Crystal-to-crystal polymerisation of monosubstituted [PW 11 O 39 Cu(H 2 O)] 5- Keggin-type anions.

Autor: Ruiz-Bilbao E; Departamento de Química Orgánica e Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain. benat.artetxe@ehu.eus.; BCMaterials Edificio Martina Casiano, 3rd Floor, UPV/EHU Science Park, Barrio Sarriena s/n, 48940 Leioa, Spain., Pache A; Departamento de Química Orgánica e Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain. benat.artetxe@ehu.eus., Barrenechea U; Departamento de Química Orgánica e Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain. benat.artetxe@ehu.eus., Reinoso S; Institute for Advanced Materials and Mathematics (INAMAT2), Departamento de Ciencias, Universidad Pública de Navarra (UPNA), Campus de Arrosadia, 31006 Pamplona, Spain., San Felices L; Servicios Generales de Investigación SGIker, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain., Vivanco MD; Cancer Heterogeneity Lab, Center for Cooperative Research in Biosciences (CIC bioGUNE), Basque Research and Technology Alliance (BRTA), Bizkaia Technology Park, 48160 Derio, Spain., Lezama L; Departamento de Química Orgánica e Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain. benat.artetxe@ehu.eus., Artetxe B; Departamento de Química Orgánica e Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain. benat.artetxe@ehu.eus., Gutiérrez-Zorrilla JM; Departamento de Química Orgánica e Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain. benat.artetxe@ehu.eus.; BCMaterials Edificio Martina Casiano, 3rd Floor, UPV/EHU Science Park, Barrio Sarriena s/n, 48940 Leioa, Spain.
Jazyk: angličtina
Zdroj: Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2024 May 28; Vol. 53 (21), pp. 9042-9051. Date of Electronic Publication: 2024 May 28.
DOI: 10.1039/d4dt00690a
Abstrakt: The reaction between neutral bis(picolinate)copper(II) complexes and copper(II)-monosubstituted Keggin-type phosphotungstate anions formed in situ leads to the formation of the hybrid [C(NH 2 ) 3 ] 10 [{PW 11 O 39 Cu(H 2 O)} 2 {Cu(pic) 2 }]·10H 2 O compound (1, pic = picolinate) in the presence of structure-directing guanidinium cations. Single-crystal X-ray diffraction studies demonstrate that 1 contains dimeric {PW 11 O 39 Cu(H 2 O)} 2 {Cu(pic) 2 } molecular species constituted by two Keggin-type anions linked by one {Cu(pic) 2 } octahedral complex through axial coordination to their terminal oxygen atoms. The extensive hydrogen-bonding network established by guanidium cations and Keggin clusters plays a key role in retaining the crystallinity of the system throughout dehydration to allow a single-crystal-to-single-crystal (SCSC) transformation into the anhydrous [C(NH 2 ) 3 ] 10 [{PW 11 O 39 Cu} 2 {Cu(pic) 2 }] (2a) at 170 °C. Structural modifications involve the re-orientation, shifting in ca . 1.5 Å and condensation of all the {PW 11 O 39 Cu} units to result in {PW 11 O 39 Cu} n chains in an unprecedented solid-state polymerisation. This phase transition also implies the cleavage of Cu-O bonds induced by the rotation and translation of Keggin-type anions, in such a way that hybrid dimeric units in 1 are dismantled and {Cu(pic) 2 } complexes become square planar. The irreversibility of the phase transition has been confirmed by combined thermal and diffractometric analyses, which evidence that the anhydrous phase adsorbs only one water molecule per cluster to become the [C(NH 2 ) 3 ] 10 [{PW 11 O 39 Cu} 2 {Cu(pic) 2 }]·2H 2 O (2h) hydrated derivative without any significant alteration in its cell parameters, nor in its crystalline structure. Phase transformations have been monitored by electron paramagnetic resonance spectroscopy.
Databáze: MEDLINE
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