M3(P2O7)22--type open frameworks featuring [M2O8] and [M3O12] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids: Na2M3(P2O7)2·ACl (M = Mn, Fe; A = Rb, Cs) and K2M3(P2O7)2·CsCl (M = Fe, Mn)

Jianhua Gao; Jian Li; Dino Sulejmanovic; Shiou Jyh Hwu

doi:10.1021/ic5024696

M₃(P₂O₇)₂^2--type open frameworks featuring [M₂O₈] and [M₃O₁₂] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids: Na₂M₃(P₂O₇)₂·ACl (M = Mn, Fe; A = Rb, Cs) and K₂M₃(P₂O₇)₂·CsCl (M = Fe, Mn)

Jianhua Gao, Jian Li, Dino Sulejmanovic, Shiou Jyh Hwu

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Single crystals of six polymorphic salt-inclusion phosphates of the A₂M₃(P₂O₇)₂·ACl type, Na₂Mn₃(P₂O₇)₂·CsCl (1), Na₂Mn₃(P₂O₇)₂·RbCl (2), Na₂Fe₃(P₂O₇)₂·CsCl (3), Na₂Fe₃(P₂O₇)₂·RbCl (4), K₂Mn₃(P₂O₇)₂·CsCl (5), and K₂Fe₃(P₂O₇)₂·CsCl (6), were grown in reactive molten chloride flux media. Compounds 1-4 are isostructural and crystallize in the space group C2/c (No. 15), while 5 and 6 crystallize in P2/c (No. 13) and P1 (No. 2), respectively. The title compounds have demonstrated an unprecedented versatility, where the M₃(P₂O₇)₂^2- covalent open frameworks contain [M₃O₁₂] (M = Mn²⁺, Fe²⁺) trimeric units in 1-4 and [M₂O₈] dimers in 5 and 6. These multinuclear, transition-metal oxide units are linked by Cl^- ions through the M-Cl bonds to form one-dimensional (1D) chains. The 1D chains and [P₂O₇] groups share common O atoms to form the extended network. The M₃(P₂O₇)₂^2- open-framework structures exhibit channels where the respective Na⁺/K⁺ ions and ACl salt (A = Rb, Cs) reside. Magnetic susceptibility of 2 and 4 suggests bulk antiferromagnetic properties as expected. The local structure and thermal decomposition are examined by IR and differential scanning calorimetry of representative compounds. The factors that determine the reticular chemistry of the M₃(P₂O₇)₂^2- type are illustrated in terms of the inclusion of ionic lattices of different sizes and contents.

Original language	English
Pages (from-to)	1136-1144
Number of pages	9
Journal	Inorganic Chemistry
Volume	54
Issue number	3
DOIs	https://doi.org/10.1021/ic5024696
State	Published - Feb 2 2015
Externally published	Yes

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Gao, J., Li, J., Sulejmanovic, D., & Hwu, S. J. (2015). M₃(P₂O₇)₂^2--type open frameworks featuring [M₂O₈] and [M₃O₁₂] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids: Na₂M₃(P₂O₇)₂·ACl (M = Mn, Fe; A = Rb, Cs) and K₂M₃(P₂O₇)₂·CsCl (M = Fe, Mn). Inorganic Chemistry, 54(3), 1136-1144. https://doi.org/10.1021/ic5024696

Gao, Jianhua ; Li, Jian ; Sulejmanovic, Dino et al. / M₃(P₂O₇)₂^2--type open frameworks featuring [M₂O₈] and [M₃O₁₂] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids : Na₂M₃(P₂O₇)₂·ACl (M = Mn, Fe; A = Rb, Cs) and K₂M₃(P₂O₇)₂·CsCl (M = Fe, Mn). In: Inorganic Chemistry. 2015 ; Vol. 54, No. 3. pp. 1136-1144.

@article{9b560b29839d442098239a22adfeb5ff,

title = "M3(P2O7)22--type open frameworks featuring [M2O8] and [M3O12] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids: Na2M3(P2O7)2·ACl (M = Mn, Fe; A = Rb, Cs) and K2M3(P2O7)2·CsCl (M = Fe, Mn)",

abstract = "Single crystals of six polymorphic salt-inclusion phosphates of the A2M3(P2O7)2·ACl type, Na2Mn3(P2O7)2·CsCl (1), Na2Mn3(P2O7)2·RbCl (2), Na2Fe3(P2O7)2·CsCl (3), Na2Fe3(P2O7)2·RbCl (4), K2Mn3(P2O7)2·CsCl (5), and K2Fe3(P2O7)2·CsCl (6), were grown in reactive molten chloride flux media. Compounds 1-4 are isostructural and crystallize in the space group C2/c (No. 15), while 5 and 6 crystallize in P2/c (No. 13) and P1 (No. 2), respectively. The title compounds have demonstrated an unprecedented versatility, where the M3(P2O7)22- covalent open frameworks contain [M3O12] (M = Mn2+, Fe2+) trimeric units in 1-4 and [M2O8] dimers in 5 and 6. These multinuclear, transition-metal oxide units are linked by Cl- ions through the M-Cl bonds to form one-dimensional (1D) chains. The 1D chains and [P2O7] groups share common O atoms to form the extended network. The M3(P2O7)22- open-framework structures exhibit channels where the respective Na+/K+ ions and ACl salt (A = Rb, Cs) reside. Magnetic susceptibility of 2 and 4 suggests bulk antiferromagnetic properties as expected. The local structure and thermal decomposition are examined by IR and differential scanning calorimetry of representative compounds. The factors that determine the reticular chemistry of the M3(P2O7)22- type are illustrated in terms of the inclusion of ionic lattices of different sizes and contents.",

author = "Jianhua Gao and Jian Li and Dino Sulejmanovic and Hwu, {Shiou Jyh}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2015",

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day = "2",

doi = "10.1021/ic5024696",

language = "English",

volume = "54",

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Gao, J, Li, J, Sulejmanovic, D & Hwu, SJ 2015, 'M₃(P₂O₇)₂^2--type open frameworks featuring [M₂O₈] and [M₃O₁₂] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids: Na₂M₃(P₂O₇)₂·ACl (M = Mn, Fe; A = Rb, Cs) and K₂M₃(P₂O₇)₂·CsCl (M = Fe, Mn)', Inorganic Chemistry, vol. 54, no. 3, pp. 1136-1144. https://doi.org/10.1021/ic5024696

M₃(P₂O₇)₂^2--type open frameworks featuring [M₂O₈] and [M₃O₁₂] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids: Na₂M₃(P₂O₇)₂·ACl (M = Mn, Fe; A = Rb, Cs) and K₂M₃(P₂O₇)₂·CsCl (M = Fe, Mn). / Gao, Jianhua; Li, Jian; Sulejmanovic, Dino et al.
In: Inorganic Chemistry, Vol. 54, No. 3, 02.02.2015, p. 1136-1144.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - M3(P2O7)22--type open frameworks featuring [M2O8] and [M3O12] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids

T2 - Na2M3(P2O7)2·ACl (M = Mn, Fe; A = Rb, Cs) and K2M3(P2O7)2·CsCl (M = Fe, Mn)

AU - Gao, Jianhua

AU - Li, Jian

AU - Sulejmanovic, Dino

AU - Hwu, Shiou Jyh

PY - 2015/2/2

Y1 - 2015/2/2

N2 - Single crystals of six polymorphic salt-inclusion phosphates of the A2M3(P2O7)2·ACl type, Na2Mn3(P2O7)2·CsCl (1), Na2Mn3(P2O7)2·RbCl (2), Na2Fe3(P2O7)2·CsCl (3), Na2Fe3(P2O7)2·RbCl (4), K2Mn3(P2O7)2·CsCl (5), and K2Fe3(P2O7)2·CsCl (6), were grown in reactive molten chloride flux media. Compounds 1-4 are isostructural and crystallize in the space group C2/c (No. 15), while 5 and 6 crystallize in P2/c (No. 13) and P1 (No. 2), respectively. The title compounds have demonstrated an unprecedented versatility, where the M3(P2O7)22- covalent open frameworks contain [M3O12] (M = Mn2+, Fe2+) trimeric units in 1-4 and [M2O8] dimers in 5 and 6. These multinuclear, transition-metal oxide units are linked by Cl- ions through the M-Cl bonds to form one-dimensional (1D) chains. The 1D chains and [P2O7] groups share common O atoms to form the extended network. The M3(P2O7)22- open-framework structures exhibit channels where the respective Na+/K+ ions and ACl salt (A = Rb, Cs) reside. Magnetic susceptibility of 2 and 4 suggests bulk antiferromagnetic properties as expected. The local structure and thermal decomposition are examined by IR and differential scanning calorimetry of representative compounds. The factors that determine the reticular chemistry of the M3(P2O7)22- type are illustrated in terms of the inclusion of ionic lattices of different sizes and contents.

AB - Single crystals of six polymorphic salt-inclusion phosphates of the A2M3(P2O7)2·ACl type, Na2Mn3(P2O7)2·CsCl (1), Na2Mn3(P2O7)2·RbCl (2), Na2Fe3(P2O7)2·CsCl (3), Na2Fe3(P2O7)2·RbCl (4), K2Mn3(P2O7)2·CsCl (5), and K2Fe3(P2O7)2·CsCl (6), were grown in reactive molten chloride flux media. Compounds 1-4 are isostructural and crystallize in the space group C2/c (No. 15), while 5 and 6 crystallize in P2/c (No. 13) and P1 (No. 2), respectively. The title compounds have demonstrated an unprecedented versatility, where the M3(P2O7)22- covalent open frameworks contain [M3O12] (M = Mn2+, Fe2+) trimeric units in 1-4 and [M2O8] dimers in 5 and 6. These multinuclear, transition-metal oxide units are linked by Cl- ions through the M-Cl bonds to form one-dimensional (1D) chains. The 1D chains and [P2O7] groups share common O atoms to form the extended network. The M3(P2O7)22- open-framework structures exhibit channels where the respective Na+/K+ ions and ACl salt (A = Rb, Cs) reside. Magnetic susceptibility of 2 and 4 suggests bulk antiferromagnetic properties as expected. The local structure and thermal decomposition are examined by IR and differential scanning calorimetry of representative compounds. The factors that determine the reticular chemistry of the M3(P2O7)22- type are illustrated in terms of the inclusion of ionic lattices of different sizes and contents.

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U2 - 10.1021/ic5024696

DO - 10.1021/ic5024696

M3 - Article

AN - SCOPUS:84961287915

SN - 0020-1669

VL - 54

SP - 1136

EP - 1144

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3