Cation Templation of Anionic Metal Dicyanamide Networks

Werff, Patricia Mary Van Der; Batten, Stuart Robert; Jensen, Paul R.; Moubaraki, Boujemaa; Murray, Keith S.

doi:10.1021/ic000978x

Cited by 120 publications

(56 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Intensities are described by the abbreviations used for infrared spectra. 19,20 have ν(CtN) bands in the ranges quoted by Köhler 29 consistent with the bidentate µ 1,5 coordination of the dca ligand. However, the IR spectra also show some significant differences.…”

Section: Methodsmentioning

confidence: 61%

“…The structures were determined by X-ray crystallography and found to be isomorphous with the previously solved structure of (MePh 3 P)[Mn-(dca) 3 ]. 20 Both the MePh 3 P + and the EtPh 3 P + structures are essentially the same and crystallize in the same chiral space group P2 1 2 1 2 1 , although the positioning of the unit cell differs between the two cations. The structures consist of anionic 3D [M(dca) 3 ] -networks, in which the cations occur in pairs within the network cavities.…”

Section: Synthesis Andmentioning

confidence: 99%

“…We have recently reported the structure and magnetism of the anionic species (Ph 4 As)[M(dca) 3 ], where M ) Co-(II), Ni(II), 19 and Mn(II), 20 and (Ph 4 P)[Mn(dca) 3 ]. 20 The anions form extended sheets with (4,4) connectivity and octahedral geometry about the individual d-block ions. The anions display the long, bidentate µ 1,5 bridging mode (i.e., they coordinate via the nitrile nitrogens only).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh₃P)[M(dca)₃] (M = Fe, Co, Ni) and (EtPh₃P)[M(dca)₃] (M = Mn, Co, Ni) Networks

Werff

Batten

Jensen

et al. 2004

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

The structures of (MePh 3 P)[M(dca) 3 ] (M ) Fe, Co, Ni and dca ) dicyanamide, N(CN) 2 -) are isomorphous and contain anionic [M(dca) 3 ] -networks in which octahedral metal ions are bridged by bidentate µ 1,5 dca anions, to generate three-dimensional (3D) five-connected networks. The structures of (EtPh 3 P)[M(dca) 3 ] (M ) Mn, Co, Ni) are also isomorphous and contain similar anionic networks to the MePh 3 P + structures. In both sets of structures, the cations appear to perform a templating function and lie in pairs within cavities in the anionic network. These cation pairs show pseudo-6-fold phenyl embraces. No long-range magnetic ordering intrinsic to these materials was observed, although traces of the ferromagnets R-[Co(dca) 2 ] and R-[Ni(dca) 2 ] were observable in very small applied fields, at 9 and 21 K, respectively.

show abstract

Section: Methodsmentioning

confidence: 61%

Section: Synthesis Andmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh₃P)[M(dca)₃] (M = Fe, Co, Ni) and (EtPh₃P)[M(dca)₃] (M = Mn, Co, Ni) Networks

Werff

Batten

Jensen

et al. 2004

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

show abstract

“…In separate work, we are investigating structure ± magnetism relations in complexes of the type [R 4 E][M(dca) 3 ], E As, P, N, in which two-dimensional sheets are separated by R 4 E organic cations of different sizes. [21] Day et al [22] have recently noted the sensitivity of the type of long-range order and the size of T c in the [R 4 (30 mg, 0.16 mmol) was dissolved in of hot methanol (5 mL). On cooling to room temperature ethanol (5 mL) was added.…”

Section: Resultsmentioning

confidence: 99%

Self-Penetration—A Structural Compromise between Single Networks and Interpenetration: Magnetic Properties and Crystal Structures of [Mn(dca)2(H2O)] and [M(dca)(tcm)], M=Co, Ni, Cu, dca=Dicyanamide, N(CN)2−, tcm=Tricyanomethanide, C(CN)3−

et al. 2000

Self Cite

View full text Add to dashboard Cite

The three-dimensional coordination polymers [Mn(dca)2(H2O)] (1) and [M(dca)(tcm)], M =Co (2), Ni (3), Cu (4), dca =dicyanamide, N(CN)2-, tcm = tricyanomethanide, C(CN)3-, have isomorphous structures. In 1 half the dca ligands coordinate directly (through all three nitrogen atoms) to three Mn atoms (all metal atoms are six-coordinate), while the other half coordinate to two Mn atoms (through the nitrile nitrogens) and hydrogen bond to water molecules coordinated to a third Mn atom (through the amide nitrogen). This dca. H2O structural moiety is disordered over a mirror plane, and is replaced by the structurally equivalent tcm ligand in compounds 2-4. The resulting structures display a new self-penetrating 3,6-connected (2:1) network topology that can be related to, but is different from, the rutile net. The self-penetrating [M(dca)(tcm)] network can be viewed as a structural compromise between the two interpenetrating rutile-like networks of [M(tcm)2] and the single rutile-like network of alpha-[M(dca)2]. The temperature and field dependence of the DC and AC magnetic susceptibilities and magnetisations has been measured for complexes 1-4. Compounds 1-3 exhibit long-range magnetic order with critical temperatures of 6.3 K for 1, 3.5 K for 2 and 8.0 K for 3. The Cu11 compound 4 does not order and is essentially a paramagnet. Hysteresis measurements of coercive field and remnant magnetisation show that 1, 2 and 3 are soft magnets, 1 being a canted-spin antiferromagnet (weak ferromagnet), while 2 and 3 are ferromagnets that display some unusual features in their high-field magnetisation isotherms in comparison to their related alpha-[M(dca)2] phases.

show abstract

“…These weak interactions generated 1D chains as shown in Figure 2(b). These 1D chains are linked by alternative 1,5 -and 1,3 -dca bridges, which are less common for the dca ligand [88][89][90][91][92][93][94][95]. The weak copper (II) coordination leads to a pseudo-Jahn-Teller elongated octahedral geometry.…”

Section: Structure Description Compound 1 Crystallizes In Mon-mentioning

confidence: 99%

Synthesis, Crystal Structures, and Magnetic Properties of Ternary M(II)-Dicyanamide-hydroxypyridine Complexes

Zheng

2013

Journal of Inorganic Chemistry

View full text Add to dashboard Cite

Three two-dimensional (2D) and 3D supramolecular coordination architectures based on ternary M(II)-dicyanamide-2-hydro- (2), and [Mn(hepH) 2 (dca) 2 ] (3) (dca = dicyanamide, hmpH = 2-(hydroxymethyl)pyridine, hepH = 2-(hydroxyethyl)pyridine), have been synthesized. 1 is a mononuclear Co(II) complex. The mononuclear units are interlinked into a 2D (4,4) hydrogen-bonded layer via O-H⋅ ⋅ ⋅ N hydrogen bonds between the hydroxyl groups and the noncoordinating nitrile ends. These 2D layers are further extended into a 3D supramolecular architecture via the interlayer pyridyl-pyridyl stacking interaction. 2 has a 1D coordination chain structure formed by the double 1,5 -dca bridged dinuclear [Cu2( 1,5 -dca) 2 (hmpH) 2 ] unit and the 1,3 -dca bridges via weak Cu-N coordination, and these 1D coordination chains are further extended into 2D hydrogen-bonded layers via strong O-H⋅ ⋅ ⋅ N hydrogen-bonding interaction between the hydroxyl groups and the noncoordinating nitrile ends. 3 is a 2D (4,4) coordination network made of 1D [Mn(hepH)( 1,5 -dca)] helical chain units and interchain double ( 1,5 -dca) bridges. Pairs of [Mn(hepH)( 1,5 -dca)] helical chains are interlinked by the double ( 1,5 -dca) bridges into a racemic coordination layer structure, which is further extended into a 3D hydrogen-bonded network. Magnetic studies reveal that weak antiferromagnetic exchange occurs in 3.

show abstract

Cation Templation of Anionic Metal Dicyanamide Networks

Cited by 120 publications

References 29 publications

Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh₃P)[M(dca)₃] (M = Fe, Co, Ni) and (EtPh₃P)[M(dca)₃] (M = Mn, Co, Ni) Networks

Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh₃P)[M(dca)₃] (M = Fe, Co, Ni) and (EtPh₃P)[M(dca)₃] (M = Mn, Co, Ni) Networks

Self-Penetration—A Structural Compromise between Single Networks and Interpenetration: Magnetic Properties and Crystal Structures of [Mn(dca)2(H2O)] and [M(dca)(tcm)], M=Co, Ni, Cu, dca=Dicyanamide, N(CN)2−, tcm=Tricyanomethanide, C(CN)3−

Synthesis, Crystal Structures, and Magnetic Properties of Ternary M(II)-Dicyanamide-hydroxypyridine Complexes

Contact Info

Product

Resources

About

Cation Templation of Anionic Metal Dicyanamide Networks

Cited by 120 publications

References 29 publications

Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh3P)[M(dca)3] (M = Fe, Co, Ni) and (EtPh3P)[M(dca)3] (M = Mn, Co, Ni) Networks

Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh3P)[M(dca)3] (M = Fe, Co, Ni) and (EtPh3P)[M(dca)3] (M = Mn, Co, Ni) Networks

Self-Penetration—A Structural Compromise between Single Networks and Interpenetration: Magnetic Properties and Crystal Structures of [Mn(dca)2(H2O)] and [M(dca)(tcm)], M=Co, Ni, Cu, dca=Dicyanamide, N(CN)2−, tcm=Tricyanomethanide, C(CN)3−

Synthesis, Crystal Structures, and Magnetic Properties of Ternary M(II)-Dicyanamide-hydroxypyridine Complexes

Contact Info

Product

Resources

About

Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh₃P)[M(dca)₃] (M = Fe, Co, Ni) and (EtPh₃P)[M(dca)₃] (M = Mn, Co, Ni) Networks

Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh₃P)[M(dca)₃] (M = Fe, Co, Ni) and (EtPh₃P)[M(dca)₃] (M = Mn, Co, Ni) Networks