The size of the organic cation dictates both the composition and the extended 3-D structure for hybrid organic/inorganic Prussian blue analogues (PBAs) of A a MnII b (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 of A3MnII 5(CN)13 composition. A3MnII 5(CN)13 forms a complex, 3-D 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)3MnII 5(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 nonmagnetic cyanides. These are rare examples of intrinsic, chemically prepared and controlled artificial antiferromagnets and have the 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]2MnII 3(CN)8, [NEt4]MnII 3(CN)7, and Mn(CN)2 form stoichiometrically related A a MnII b (CN) a+2b (a = 0, b = 1; a = 2, b = 3; a = 1, b = 3; and a = 3, b = 5) series possessing unprecedented stoichiometries and lattice motifs. 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 ∠MnNC. This A a MnII b (CN) a+2b family of compounds are referred to as being cation adaptive in which size and shape dictate both the stoichiometry and structure.
[NMe4 ]2 [TCNE]2 (TCNE=tetracyanoethenide) formed from the reaction of TCNE and (NMe4 )CN in MeCN has νCN IR absorptions at 2195, 2191, 2172, and 2156 cm(-1) and a νCC absorption at 1383 cm(-1) that are characteristic of reduced TCNE. The TCNEs have an average central CC distance of 1.423 Å that is also characteristic of reduced TCNE. The reduced TCNE forms a previously unknown non-eclipsed, centrosymmetric π-[TCNE]2 (2-) dimer with nominal C2 symmetry, 12 sub van der Waals interatomic contacts <3.3 Å, a central intradimer separation of 3.039(3) Å, and comparable intradimer C⋅⋅⋅N distances of 3.050(3) and 2.984(3) Å. The two pairs of central C⋅⋅⋅C atoms form a ∢C-C⋅⋅⋅C-C of 112.6° that is substantially greater than the 0° observed for the eclipsed D2h π-[TCNE]2 (2-) dimer possessing a two-electron, four-center (2e(-) /4c) bond with two C⋅⋅⋅C components from a molecular orbital (MO) analysis. A MO study combining CAS(2,2)/MRMP2/cc-pVTZ and atoms-in-molecules (AIM) calculations indicates that the non-eclipsed, C2 π-[TCNE]2 (2-) dimer exhibits a new type of a long, intradimer bond involving one strong C⋅⋅⋅C and two weak C⋅⋅⋅N components, that is, a 2e(-) /6c bond. The C2 π-[TCNE]2 (2-) conformer has a singlet, diamagnetic ground state with a thermally populated triplet excited state with J/kB =1000 K (700 cm(-1) ; 86.8 meV; 2.00 kcal mol(-1) ; H=-2 JSa ⋅Sb ); at the CAS(2,2)/MBMP2 level the triplet is computed to be 9.0 kcal mol(-1) higher in energy than the closed-shell singlet ground state. The results from CAS(2,2)/NEVPT2/cc-pVTZ calculations indicate that the C2 and D2h conformers have two different local metastable minima with the C2 conformer being 1.3 kcal mol(-1) less stable. The different natures of the C2 and D2h conformers are also noted from the results of valence bond (VB) qualitative diagram that shows a 10e(-) /6c bond with one C⋅⋅⋅C and two C⋅⋅⋅N bonding components for the C2 conformer as compared to the 6e(-) /4c bond for the D2h conformer with two C⋅⋅⋅C bonding components.
An S = 1 antiferromagnetic polymeric chain, [Ni(HF2)(3-Clpy)4]BF4 (py = pyridine), has previously been identified to have intrachain, nearest-neighbor antiferromagnetic interaction strength J/kB = 4.86 K and single-ion anisotropy (zero-field splitting) D/kB = 4.3 K, so the ratio D/J = 0.88 places this system close to the D/J ≈ 1 gapless critical point between the topologically distinct Haldane and Large-D phases. The magnetization was studied over a range of temperatures, 50 mK ≤ T ≤ 1 K, and magnetic fields, B ≤ 10 T, in an attempt to identify a critical field, Bc, associated with the closing of the Haldane gap, and the present work places an upper bound of Bc ≤ (35 ± 10) mT. At higher fields, the observed magnetic response is qualitatively similar to the "excess" signal observed by other workers at 0.5 K and below 3 T. The high-field (up to 14.5 T), multi-frequency (nomially 200 GHz to 425 GHz) ESR spectra at 3 K reveal several broad features considered to be associated with the linear-chain sample.PACS numbers: 75.50. Ee, 75.10.Kt, 74.40.Kb After Haldane reported the fundamental differences between one-dimensional Heisenberg antiferromagnets with integer and half-integer spins [1,2], theoretical [3][4][5] and experimental [6] activities focused on clarifying the magnetic phases and properties of a broad range of linear-chain magnets described by the Hamiltonian
The reactions of MnII(O2CCH3)2 with NEt3Me+CN− and NEt2Me2+CN− form (NEt3Me)2MnII5(CN)12 (1) and (NEt2Me2)2MnII5(CN)12 (2), respectively. Structure model‐building and Rietveld refinement of high‐resolution synchrotron powder diffraction data revealed a cubic [a=24.0093 Å (1), 23.8804 Å (2)] 3D extended structural motif with adjacent tetrahedral and octahedral MnII sites in a 3:2 ratio. Each tetrahedral MnII site is surrounded by four low‐spin octahedral MnII sites, and each octahedral MnII site is surrounded by six high‐spin tetrahedral MnII sites; adjacent sites are antiferromagnetically coupled in 3D. Compensation does not occur, and magnetic ordering as a ferrimagnet is observed at Tc=13 K for 2 based on the temperature at which remnant magnetization, Mr(T)→0. The hysteresis has an unusual constricted shape with inflection points around 50 and 1.2 kOe with a 5 K coercivity of 16 Oe and remnant magnetization, Mr, of 2050 emuOe mol−1. The unusual structure and stoichiometry are attributed to the very ionic nature of the high‐spin N‐bonded MnII ion, which enables the maximization of the attractive van der Waals interactions through minimization of void space via a reduced ∠ MnNC. This results in an additional example of the AxMnIIy(CN)x+2y (x=0, y=1; x=1, y=3; x=2, y=1; x=2, y=2; x=2, y=3; x=3, y=5; and x=4, y=1) family of compounds possessing an unprecedented stoichiometry and lattice motif that are cation adaptive structured materials.
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