Synthesis and characterization of one- and two-dimensional octacyanometalate(V) networks: {[trans-MII(DMF)4][cis-MII(DMF)4]2[MV(CN)8]2}n (MII = Mn, Fe, Ni; MV = Mo, W)

Jeffrey R. Withers; Dongfeng Li; Jeremy Triplet; Chad Ruschman; Sean Parkin; Guangbin Wang; Gordon T. Yee; Stephen M. Holmes

doi:10.1016/j.poly.2007.01.049

Synthesis and characterization of one- and two-dimensional octacyanometalate(V) networks: {[trans-M^II(DMF)₄][cis-M^II(DMF)₄]₂[M^V(CN)₈]₂}_n (M^II = Mn, Fe, Ni; M^V = Mo, W)

Jeffrey R. Withers, Dongfeng Li, Jeremy Triplet, Chad Ruschman, Sean Parkin, Guangbin Wang, Gordon T. Yee, Stephen M. Holmes

Chemistry

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

29 Scopus citations

Abstract

Treatment of several binary transition metal p-toluenesulfonates [M^II(OTs)₂] with tri(butyl)ammonium octacyanomolybdate(V) or -tungstate(V) in DMF readily affords a series of one- and two-dimensional crystalline octacyanometalate networks of [M^II(DMF)₄]₃[M^V(CN)₈]₂ (M^V = Mo, W; M^II = Mn, 5, 6; Ni, 7, 8) stoichiometry. Treatment of Fe(OTs)₂ with [HBu₃N]₃[W^V(CN)₈] in DMF affords amorphous precipitates while FeCl₃ affords crystalline [Fe^II(DMF)₆]₂[W^IV(CN)₈] (9) salts; two-dimensional [Fe^II(DMF)₄]₃[W^V(CN)₈]₂ (10) lattices are obtained from 9 after standing several months. The structures of 5 and 8 contain [cis-M^II(DMF)₄(μ-NC)₂]²⁺ and [trans-M^II(DMF)₄(μ-NC)₂]²⁺ units that are linked via cyanides to three-connected [M^V(CN)₅(μ-CN)₃]^3- centers, forming a one-dimensional chain of {M₂^II (μ -CN)₄ M₂^V} squares that crystallize in the monoclinic (5, P2₁/n) and triclinic (8,P over(1, ̄)) space groups; 6 (P2₁/n) and 10 (P2₁/c) crystallize as two-dimensional corrugated sheets containing [cis-M^II(DMF)₄(μ-NC)₂]²⁺, [trans-M^II(DMF)₄(μ-NC)₂]²⁺, and [M^V(CN)₅(μ-CN)₃]^3- units in a 4:2:6 ratio. Magnetic measurements indicate that 6 is a ferrimagnet (T_N = 8 K) that exhibits frequency-dependent behavior in χ″ that is qualitatively similar to 1- and 2-D lattices reported by Tang and Holmes, respectively; dc magnetic measurements suggest that 5, 7, and 8 exhibit incipient magnetic ordering while ac measurements show no frequency-dependent behavior in χ″. Surprisingly, conversion of 5 to 6 in the presence of counterions occurs while heating crystalline samples introduces additional magnetic phases without linkage isomerism; two-dimensional phases containing Mn^II centers appear to be the sole product when wet DMF is used as a reaction solvent. The experimental evidence suggests that coordinated DMF ligands are labile and the M^II(μ-NC)M^V linkages are susceptible to fragmentation.

Original language	English
Pages (from-to)	2353-2366
Number of pages	14
Journal	Polyhedron
Volume	26
Issue number	9-11
DOIs	https://doi.org/10.1016/j.poly.2007.01.049
State	Published - Jun 15 2007

Bibliographical note

Funding Information:
S.M.H. gratefully acknowledges the donors of the American Chemical Society Petroleum Research Fund (PRF 38388-G3), the University of Kentucky Summer Faculty Research Fellow, and the National Science Foundation Research Experience for Undergraduates (CHE-0097668) programs for financial support. We are indebted to the Frederick Seitz Materials Research Laboratory at the University of Illinois at Urbana-Champaign for access to their Magnetometer facility. G.T.Y. thanks the National Science Foundation (CHE-0210395) for partial financial support.

Keywords

Building block approach
Cyanide networks
Magnetic
Octacyanometalate

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.poly.2007.01.049

Cite this

@article{d73e8ec5cfef47a98bffa4a722b81ead,

title = "Synthesis and characterization of one- and two-dimensional octacyanometalate(V) networks: {[trans-MII(DMF)4][cis-MII(DMF)4]2[MV(CN)8]2}n (MII = Mn, Fe, Ni; MV = Mo, W)",

abstract = "Treatment of several binary transition metal p-toluenesulfonates [MII(OTs)2] with tri(butyl)ammonium octacyanomolybdate(V) or -tungstate(V) in DMF readily affords a series of one- and two-dimensional crystalline octacyanometalate networks of [MII(DMF)4]3[MV(CN)8]2 (MV = Mo, W; MII = Mn, 5, 6; Ni, 7, 8) stoichiometry. Treatment of Fe(OTs)2 with [HBu3N]3[WV(CN)8] in DMF affords amorphous precipitates while FeCl3 affords crystalline [FeII(DMF)6]2[WIV(CN)8] (9) salts; two-dimensional [FeII(DMF)4]3[WV(CN)8]2 (10) lattices are obtained from 9 after standing several months. The structures of 5 and 8 contain [cis-MII(DMF)4(μ-NC)2]2+ and [trans-MII(DMF)4(μ-NC)2]2+ units that are linked via cyanides to three-connected [MV(CN)5(μ-CN)3]3- centers, forming a one-dimensional chain of {M2II (μ -CN)4 M2V} squares that crystallize in the monoclinic (5, P21/n) and triclinic (8,P over(1,{\= })) space groups; 6 (P21/n) and 10 (P21/c) crystallize as two-dimensional corrugated sheets containing [cis-MII(DMF)4(μ-NC)2]2+, [trans-MII(DMF)4(μ-NC)2]2+, and [MV(CN)5(μ-CN)3]3- units in a 4:2:6 ratio. Magnetic measurements indicate that 6 is a ferrimagnet (TN = 8 K) that exhibits frequency-dependent behavior in χ″ that is qualitatively similar to 1- and 2-D lattices reported by Tang and Holmes, respectively; dc magnetic measurements suggest that 5, 7, and 8 exhibit incipient magnetic ordering while ac measurements show no frequency-dependent behavior in χ″. Surprisingly, conversion of 5 to 6 in the presence of counterions occurs while heating crystalline samples introduces additional magnetic phases without linkage isomerism; two-dimensional phases containing MnII centers appear to be the sole product when wet DMF is used as a reaction solvent. The experimental evidence suggests that coordinated DMF ligands are labile and the MII(μ-NC)MV linkages are susceptible to fragmentation.",

keywords = "Building block approach, Cyanide networks, Magnetic, Octacyanometalate",

author = "Withers, {Jeffrey R.} and Dongfeng Li and Jeremy Triplet and Chad Ruschman and Sean Parkin and Guangbin Wang and Yee, {Gordon T.} and Holmes, {Stephen M.}",

note = "Funding Information: S.M.H. gratefully acknowledges the donors of the American Chemical Society Petroleum Research Fund (PRF 38388-G3), the University of Kentucky Summer Faculty Research Fellow, and the National Science Foundation Research Experience for Undergraduates (CHE-0097668) programs for financial support. We are indebted to the Frederick Seitz Materials Research Laboratory at the University of Illinois at Urbana-Champaign for access to their Magnetometer facility. G.T.Y. thanks the National Science Foundation (CHE-0210395) for partial financial support. ",

year = "2007",

month = jun,

day = "15",

doi = "10.1016/j.poly.2007.01.049",

language = "English",

volume = "26",

pages = "2353--2366",

number = "9-11",

}

TY - JOUR

T1 - Synthesis and characterization of one- and two-dimensional octacyanometalate(V) networks

T2 - {[trans-MII(DMF)4][cis-MII(DMF)4]2[MV(CN)8]2}n (MII = Mn, Fe, Ni; MV = Mo, W)

AU - Withers, Jeffrey R.

AU - Li, Dongfeng

AU - Triplet, Jeremy

AU - Ruschman, Chad

AU - Parkin, Sean

AU - Wang, Guangbin

AU - Yee, Gordon T.

AU - Holmes, Stephen M.

N1 - Funding Information: S.M.H. gratefully acknowledges the donors of the American Chemical Society Petroleum Research Fund (PRF 38388-G3), the University of Kentucky Summer Faculty Research Fellow, and the National Science Foundation Research Experience for Undergraduates (CHE-0097668) programs for financial support. We are indebted to the Frederick Seitz Materials Research Laboratory at the University of Illinois at Urbana-Champaign for access to their Magnetometer facility. G.T.Y. thanks the National Science Foundation (CHE-0210395) for partial financial support.

PY - 2007/6/15

Y1 - 2007/6/15

N2 - Treatment of several binary transition metal p-toluenesulfonates [MII(OTs)2] with tri(butyl)ammonium octacyanomolybdate(V) or -tungstate(V) in DMF readily affords a series of one- and two-dimensional crystalline octacyanometalate networks of [MII(DMF)4]3[MV(CN)8]2 (MV = Mo, W; MII = Mn, 5, 6; Ni, 7, 8) stoichiometry. Treatment of Fe(OTs)2 with [HBu3N]3[WV(CN)8] in DMF affords amorphous precipitates while FeCl3 affords crystalline [FeII(DMF)6]2[WIV(CN)8] (9) salts; two-dimensional [FeII(DMF)4]3[WV(CN)8]2 (10) lattices are obtained from 9 after standing several months. The structures of 5 and 8 contain [cis-MII(DMF)4(μ-NC)2]2+ and [trans-MII(DMF)4(μ-NC)2]2+ units that are linked via cyanides to three-connected [MV(CN)5(μ-CN)3]3- centers, forming a one-dimensional chain of {M2II (μ -CN)4 M2V} squares that crystallize in the monoclinic (5, P21/n) and triclinic (8,P over(1, ̄)) space groups; 6 (P21/n) and 10 (P21/c) crystallize as two-dimensional corrugated sheets containing [cis-MII(DMF)4(μ-NC)2]2+, [trans-MII(DMF)4(μ-NC)2]2+, and [MV(CN)5(μ-CN)3]3- units in a 4:2:6 ratio. Magnetic measurements indicate that 6 is a ferrimagnet (TN = 8 K) that exhibits frequency-dependent behavior in χ″ that is qualitatively similar to 1- and 2-D lattices reported by Tang and Holmes, respectively; dc magnetic measurements suggest that 5, 7, and 8 exhibit incipient magnetic ordering while ac measurements show no frequency-dependent behavior in χ″. Surprisingly, conversion of 5 to 6 in the presence of counterions occurs while heating crystalline samples introduces additional magnetic phases without linkage isomerism; two-dimensional phases containing MnII centers appear to be the sole product when wet DMF is used as a reaction solvent. The experimental evidence suggests that coordinated DMF ligands are labile and the MII(μ-NC)MV linkages are susceptible to fragmentation.

AB - Treatment of several binary transition metal p-toluenesulfonates [MII(OTs)2] with tri(butyl)ammonium octacyanomolybdate(V) or -tungstate(V) in DMF readily affords a series of one- and two-dimensional crystalline octacyanometalate networks of [MII(DMF)4]3[MV(CN)8]2 (MV = Mo, W; MII = Mn, 5, 6; Ni, 7, 8) stoichiometry. Treatment of Fe(OTs)2 with [HBu3N]3[WV(CN)8] in DMF affords amorphous precipitates while FeCl3 affords crystalline [FeII(DMF)6]2[WIV(CN)8] (9) salts; two-dimensional [FeII(DMF)4]3[WV(CN)8]2 (10) lattices are obtained from 9 after standing several months. The structures of 5 and 8 contain [cis-MII(DMF)4(μ-NC)2]2+ and [trans-MII(DMF)4(μ-NC)2]2+ units that are linked via cyanides to three-connected [MV(CN)5(μ-CN)3]3- centers, forming a one-dimensional chain of {M2II (μ -CN)4 M2V} squares that crystallize in the monoclinic (5, P21/n) and triclinic (8,P over(1, ̄)) space groups; 6 (P21/n) and 10 (P21/c) crystallize as two-dimensional corrugated sheets containing [cis-MII(DMF)4(μ-NC)2]2+, [trans-MII(DMF)4(μ-NC)2]2+, and [MV(CN)5(μ-CN)3]3- units in a 4:2:6 ratio. Magnetic measurements indicate that 6 is a ferrimagnet (TN = 8 K) that exhibits frequency-dependent behavior in χ″ that is qualitatively similar to 1- and 2-D lattices reported by Tang and Holmes, respectively; dc magnetic measurements suggest that 5, 7, and 8 exhibit incipient magnetic ordering while ac measurements show no frequency-dependent behavior in χ″. Surprisingly, conversion of 5 to 6 in the presence of counterions occurs while heating crystalline samples introduces additional magnetic phases without linkage isomerism; two-dimensional phases containing MnII centers appear to be the sole product when wet DMF is used as a reaction solvent. The experimental evidence suggests that coordinated DMF ligands are labile and the MII(μ-NC)MV linkages are susceptible to fragmentation.

KW - Building block approach

KW - Cyanide networks

KW - Magnetic

KW - Octacyanometalate

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