{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T15:48:53Z","timestamp":1791301733387,"version":"4.1.0"},"reference-count":55,"publisher":"Wiley","issue":"30","license":[{"start":{"date-parts":[[2012,6,19]],"date-time":"2012-06-19T00:00:00Z","timestamp":1340064000000},"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":[[2012,7,23]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The reaction of Mn<jats:sup>II<\/jats:sup> and [NEt<jats:sub>4<\/jats:sub>]CN leads to the isolation of solvated [NEt<jats:sub>4<\/jats:sub>]Mn<jats:sub>3<\/jats:sub>(CN)<jats:sub>7<\/jats:sub> (<jats:bold>1<\/jats:bold>) and [NEt<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub>Mn<jats:sub>3<\/jats:sub>(CN)<jats:sub>8<\/jats:sub> (<jats:bold>2<\/jats:bold>), which have hexagonal unit cells [<jats:bold>1<\/jats:bold>: <jats:italic>R<\/jats:italic><jats:styled-content>$\\bar 3$<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-ueqn-1.gif\" xlink:title=\"equation image\"\/><\/jats:styled-content><jats:italic>m<\/jats:italic>, <jats:italic>a=<\/jats:italic>8.0738(1), <jats:italic>c<\/jats:italic>=29.086(1)\u2005\u00c5; <jats:bold>2<\/jats:bold>: <jats:italic>P<\/jats:italic><jats:styled-content>$\\bar 3$<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-ueqn-2.gif\" xlink:title=\"equation image\"\/><\/jats:styled-content><jats:italic>m<\/jats:italic>1, <jats:italic>a<\/jats:italic>=7.9992(3), <jats:italic>c<\/jats:italic>=14.014(1)\u2005\u00c5] rather than the face centered cubic lattice that is typical of Prussian blue structured materials. The formula units of both <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> are composed of one low\u2010 and two high\u2010spin Mn<jats:sup>II<\/jats:sup> ions. Each low\u2010spin, octahedral [Mn<jats:sup>II<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>]<jats:sup>4\u2212<\/jats:sup> bonds to six high\u2010spin tetrahedral Mn<jats:sup>II<\/jats:sup> ions through the N\u2005atoms, and each of the tetrahedral Mn<jats:sup>II<\/jats:sup> ions are bound to three low\u2010spin octahedral [Mn<jats:sup>II<\/jats:sup>(CN)<jats:sub>6<\/jats:sub>]<jats:sup>4\u2212<\/jats:sup> moieties. For <jats:bold>2<\/jats:bold>, the fourth cyanide on the tetrahedral Mn<jats:sup>II<\/jats:sup> site is C\u2005bound and is terminal. In contrast, it is orientationally disordered and bridges two tetrahedral Mn<jats:sup>II<\/jats:sup> centers for <jats:bold>1<\/jats:bold> forming an extended 3D network structure. The layers of octahedra are separated by 14.01\u2005\u00c5 (<jats:italic>c<\/jats:italic>\u2005axis) for <jats:bold>2<\/jats:bold>, and 9.70\u2005\u00c5 (<jats:italic>c<\/jats:italic>\/3) for <jats:bold>1<\/jats:bold>. The [NEt<jats:sub>4<\/jats:sub>]<jats:sup>+<\/jats:sup> cations and solvent are disordered and reside between the layers. Both <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> possess antiferromagnetic superexchange coupling between each low\u2010spin (<jats:italic>S<\/jats:italic>=1\/2) octahedral Mn<jats:sup>II<\/jats:sup> site and two high\u2010spin (<jats:italic>S<\/jats:italic>=5\/2) tetrahedral Mn<jats:sup>II<\/jats:sup> sites within a layer. Analogue <jats:bold>2<\/jats:bold> orders as a ferrimagnet at 27(\u00b11)\u2005K with a coercive field and remanent magnetization of 1140\u2005Oe and 22\u2009800\u2005emuOe\u2009mol<jats:sup>\u22121<\/jats:sup>, respectively, and the magnetization approaches saturation of 49\u2009800\u2005emuOe\u2009mol<jats:sup>\u22121<\/jats:sup> at 90\u2009000\u2005Oe. In contrast, the bonding via bridging cyanides between the ferrimagnetic layers leads to antiferromagnetic coupling, and 3D structured <jats:bold>1<\/jats:bold> has a different magnetic behavior to <jats:bold>2<\/jats:bold>. Thus, <jats:bold>1<\/jats:bold> is a Prussian blue analogue with an antiferromagnetic ground state [<jats:italic>T<\/jats:italic><jats:sub>c<\/jats:sub>=27\u2005K from d(<jats:italic>\u03c7T<\/jats:italic>)\/d<jats:italic>T<\/jats:italic>].<\/jats:p>","DOI":"10.1002\/chem.201200672","type":"journal-article","created":{"date-parts":[[2012,6,19]],"date-time":"2012-06-19T16:19:17Z","timestamp":1340122757000},"page":"9281-9288","source":"Crossref","is-referenced-by-count":21,"title":["Structure and Magnetic Ordering of the Anomalous Layered (2D) Ferrimagnet [NEt<sub>4<\/sub>]<sub>2<\/sub>Mn<sup>II<\/sup><sub>3<\/sub>(CN)<sub>8<\/sub> and 3D Bridged\u2010Layered Antiferromagnet [NEt<sub>4<\/sub>]Mn<sup>II<\/sup><sub>3<\/sub>(CN)<sub>7<\/sub> Prussian Blue Analogues"],"prefix":"10.1002","volume":"18","author":[{"given":"Christopher 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