{Co(HBpe)2}(V4O12): pedal motion induced order–disorder P1̄→C1̄ transition and disrupted C1̄→C2/m displacive transition due to thermal instability

Kanpo-estimuluen bitartez aktibatutako fase-trantsizioak, eta haien artean kristal bakun izaera mantentzen duten kasuak, hots monokristal-monokristal (MKMK) eraldaketak, interes handikoak dira; izan ere, gai dira i) ezaugarri berriak dituzten produktuak emateko eta ii) materialaren propietateetan gertatzen diren aldaketak, egitura kristalinoak jasaten dituenekin erlazionatzeko. Polioxometalatoen (POMen) kasuan bezala, egiturei zurruntasuna ematen dieten oinarrizko unitateak erabiltzea bide egokia da prozesuan zehar gerta litekeen kristalinitatearen galera saihesteko. Gaur egun POMetan oinarritutako sistemetan aurki daitezkeen MKMK eraldaketa urrien artean, aipatzekoak dira termikoki aktibatutako adibideak. Lan honetan azken hauek laburbilduko dira eta bereziki gure ikerketa taldean prestatutako konposatuak eta haien erabilerak (katalisia eta gasen xurgapen selektiboa) goraipatuko ditugu.

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“…suen [18], argiaren [19] edo espezie kimiko desberdinen akzioaren ondorioz [20] ], non bpe = bipiridiletenoa [24]).…”

Section: Monokristal-monokristal Eraldaketak Polioxometalatoetan Oina...unclassified

Monokristal-monokristal eraldaketak polioxometalatoetan oinarritutako sistemetan: termikoki aktibatutako zenbait adibide

Fernández-Navarro¹,

Ruiz-Bilbao²,

Artetxe

et al. 2020

EKAIA

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“…Examples of the first type of I 1 O 0 (Scheme 9(a)) are {Co(HBpe) 2 }(V 4 O 12 ), 54,55 {Cd(HBbi) 2 }(V 4 O 12 ), 60 [{Mn(Phen)}(V 4 O 12 )]•0.5H 2 O, 87 and {Co(2Bpy) 2 }(V 4 O 12 ), 88 among others. In these crystal structures, metal-organic complexes are joined through VOS, giving rise to a one-dimensional inorganic framework.…”

Section: O N (N = 0-3) Architectures: Hybrid Vanadate Archetypes Cont...mentioning

confidence: 99%

Hybrid vanadates constructed from extended metal–organic arrays: crystal architectures and properties

et al. 2014

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“…(bpe = 1,2-di(4-pyridyl)ethane), 27 [C(NH2)3]6[Mo7O24]•H2O, 28 and [Tm2(H2O)14(H6CrMo6O24)]-[H6CrMo6O24]•16H2O. 29 These examples are associated with the structural response of certain POM-based molecular compounds or extended lattices to the thermal evacuation of guest solvent molecules 30 and they include: the monitoring of the packing compaction in H5PV2Mo10O40•36H2O; 31 the crystal dynamics leading to the collapse of the porous [Co4(ppca)4(H2O)2(V4O12)]•7.2H2O 3-dimensional framework (ppca = 4-(pyridine-4-yl)pyridine-2-carboxylate); 32 the robustness of the porous Cs5[Cr3O(O2CH)6(H2O)3]-[CoW12O40]•7.5H2O ionic crystal; 33 the reversible grafting of metal-organic subunits at POM surfaces and the ligand conformation changes found in hybrids made of [α-XW12O40] 4anions (X = Ge, Si) and Cu II complexes of bis(aminopyridyl)type ligands; 34,35 or the reversible dissociation of dimeric Cu II -picolinate species in [C(NH2)3]4[{XW12O40}{Cu2(pic)4}]-•[Cu2(pic)4(H2O)]2•6H2O (X = Ge, Si).…”

Section: Introductionmentioning

confidence: 99%

“…To date, a large number of SCSC transitions have been described for organic − or coordination − compounds, but reports on such phenomenon are comparatively uncommon for polyoxometalate (POM)-based structures . Among the latter, thermally triggered transformations are limited to a few examples besides the polymorphic transitions in [Co(Hbpe) 2 (V 4 O 12 )] [bpe = 1,2-di(4-pyridyl)ethane], [C(NH 2 ) 3 ] 6 [Mo 7 O 24 ]·H 2 O, and [Tm 2 (H 2 O) 14 (H 6 CrMo 6 O 24 )][H 6 CrMo 6 O 24 ]·16H 2 O . These examples are associated with the structural response of certain POM-based molecular compounds or extended lattices to the thermal evacuation of guest solvent molecules, and they include monitoring of the packing compaction in H 5 PV 2 Mo 10 O 40 ·36H 2 O, the crystal dynamics leading to the collapse of the porous [Co 4 (ppca) 4 (H 2 O) 2 (V 4 O 12 )]·7.2H 2 O three-dimensional framework [ppca = 4-(pyridin-4-yl)pyridine-2-carboxylate], the robustness of the porous Cs 5 [Cr 3 O(O 2 CH) 6 (H 2 O) 3 ][CoW 12 O 40 ]·7.5H 2 O ionic crystal, the reversible grafting of metal–organic subunits at POM surfaces and the changes in ligand conformation found in hybrids made of [α-XW 12 O 40 ] 4– anions (X = Ge or Si) and Cu II complexes of bis(aminopyridyl)-type ligands, , and the reversible dissociation of dimeric Cu II –picolinate species in [C(NH 2 ) 3 ] 4 [{XW 12 O 40 }{Cu 2 (pic) 4 }]·[Cu 2 (pic) 4 (H 2 O)] 2 ·6H 2 O (X = Ge or Si) .…”

Section: Introductionmentioning

confidence: 99%

Thermostructural Behavior in a Series of Lanthanide-Containing Polyoxotungstate Hybrids with Copper(II) Complexes of the Tetraazamacrocycle Cyclam: A Single-Crystal-to-Single-Crystal Transformation Study

et al. 2019

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The series of fourteen isostructural [Cu(cyclam)]2[{Cu(cyclam)}4{(α-GeW11O39)Ln(H2O)(OAc)}2]•18H2O (1-Ln, Ln = La to Lu; cyclam = 1,4,8,11-tetraazacyclotetradecane) polyoxometalate-based hybrids reported herein represent: (i) the first example of a 2-dimensional covalent hybrid lattice involving the [{(α-XW11O39)Ln(H2O)(OAc)}2] narchetype; and (ii) the first structural characterization of such dimeric polyoxotungste for Ln = La and Pr, as well as for the combination of X = Ge and Ln = Ce, Nd, Sm or Lu. Compounds 1-Ln have been characterized by elemental analyses, infrared spectroscopy and thermogravimetry, and their thermo-structural behavior has been monitored by powder and single-crystal X-ray diffraction. The title compounds undergo two single-crystal-to-single-crystal transformations triggered by thermal dehydration to lead to the [{Cu(cyclam)}6{(α-GeW11O39)Ln(H2O)(OAc)}2]•4H2O intermediate (2-Ln, Ln = Eu, Er) and [Cu(cyclam)]0.5[{Cu(cyclam)}5.5{(α-GeW11O39)Ln(OAc)}2] (3-Ln, Ln = Ce, Eu) final anhydrous phases, the latter evidencing a coordinatively unsaturated derivative of the dimeric archetype for the first time. These transitions involve formation and disruption of Cu-OPOM bonds that result in different {Cu(cyclam)} 2+ moieties grafting at and releasing from Keggin surfaces, which reduces the dimensionality of 1-Ln to 1-dimensional covalent assemblies for 2-Ln and 3-Ln. While all 3-Ln phases rehydrate fully upon exposure to air for 24 h, the kinetics governing the crystal transitions back toward 1-Ln through 2-Ln depend on the nature of Ln. Under ambient moisture, the anhydrous structures fully revert back to the parent framework for Ln = La-to-Sm, while the Eu-to-Lu-containing samples afford mixtures of 1-Ln and 2-Ln and require immersion in water for the structural reversion to be completed. Single-crystal X-ray diffraction analyses on the rehydrated 1R-Ln samples (Ln = Ce, Eu and Er) support these observations.

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{Co(HBpe)2}(V4O12): pedal motion induced order–disorder P1̄→C1̄ transition and disrupted C1̄→C2/m displacive transition due to thermal instability

Cited by 11 publications

References 29 publications

Monokristal-monokristal eraldaketak polioxometalatoetan oinarritutako sistemetan: termikoki aktibatutako zenbait adibide

Monokristal-monokristal eraldaketak polioxometalatoetan oinarritutako sistemetan: termikoki aktibatutako zenbait adibide

Hybrid vanadates constructed from extended metal–organic arrays: crystal architectures and properties

Thermostructural Behavior in a Series of Lanthanide-Containing Polyoxotungstate Hybrids with Copper(II) Complexes of the Tetraazamacrocycle Cyclam: A Single-Crystal-to-Single-Crystal Transformation Study

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