{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T18:28:33Z","timestamp":1790274513290,"version":"4.1.0"},"reference-count":71,"publisher":"Wiley","issue":"41","license":[{"start":{"date-parts":[[2011,8,31]],"date-time":"2011-08-31T00:00:00Z","timestamp":1314748800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2011,10,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Magic\u2010angle spinning (MAS) NMR spectroscopy is used to study the local structure and spin delocalisation in Prussian blue analogues (PBAs). We selected two common archetypes of PBAs (A<jats:sup>I<\/jats:sup>M<jats:sup>II<\/jats:sup>[M<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>]\u22c5<jats:italic>x<\/jats:italic>\u2009H<jats:sub>2<\/jats:sub>O and M<jats:sup>II<\/jats:sup><jats:sub>3<\/jats:sub>[M<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>]<jats:sub>2<\/jats:sub>\u22c5<jats:italic>x<\/jats:italic>\u2009H<jats:sub>2<\/jats:sub>O, in which A<jats:sup>I<\/jats:sup> is an alkali ion, and M<jats:sup>II<\/jats:sup> and M<jats:sup>III<\/jats:sup> are transition\u2010metal ions) that exhibit similar cubic frameworks but different microscopic structures. Whereas the first type of PBA contains interstitial alkali ions and does not exhibit any [M<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>]<jats:sup>3\u2212<\/jats:sup> vacancies, the second type of PBA exhibits [M<jats:sup>III<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>]<jats:sup>3\u2212<\/jats:sup> vacancies, but does not contain inserted alkali ions. In this study, we selected Cd<jats:sup>II<\/jats:sup> as a divalent metal in order to use the <jats:sup>113<\/jats:sup>Cd nuclei (<jats:italic>I<\/jats:italic>=1\/2) as a probe of the local structure. Here, we present a complete MAS NMR study on two series of PBAs of the formulas Cd<jats:sup>II<\/jats:sup><jats:sub>3<\/jats:sub>[Fe<jats:sup>III<\/jats:sup><jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>Co<jats:sup>III<\/jats:sup><jats:sub>1\u2212<jats:italic>x<\/jats:italic><\/jats:sub>(CN)<jats:sub>6<\/jats:sub>]<jats:sub>2<\/jats:sub>\u22c515\u2009H<jats:sub>2<\/jats:sub>O with <jats:italic>x<\/jats:italic>=0 (<jats:bold>1<\/jats:bold>), 0.25 (<jats:bold>2<\/jats:bold>), 0.5 (<jats:bold>3<\/jats:bold>), 0.75 (<jats:bold>4<\/jats:bold>) and 1 (<jats:bold>5<\/jats:bold>), and CsCd<jats:sup>II<\/jats:sup>[Fe<jats:sup>III<\/jats:sup><jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>Co<jats:sup>III<\/jats:sup><jats:sub>1\u2212<jats:italic>x<\/jats:italic><\/jats:sub>(CN)<jats:sub>6<\/jats:sub>]\u22c5 0.5\u2009H<jats:sub>2<\/jats:sub>O with <jats:italic>x<\/jats:italic>=0 (<jats:bold>6<\/jats:bold>), 0.25 (<jats:bold>7<\/jats:bold>), 0.5 (<jats:bold>8<\/jats:bold>), 0.75 (<jats:bold>9<\/jats:bold>) and 1 (<jats:bold>10<\/jats:bold>). Interestingly, the presence of Fe<jats:sup>III<\/jats:sup> magnetic centres in the vicinity of the cadmium sites has a magnifying\u2010glass effect on the NMR spectrum: it induces a striking signal spread such that the resolution is notably improved compared to that achieved for the diamagnetic PBAs. By doping the sample with varying amounts of diamagnetic Co<jats:sup>III<\/jats:sup> and comparing the NMR spectra of both types of PBAs, we have been able to give a view of the structure which is complementary to that usually obtained from X\u2010ray diffraction studies. In particular, this study has shown that the vacancies are not randomly distributed in the mesoporous PBAs. Moreover the cadmium chemical shift, which is a measure of the hyperfine coupling, allows the estimation of the spin density on the cadmium nucleus, and consequently, the elucidation of the spin delocalisation mechanism in these compounds along with its dependency on structural parameters.<\/jats:p>","DOI":"10.1002\/chem.201100778","type":"journal-article","created":{"date-parts":[[2011,9,1]],"date-time":"2011-09-01T02:53:35Z","timestamp":1314845615000},"page":"11567-11575","source":"Crossref","is-referenced-by-count":33,"title":["Probing Spin Density and Local Structure in the Prussian Blue Analogues CsCd[Fe\/Co(CN)<sub>6<\/sub>]\u22c50.5\u2009H<sub>2<\/sub>O and Cd<sub>3<\/sub>[Fe\/Co(CN)<sub>6<\/sub>]<sub>2<\/sub>\u22c515\u2009H<sub>2<\/sub>O with Solid\u2010State MAS NMR Spectroscopy"],"prefix":"10.1002","volume":"17","author":[{"given":"Alexandrine","family":"Flambard","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Frank H.","family":"K\u00f6hler","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rodrigue","family":"Lescou\u00ebzec","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bertrand","family":"Revel","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2011,8,31]]},"reference":[{"key":"e_1_2_6_1_2","first-page":"33","author":"Woodward J.","year":"1724","journal-title":"Philos. Trans. R. Soc. London"},{"key":"e_1_2_6_2_2","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja051168t"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/b502850g"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp803714j"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp7117339"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic902397w"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39850001305"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ac990801o"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.200400068"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF02048881"},{"key":"e_1_2_6_13_2","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","unstructured":"Shell Int. ResearchMij B. Pat Appl. 84\/00796 1984;"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39850001305"},{"key":"e_1_2_6_16_2","volume-title":"Molecular Magnetism","author":"Kahn O.","year":"1993"},{"key":"e_1_2_6_17_2","unstructured":"\u00a0"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(99)00156-3"},{"key":"e_1_2_6_18_3","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(99)00156-3"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1038\/378701a0"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja990946c"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.272.5262.704"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200604452"},{"key":"e_1_2_6_22_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200604452"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200460086"},{"key":"e_1_2_6_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200460086"},{"key":"e_1_2_6_24_2","doi-asserted-by":"crossref","unstructured":"V. Escax G. Champion M.\u2010A. Arrio M. Zacchigna C. Cartier dit Moulin A. Bleuzen Angew. Chem.2005 117 4876;Angew. Chem. Int. Ed.2005 44 4798.","DOI":"10.1002\/anie.200500647"},{"key":"e_1_2_6_25_2","unstructured":"Recent examples:"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm052521x"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp044739x"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0703980"},{"key":"e_1_2_6_29_2","unstructured":"\u00a0"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja068105a"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0438314"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja063510n"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja043461j"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020734p"},{"key":"e_1_2_6_35_2","unstructured":"\u00a0"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00106a033"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja020026l"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.65.224425"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja991188t"},{"key":"e_1_2_6_40_2","unstructured":"Recent examples:"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0352710"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm7032965"},{"key":"e_1_2_6_43_2","unstructured":"Recent examples:"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3749(200009)626:9<1921::AID-ZAAC1921>3.0.CO;2-#"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0465451"},{"key":"e_1_2_6_46_2","unstructured":"\u00a0"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.19680510820"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50177a010"},{"key":"e_1_2_6_49_2","unstructured":"\u00a0"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1999-0708"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1387-1811(02)00389-X"},{"key":"e_1_2_6_52_2","unstructured":"Seven different cadmium sites are expected in principle but statistical calculation based on binomial law shows that only six signals could be observed as the CdII(OH2\u25a1)6surrounding has a very low probability of existence (see the Supporting Information)."},{"key":"e_1_2_6_53_2","unstructured":"\u00a0"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200453726"},{"key":"e_1_2_6_54_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200453726"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200805415"},{"key":"e_1_2_6_55_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200805415"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja061650r"},{"key":"e_1_2_6_57_2","unstructured":"Baseline deformations occur when measuring over very large spectral windows Typically in these experiment the spectral windows used may reached 300\u2009000\u2005Hz."},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/j150614a027"},{"key":"e_1_2_6_59_2","unstructured":"${C{{p\\hfill \\atop x\\hfill}}}$=x!\/[(x\u2212p)!p!]."},{"key":"e_1_2_6_60_2","unstructured":"On a statistical basis 80\u2009% of the Cd(NC\uf8ffFe)4(H2O)2sites should exhibit thecisconfiguration whereas 20\u2009% of the cadmium site should exhibit thetransconfiguration."},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1002\/3527600841.ch12"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-2364(70)90100-9"},{"key":"e_1_2_6_63_2","unstructured":"\u00a0"},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1097-458X(199707)35:7<487::AID-OMR115>3.0.CO;2-0"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1006\/jmre.2001.2343"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1002\/mrc.984"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201100778","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201100778","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T14:12:04Z","timestamp":1760278324000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201100778"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2011,8,31]]},"references-count":71,"journal-issue":{"issue":"41","published-print":{"date-parts":[[2011,10,4]]}},"alternative-id":["10.1002\/chem.201100778"],"URL":"https:\/\/doi.org\/10.1002\/chem.201100778","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2011,8,31]]}}}