Mixed‐Metal Monophosphate Tungsten Bronzes Containing Rhodium and Iridium

dc.contributor.authorKarbstein, Alexander
dc.contributor.authorWeber, Markus
dc.contributor.authorLahr, Dominic
dc.contributor.authorDaniels, Jörg
dc.contributor.authorAssenmacher, Wilfried
dc.contributor.authorMader, Werner
dc.contributor.authorRosowski, Frank
dc.contributor.authorSchunk, Stephan A.
dc.contributor.authorGlaum, Robert
dc.date.accessioned2021-06-25T07:01:08Z
dc.date.available2021-06-25T07:01:08Z
dc.date.issued2021-04-09
dc.date.updated2021-06-14T12:46:45Z
dc.description.abstractSolution combustion synthesis followed by annealing in air led to the MPTB‐related phosphates (Rh1/6W5/6O3)8(PO2)4, (Ir1/6W5/6O3)8(PO2)4 (a=5.258(2) Å, b=6.538(3) Å, c=17.322(8) Å), (Rh1/9W8/9O3)12(PO2)4 and (Rh2/21W19/21O3)14(PO2)4. Single‐crystals of the mixed‐metal (Rh,W)‐MPTBs at m=4 and at m=7 were grown by chemical vapor transport (CVT). Their crystal structures have been refined from X‐ray single‐crystal data {(Rh,W)‐MPTB at m=4: P212121, Z=1, a=5.2232(3) Å, b=6.4966(3) Å, c=17.3819(9) Å, R1=0.032, wR2=0.075 for 1714 unique reflections, 1524 with Fo>4σ(Fo), 66 variables, 1 constraint, composition from refinement (Rh0.15W0.85O3)8(PO2)4; (Rh,W)‐MPTB at m=7: P21/n, Z=1, a=5.2510(4) Å, b=6.4949(5) Å, c=26.685(2) Å, β=90.30(1)°, R1=0.060, wR2=0.163 for 2074 unique reflections, 1894 with Fo>4σ(Fo), 100 variables, comp. from ref. (Rh0.07W0.93O3)14(PO2)4}. These structure refinements show unexpected distribution of Rh and W over the available metal sites. Further characterization (powder reflectance and magnetic measurements) of the (Rh,W)‐MPTB at m=4 and at m=7 suggest for both phases a homogeneity range with respect to the Rh/W ratio and the presence of small amounts of W5+ besides Rh3+ and W6+. Results of the ligand field analysis for the reference material Rh(PO3)3, which is containing the octahedral chromophore [RhIIIO6], are reported (Δo=23200 cm−1, B=490 cm−1).en
dc.identifier.eissn1099-0682
dc.identifier.issn1099-0682
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/13292
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-12084
dc.language.isoenen
dc.rights.urihttps://creativecommons.org/licenses/by-nc/4.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.subject.otherequilibrium relationsen
dc.subject.otherMPTBen
dc.subject.otherRhodiumen
dc.subject.otherIridiumen
dc.subject.othersolid-state chemistryen
dc.subject.othersolid-state structureen
dc.titleMixed‐Metal Monophosphate Tungsten Bronzes Containing Rhodium and Iridiumen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1002/ejic.202100047en
dcterms.bibliographicCitation.issue15en
dcterms.bibliographicCitation.journaltitleEuropean Journal of Inorganic Chemistryen
dcterms.bibliographicCitation.originalpublishernameWileyen
dcterms.bibliographicCitation.originalpublisherplaceNew York, NYen
dcterms.bibliographicCitation.pageend1469en
dcterms.bibliographicCitation.pagestart1459en
dcterms.bibliographicCitation.volume2021en
tub.accessrights.dnbfreeen
tub.affiliationVerbundforschung>Exzellenzcluster (EXC)>BasCat Joint Labde
tub.affiliation.facultyVerbundforschungde
tub.affiliation.groupBasCat Joint Labde
tub.affiliation.instituteExzellenzcluster (EXC)de
tub.publisher.universityorinstitutionTechnische Universität Berlinen
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