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).

Single crystals of six polymorphic salt-inclusion phosphates of the A(2)M(3)(P(2)O(7))(2)·A'Cl type, Na(2)Mn(3)(P(2)O(7))(2)·CsCl (1), Na(2)Mn(3)(P(2)O(7))(2)·RbCl (2), Na(2)Fe(3)(P(2)O(7))(2)·CsCl (3), Na(2)Fe(3)(P(2)O(7))(2)·RbCl (4), K(2)Mn(3)(P(2)O(7))(2)·CsCl (5), and K(2)Fe(3)(P(2)O(7))(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 P1̅ (No. 2), respectively. The title compounds have demonstrated an unprecedented versatility, where the M(3)(P(2)O(7))(2)(2-) covalent open frameworks contain [M(3)O(12)] (M = Mn(2+), Fe(2+)) trimeric units in 1-4 and [M(2)O(8)] 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 [P(2)O(7)] groups share common O atoms to form the extended network. The M(3)(P(2)O(7))(2)(2-) open-framework structures exhibit channels where the respective Na(+)/K(+) ions and A'Cl 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 M(3)(P(2)O(7))(2)(2-) type are illustrated in terms of the inclusion of ionic lattices of different sizes and contents.

[1]  S. Hwu,et al.  KMn3O2(Ge2O7): An S = 2 Magnetic Insulator Featuring Pillared Kagome Lattice , 2014 .

[2]  Zhihua Yang,et al.  Effect of Rigid Units on the Symmetry of the Framework: Design and Synthesis of Centrosymmetric NaBa4(B5O9)2F2Cl and Noncentrosymmetric NaBa4(AlB4O9)2Br3 , 2013 .

[3]  K. Lii,et al.  High-temperature, high-pressure hydrothermal synthesis and characterization of a salt-inclusion mixed-valence uranium(V,VI) silicate: [Na9F2][(U(V)O2)(U(VI)O2)2(Si2O7)2]. , 2013, Inorganic chemistry.

[4]  Zhihua Yang,et al.  New salt-inclusion borate, Li3Ca9(BO3)7·2[LiF]: a promising UV NLO material with the coplanar and high density BO3 triangles. , 2013, Inorganic chemistry.

[5]  S. Hwu,et al.  Noncentrosymmetric Salt Inclusion Oxides: Role of Salt Lattices and Counter Ions in Bulk Polarity , 2012 .

[6]  D. VanDerveer,et al.  Synthesis and structure of bismuth(III)-containing noncentrosymmetric phosphates, Cs3KBi2M4(PO4)6Cl (M = Mn, Fe). Monoclinic (Cc) and tetragonal (P43) polymorphs templated by chlorine-centered Cl(Bi2Cs) acentric units. , 2012, Inorganic chemistry.

[7]  D. VanDerveer,et al.  Symmetry preservation in a new noncentrosymmetric lattice comprised of acentric POM clusters residing in bowls of Cs(+)-based half SOD β-cage. , 2012, Chemical communications.

[8]  J. Hudson,et al.  Extended utility of molten-salt chemistry: unprecedented synthesis of a water-soluble salt-inclusion solid comprised of high-nuclearity vanadium oxide clusters. , 2011, Inorganic chemistry.

[9]  W. Cheng,et al.  Synthesis and characterizations of two anhydrous metal borophosphates: MIII2BP3O12 (M=Fe, In) , 2010 .

[10]  S. Hwu,et al.  Salt-templated mesoporous solids comprised of interlinked polyoxovanadate clusters. , 2010, Inorganic chemistry.

[11]  B. Raveau,et al.  A new lithium manganese phosphate with an original tunnel structure in the A2MP2O7 family , 2008 .

[12]  D. VanDerveer,et al.  The versatile chemistry and noncentrosymmetric crystal structures of salt-inclusion vanadate hybrids. , 2008, Angewandte Chemie.

[13]  Y. Pashkevich,et al.  Structural phase transition in two-dimensional tetramer-cuprate Na5RbCu4(AsO4)4Cl2 , 2007 .

[14]  S. Hwu,et al.  New cuprates featuring ladderlike periodic arrays of [Cu3O8]10- trimeric magnetic nanostructures. , 2006, Inorganic chemistry.

[15]  S. Hwu,et al.  Synthesis, structure, and magnetic properties of Cs(2-x)RbxCu3P4O14 (0.0 , 2006, Inorganic chemistry.

[16]  M. Azuma,et al.  Investigation of the crystal structure and the structural and magnetic properties of SrCu2(PO4)2. , 2005, Inorganic chemistry.

[17]  S. Hwu,et al.  Salt-inclusion synthesis of two new polar solids, Ba6Mn4Si12O34Cl3 and Ba6Fe5Si11O34Cl3. , 2005, Inorganic chemistry.

[18]  Shiou-Jyh Hwu,et al.  Salt-inclusion synthesis of Ba2MnSi2O7Cl. A fresnoite-type polar framework containing the acentric [Si2O7]6 - polyanion in the anti-ReO3 type [(Ba2Mn)Cl]6+) cage. , 2003, Inorganic chemistry.

[19]  S. Hwu,et al.  The fascinating noncentrosymmetric copper(II) phosphates synthesized via CsCl salt-inclusion. , 2003, Inorganic chemistry.

[20]  Richard Mackay,et al.  A new class of hybrid materials via salt inclusion: novel copper(II) arsenates Na(5)ACu(4)(AsO(4))(4)Cl(2) (A = Rb, Cs) composed of alternating covalent and ionic lattices. , 2002, Journal of the American Chemical Society.

[21]  Shiou-Jyh Hwu,et al.  High-Temperature Synthesis of an Open-Framework Compound, Na2Cs2Cu3(P2O7)2Cl2 (CU-4), by Molten-Salt Methods , 2001 .

[22]  Shiou-Jyh Hwu,et al.  Salt-Templated Open Frameworks (CU-2): Novel Phosphates and Arsenates Containing M3(X2O7)22- (M = Mn, Cu; X = P, As) Micropores 5.3 Å and 12.7 Å in Diameter , 1999 .

[23]  S. Hwu,et al.  Synthesis and Characterization of Three New Layered Phosphates, Na2MnP2O7, NaCsMnP2O7, and NaCsMn0.35Cu0.65P2O7 , 1998 .

[24]  S. Hwu,et al.  Coordination Intercalation of NbAsO5 with Alkali-Metal Chloride. Synthesis, Structure, and Spectroscopy of Two New Layered Niobium(V) Arsenate Compounds, ANbAsO5Cl (A = Rb, Cs) , 1998 .

[25]  I. Brown.  VALENCE: a program for calculating bond valences , 1996 .

[26]  S. Hwu,et al.  A Novel Copper(I/II) Oxophosphate Chloride with a Quasi-One-Dimensional μ4-Oxo-Bridged Copper(II) Chain. Crystal Structure and Magnetic Properties of [Na2CuII3(PO4)2][CuIOCl] , 1996 .

[27]  E. M. Holt,et al.  Synthesis and crystal structure of K2CuP2O7 , 1995 .

[28]  S. Hwu,et al.  A Novel Honeycomb-like Copper(II) Phosphate Framework, [BaCl][CuPO4] , 1995 .

[29]  Juan Rodríguez-Carvajal,et al.  Recent advances in magnetic structure determination by neutron powder diffraction , 1993 .

[30]  I. D. Brown,et al.  Bond‐valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database , 1985 .

[31]  J. Corbett.  New materials from high temperature synthesis , 1984 .

[32]  R. D. Shannon.  Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .