vaporization and equilibrium gas phase dissociation of the AlBr 3 ·pyz complex have been determined. Comprehensive theoretical studies of (MX 3 ) n ·( pyz) m complexes (M = Al, Ga; X = Cl, Br, I; n = 1, 2; m = 1-3) have been carried out at the B3LYP/ TZVP level of theory. Donor-acceptor bond energies were obtained taking into account reorganization energies of the fragments. Computational data indicate that the formation of (MX 3 ·pyz) ∞ polymers with coordination number 5 is only slightly more energetically favorable than the formation of molecular complexes of type MX 3 ·pyz for X = Cl, Br. It is expected that on melting (MX 3 ·pyz) ∞ polymers dissociate into individual MX 3 ·pyz molecules. This dovetails with low melting enthalpies of the (MX 3 ·pyz) ∞ complexes.Polymer stability decreases in the order AlCl 3 > AlBr 3 > GaCl 3 > AlI 3 > GaBr 3 > GaI 3 . For MI 3 ·pyz complexes computations predict that the monomeric structure motif is more energetically favorable compared to the catena polymer. These theoretical predictions agree well with the experimentally observed monomeric complex GaI 3 ·pyz in the solid state. Thus, the Lewis acidity of the group 13 halides may play a decisive role in the formation of 1D polymeric networks.

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The Field of Main Group Lewis Acids and Lewis Superacids: Important Basics and Recent Developments

Timoshkin

2023

Chemistry A European J

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New developments in the field of Lewis acidity are highlighted, with the focus of novel Lewis acids and Lewis superacids of group 2, 13, 14, and 15 elements. Several important basics, illustrated by modern examples (classification of Donor‐Acceptor (DA) complexes, amphoteric nature of any compound in terms of DA interactions, reorganization energies of main group Lewis acids and the role of the energies of frontier orbitals) are presented and discussed. It is emphasized that the Lewis acidity phenomena are general and play vital role in different areas of chemistry: from weak “atomophilic” interactions to the complexes of Lewis superacids.

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From gallium to thallium: Group 13 one-dimensional polymers

Cited by 19 publications

References 33 publications

Versatile structures of group 13 metal halide complexes with 4,4′-bipy: from 1D coordination polymers to 2D and 3D metal–organic frameworks

Versatile structures of group 13 metal halide complexes with 4,4′-bipy: from 1D coordination polymers to 2D and 3D metal–organic frameworks

Structural and thermodynamic properties of molecular complexes of aluminum and gallium trihalides with bifunctional donor pyrazine: decisive role of Lewis acidity in 1D polymer formation

The Field of Main Group Lewis Acids and Lewis Superacids: Important Basics and Recent Developments

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