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Anomalous Stoichiometry, 3-D Bridged Triangular/pentagonal Layered Structured Artificial Antiferromagnet for the Prussian Blue Analog A3MnII5(CN)13 (A = NMe4, NEtMe3). A Cation Adaptive Structure Saul H. Lapidus, Adora G. Graham, Christopher M Kareis, Casey G. Hawkins, Peter W. Stephens, and Joel S. Miller J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b10638 • Publication Date (Web): 17 Dec 2018 Downloaded from http://pubs.acs.org on December 17, 2018

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Journal of the American Chemical Society

Anomalous Stoichiometry, 3-D Bridged Triangular/pentagonal Layered Structured Artificial Antiferromagnet for the Prussian Blue Analog A3MnII5(CN)13 (A = NMe4, NEtMe3). A Cation Adaptive Structure Saul H. Lapidus,†‡ Adora G. Graham,§ Christopher M. Kareis,§ Casey G. Hawkins,§ Peter W. Stephens,*† Joel S. Miller*§ † Department

of Physics & Astronomy State, University of New York. Stony Brook, NY 11794-3800 USA

§

Department of Chemistry, University of Utah, Salt Lake City, UT 84112-0850 USA

‡

Current Address: X-ray Science Division, Argonne National Laboratory, Lemont IL 60439

ABSTRACT: The shape of the organic cation dictates both the composition and the extended 3-D structure for hybrid organic/inorganic Prussian blue analogs (PBAs) of AaMnIIb(CN)a+2b (A = cation) stoichiometry. Alkali PBAs are typically cubic with both MC6 and

M'N6

octahedral

coordination sites, and the alkali cation content depends on the M and M' oxidation states.

The

reaction

of

MnII(O2CCH3)2 and A+CN- (A = NMe4, NEtMe3) forms a hydrated

material

A3MnII5(CN)13 A3MnII5(CN)13 complex,

3-D

of

composition. forms

a

extended

structural motif with octahedral and rarely observed square pyramidal and trigonal bipyramidal MnII sites with a single layer motif of three pentagonal and one triangular fused rings. A complex pattern of MnIICN chains bridge the layers. (NMe4)3MnII5(CN)13 possesses one low-spin octahedral and four high-spin pentacoordinate MnII sites, and orders as an antiferromagnet at 11 K due to the layers being bridged and antiferromagnetically coupled by the non-magnetic cyanides. These are rare examples of intrinsic, chemically prepared and controlled artificial antiferromagnets, and have the

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advantage of having controlled uniform spacing between the layers as they are not physically prepared via deposition methods. A3Mn5(CN)13 (A = NMe4, NEtMe3) along with [NEt4]2MnII3(CN)8, [NEt4]MnII3(CN)7, and Mn(CN)2 form stoichiometrically related AaMnIIb(CN)a+2b (a = 0, b = 1; a = 2, b = 3; a = 1, b = 3; and a = 3, b = 5) series possessing an unprecedented stoichiometries and lattice motifs. This These unusual structures and stoichiometries are attributed to the very ionic nature of the high-spin N-bonded MnII ion that enables the maximization of the attractive van der Waals interactions via minimization of void space via a reduced ÐMnNC. This AaMnIIb(CN)a+2b family of compounds are referred to as being cation adaptive which size and shape dictates both the stoichiometry and structure. INTRODUCTION Several mixed-metal hexacyanometalates possessing the face centered cubic (fcc) (a ~ 10.5 Å) Prussian blue structural motif magnetically order with critical temperatures, Tc, as high as ~100 oC.1-3 The relatively high Tc’s are attributed to the strong superexchange via the conjugated -M'-NºC-M-CºN-M'- linkages.4 Albeit structurally related, Prussian blues

can

have

several

compositions,

e.g.

M'III4[MII(CN)6]3,

A+M'II[MIII(CN)6],

M'II3[MIII(CN)6]2, A+M'III[MII(CN)6], A+2M'II[MII(CN)6], and M'III[MIII(CN)6] (A+ = alkali cation) that are typically solvated. The canonical unit cell contains significant void space that can accommodate the A+ and/or water, and in some cases [M(CN)6]n- anions are missing. A2MnII[MnII(CN)6] (A = Na,5 K,6 Rb6), however, has the same framework topology, but a distorted lattice with nonlinear -M'-NºC- linkages with an average ÐM'-NºC 10 it is significant, as occurs for many compounds.26,33-35 The f values are n > 1.75)], and M2xO(16x-2)/3 (M = Mo, Ta) [= y M10O26 + z M22O58]. This is attributed to different and shifting crystallographic shear planes, or ordered stacking for the latter family. Alternatively, the structures of [NMe4]3Mn5(CN)13 and [NEtMe3]3Mn5(CN)13 may be viewed as "dimensional reduction" albeit with an increase in connectivity that is well known for monoatomic anionic oxides/sulfides and halides.40 Hence, it is extended to more complex anions as well as polyatomic cations. Zero dimensional (no extended

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structure) is observed for both [MnII(CN)6]4- and [MnII(CN)4]2- with Mn:CN ratios of 1:6 and 1:4, respectively, while 2-D [NEt4]2MnII3(CN)8 has Mn:CN of 1:2.67, and 3-D K2MnII[MnII(CN)6], [NEt4]MnII3(CN)7, and [NMe4]3MnII5(CN)13 have Mn:CN of 1:3.0, 1:2.33, and 1:2.60, respectively. Such complex, but variable stoichiometries are observed for several transition metal oxides.40 CONCLUSIONS The structure of A3MnII5(CN)13 (A = NMe4, NEtMe3) has a complex (and in the case of NMe4+ a very disordered) structure with octahedral, and rare square pyramidal, and trigonal bipyramidal MnII sites. It has a layer motif based on three pentagons and one triangle

perpendicularly

interconnected

by

orientationally

disordered

cyanides.

A3MnII5(CN)13 is key member of AaMnIIb(CN)a+2b (a = 0, b = 1; a = 1, b = 3; a = 2, b = 3; and a = 3, b = 5) that form cation adaptive structures. These unusual stoichiometries and extended lattices are attributed to the highly ionic nature of the high-spin N-bonded MnII ion that enables the maximization of the attractive van der Waals interactions via a reduced ÐMnNC.

A3MnII5(CN)13 magnetically order as antiferromagnets, and are

minimally magnetically frustrated. The intrinsic antiferromagnetic ordering arises from the non-magnetic cyanide layer providing antiferromagnetic coupling between the ferrimagnetic layers that result, as occurs for artificial antiferromagnets used in spin valves. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.XXXXXX. The powder X-ray crystallographic CIF files for 1•H O (295 and 22 K) and 2•H O 2

(CCDC1543750 -1543752). A movie showing the interlayer connectivity. AUTHOR INFORMATION Corresponding Authors * [email protected] * [email protected] 22


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DEDICATION Dedicated to the late Hugo Rietveld, on the fiftieth anniversary of the invention of the technique that bears his name, which has revolutionized the applicability of powder diffraction to crystallography ORCID Peter W. Stephens 0000-0002-8311-7305 Joel S Miller 0000-0001-5743-8327 Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS We appreciate the insightful discussion on network structures with Prof. Lars Öhrström (Chalmers University of Technology), and spin frustration with Prof. Arthur P. Ramirez (University of California, Santa Cruz) and the initial support by the Department of Energy Division of Material Science (Grant No. DE-FG03-93ER45504) for the chemical synthesis and magnetic studies (C.M.K., C.G.H., and J.S.M.). Use of the National Synchrotron Light Source, Brookhaven National Laboratory for powder X-ray diffraction studies (S.H.L. and P.W.S.) was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC0298CH10886. All authors contributed to writing of the manuscript. C.M.K. was also supported by the NSF MRSEC Grant # DMR-1121252 CFDA NO. 47.049. REFERENCES

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ToC

Anomalous Stoichiometry, 3-D Bridged Triangular/pentagonal Layered Structured Artificial Antiferromagnet for the Prussian Blue Analog A3MnII5(CN)13 (A = NMe4, NEtMe3). A Cation Adaptive Structure Saul H. Lapidus, Peter W. Stephens, Christopher M. Kareis, Casey G. Hawkins, and Joel S. Miller Atypical of Prussian blue structured materials, MnII and A(CN) (A = NMe4, NEtMe3) react to form A3Mn5(CN)13 possessing layers of triangles and pentagons. These layers are bridged together in a complex manner, and form non-frustrated artificial antiferromagnets. Unusual square-pyramid and trigonal bipyramid coordination of MnII cyano coordination is observed in these materials.

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pentagonal

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