Topology Control of Porous Coordination Polymers by Building Block Symmetry

Polunin, Ruslan A.; Kolotilov, Sergey V.; Кискин, М. А.; Cador, Olivier; Mikhalyova, Elena A.; Lytvynenko, Anton; Golhen, Stéphane; Ouahab, Lahcène; Овчаренко, В. И.; Еременко, И. Л.; Новоторцев, В. М.; Pavlishchuk, V. V.

doi:10.1002/ejic.201000929

Cited by 51 publications

(43 citation statements)

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“…As we previously reported, [9] the crystal structures of 1 and 2 are built from interpenetrating 2D layers with a pseudo-honeycomb topology (Figure 1, a). Each 2D layer is formed by trinuclear μ 3 -oxocentered Fe 2 CoO(Piv) 6 units connected by bipy molecules.…”

Section: Temperature-and Solvent-induced Structural Variation Of 1·2smentioning

confidence: 88%

“…This agrees with the result of N 2 and H 2 sorption measurements of samples 1 and 2 which showed considerably lower sorption capacities for 2 than for 1 in the case of N 2 and H 2 sorption. [9] However, residual solvent can not be detected in 2 (as well as in 1) by CHN analysis. It could be that few DMF molecules block the long channel and "fix" 2D layers, preventing their rearrangement.…”

Section: Thermal Behaviour and Powder X-ray Diffractionmentioning

confidence: 96%

“…The structures of 1·2DMF were determined by using the data collected at three temperatures between 160 and 296 K and a previous experiment performed at 150 K [9] was used to analyse structural variations over a wide temperature range (Table 1). In addition, the X-ray structures of 2·2DMF (at 120 K) [9] as well as those of 1·2DEF at 173 and 260 K were analysed to provide additional information about the possible range of crystal structure changes. Compounds 1·2DMF and 2·2DMF are isostructural and crystallise in the monoclinic system (space group P2 1 /n).…”

Section: Temperature-and Solvent-induced Structural Variation Of 1·2smentioning

confidence: 99%

“…[9] It was shown that these complexes, in unsolvated forms, could adsorb N 2 and H 2 . Unusual hysteresis of nitrogen adsorption-desorption was found and as possible reasons we proposed some steric hindrances for N 2 molecules passing deeply into the channels or "gate-opening" which could involve changes in the crystal packing of the coordination polymers.…”

Section: Introductionmentioning

confidence: 99%

“…Differential scanning calorimetry (DSC) measurements were performed in order to obtain information about possible phase changes. The range of adsorbates was extended to alkanes and alcohols (compared with previously studied N 2 and H 2 ) [9] which enabled the identification of significant differences between sorption of adsorbates of different classes which may be associated with structural flexibility of the MOF as well as the hydrophobic nature of their pores.…”

Section: Introductionmentioning

confidence: 99%

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Structural Flexibility and Sorption Properties of 2D Porous Coordination Polymers Constructed from Trinuclear Heterometallic Pivalates and 4,4′‐Bipyridine

et al. 2011

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International audienceThe temperature dependence of crystal structure parameters of isostructural coordination polymers Fe2MO(Piv)6(bipy)1.5*2DMF [1*2DMF and 2*2DMF, where M = NiII or CoII, respectively, Piv = (CH3)3CCO2-, bipy = 4,4-bipyridine and DMF is N,N-dimethylformamide] was studied at five temperatures in the range from 120 to 296 K. The X-ray structure of the N,N-diethylformamide (DEF) solvate of the same coordination polymer 1, Fe2NiO(Piv)6(bipy)1.5*2DEF (1*2DEF), was studied at 173 and 260 K. Both the DMF and DEF solvates possess similar crystal structures, consisting of a series of parallel 2D polymeric layers with honeycomb voids. These series of parallel layers intersect, leading to their interpenetration and formation of zig-zag channels. It was found that the change of temperature and/or solvent molecule in the pores causes significant structural rearrangement associated with a change of the separation between parallel layers and the angle between intersecting layers. These structural changes lead to a variation of the calculated solvent-accessible volume from 0.21 cm3 g-1 (120 K, 2*2DMF) to 0.30 cm3 g-1 (260 K, 1*2DEF) for a probe molecule with r = 1.4 Å. These changes can model structural transformations which can occur at desolvation and adsorption of guests. Adsorption of n-hexane, n-octane, methanol and ethanol by Fe2MO(Piv)6(bipy)1.5 was studied. The sorption isotherms of alkanes were typical for microporous sorbents and in this case the behaviour of the coordination polymers resembled that which is typical for sorbents with a rigid structure. In a contrast, alcohol sorption capacity continuously grew at increasing pressure which may be caused by structural transformations, similar to temperature-induced structural transformations. Among the studied sorbates, sorption capacity grew in order methanol < ethanol < n-hexane < n-octane which may be caused by the hydrophobic nature of the channels (due to the presence of tert-butyl groups)

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Section: Temperature-and Solvent-induced Structural Variation Of 1·2smentioning

confidence: 88%

Section: Thermal Behaviour and Powder X-ray Diffractionmentioning

confidence: 96%

Section: Temperature-and Solvent-induced Structural Variation Of 1·2smentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural Flexibility and Sorption Properties of 2D Porous Coordination Polymers Constructed from Trinuclear Heterometallic Pivalates and 4,4′‐Bipyridine

et al. 2011

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2D Porous Honeycomb Polymers versus Discrete Nanocubes from Trigonal Trinuclear Complexes and Ligands with Variable Topology

Дорофеева

Kolotilov

Кискин

et al. 2012

Chemistry A European J

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Trinuclear building block {Fe(2)NiO(Piv)(6)} (Piv = pivalate), which possessed pseudo-D(3h) symmetry, was linked by two ligands, pseudo-D(3h) ligand tris-(4-pyridyl)pyridine (L1) and C(2v) ligand 4-(N,N-dimethylamino)phenyl-2,6-bis(4-pyridyl)pyridine (L2) into two products with different topologies: 2D coordination polymer [Fe(2)NiO(Piv)(6)(L1)](n) (1), and discrete molecule [{Fe(2)NiO(Piv)(6)}(8) {L2}(12)], which had a nanocube structure (2). In compound 1, trinuclear {Fe(2)NiO(Piv)(6)} blocks were linked through ligand L1 into layers with honeycomb topology. In compound 2, eight trinuclear blocks were located in the vertices of the nanocube, with each L2 ligand linked to two {Fe(2)NiO(Piv)(6)} units. In the crystal structure, these nanocubes formed infinite catenated chains. Analysis of possible structures that could be assembled from these building blocks showed that compounds 1 and 2 corresponded to their respective predicted topologies. Compound [1⋅solvent] possessed a porous structure, in which the voids were filled by solvent molecules (DMF or DMSO). This structure was retained following desolvation, and compound 1 absorbed significant quantities of N(2) and H(2) at 78 K (S(BET) = 730 m(2) g(-1), H(2) sorption capacity: 0.9 % by weight at 865 Torr). Desolvation of [2⋅solvent] led to disorder of its crystal structure, and compound 2 only adsorbed negligible quantities of N(2) but adsorbed 0.27 % H(2) (by weight) at 855 Torr and 78 K. The magnetic properties of these complexes (temperature dependence of molar magnetic susceptibility) were governed by the magnetic properties of the trinuclear "building block".

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Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me₂mal)₂} Fragment

et al. 2016

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Topological methods of analysis of coordination networks have become an integral part of design of coordination polymers, MOFs, and zeolites. It helps to chemists to understand the novelty of findings, to reveal relations between different structures, to propose new design concepts, and to communicate effectively with each other. However, this is not the limit of the methods. Description of coordination environment of structural units (metal atoms, ligands, SBUs), network topology (topological type), and topology of entanglement (entanglement pattern) intrinsically leads to finding relations between the topological parameters. Further, the correlations can be grouped (systematized) in a hierarchical manner to produce a knowledge database for design and prediction of new materials (their structure and properties) [1, 2]. Thus, new structural characteristics, the so-called descriptors, have to be invented for prediction of particular structural features. For example, we have proposed to use topological type of Hopf ring net for analysis of topology entanglements in coordination networks. Now we put forward Extended ring net (ERN), which incorporates information about topology of entangled nets and topology of entanglements. ERN is able to distinguish patterns of entanglements up to isomorphism and polymorphism, that allowed us to describe new type of isomerism of coordination polymers, entanglement isomerism. MOF structures are usually considered as a result of assembly of secondary building units in an isoreticular manner. Usually SBU is considered as a topologically dense 0D polynuclear complex group, which coordination figure is predetermined by orientation of points of extension (functional groups of ligands connected by linkers). However, many practically important MOFs contain infinite SBUs; e.g. rod-shaped 1D {AlOH(CO2)2} groups are connected by benzene linkers in parallel fashion into framework MIL-53. We have produced a comprehensive systematics of infinite SBUs and ways for their connection with new algorithms of rod-MOFs description as 2D net of rods connections. Selection of correct structural groups is also important for design of self-catenated networks. We proposed a universal algorithm for selection of all reasonable subnets and determining the structure driving ones. To describe the geometry and topology of voids and channels in porous structures we combined topological methods and Voronoi partitioning. The improved Voronoi partitioning provides much more characteristics of porous structures, e.g. periodicity, topology and crystallographic orientation of channels, minimal cages of framework, open sights of metal atoms etc. These descriptors give us an opportunity to define metal-organic nanotube as a 1-periodic tiling of face-shared 3D tiles. To enhance the usability of the results of topological analysis we collected values of descriptors into a knowledge database [2]. The database was applied in finding relations between topological parameters for heterometallic coordination polymers based on {C...

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Topology Control of Porous Coordination Polymers by Building Block Symmetry

Cited by 51 publications

References 18 publications

Structural Flexibility and Sorption Properties of 2D Porous Coordination Polymers Constructed from Trinuclear Heterometallic Pivalates and 4,4′‐Bipyridine

Structural Flexibility and Sorption Properties of 2D Porous Coordination Polymers Constructed from Trinuclear Heterometallic Pivalates and 4,4′‐Bipyridine

2D Porous Honeycomb Polymers versus Discrete Nanocubes from Trigonal Trinuclear Complexes and Ligands with Variable Topology

Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me₂mal)₂} Fragment

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Topology Control of Porous Coordination Polymers by Building Block Symmetry

Cited by 51 publications

References 18 publications

Structural Flexibility and Sorption Properties of 2D Porous Coordination Polymers Constructed from Trinuclear Heterometallic Pivalates and 4,4′‐Bipyridine

Structural Flexibility and Sorption Properties of 2D Porous Coordination Polymers Constructed from Trinuclear Heterometallic Pivalates and 4,4′‐Bipyridine

2D Porous Honeycomb Polymers versus Discrete Nanocubes from Trigonal Trinuclear Complexes and Ligands with Variable Topology

Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me2mal)2} Fragment

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Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me₂mal)₂} Fragment