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Vapochromic behaviour of M[Au(CN)2]2-based coordination polymers (M = Co, Ni).

Lefebvre J, Korčok JL, Katz MJ, Leznoff DB - Sensors (Basel) (2012)

Bottom Line: Co[Au(CN)(2)](2)(DMSO)(2) and M[Au(CN)(2)](2)(DMF)(2) (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH(2))[Au(CN)(2)](2) and from DMSO or DMF solution synthesis.Absorption of pyridine vapour by solid Ni(μ-OH(2))[Au(CN)(2)](2) was incomplete, generating a mixture of pyridine-bound complexes.Analyte-free Co[Au(CN)(2)](2) was prepared by dehydration of Co(μ-OH(2))[Au(CN)(2)](2) at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Simon Fraser University, Burnaby, BC, Canada. jlefebvr@ucalgary.ca

ABSTRACT
A series of M[Au(CN)(2)](2)(analyte)(x) coordination polymers (M = Co, Ni; analyte = dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), pyridine; x = 2 or 4) was prepared and characterized. Addition of analyte vapours to solid M(μ-OH(2))[Au(CN)(2)](2) yielded visible vapochromic responses for M = Co but not M = Ni; the IR ν(CN) spectral region changed in every case. A single crystal structure of Zn[Au(CN)(2)](2)(DMSO)(2) revealed a corrugated 2-D layer structure with cis-DMSO units. Reacting a Ni(II) salt and K[Au(CN)(2)] in DMSO yielded the isostructural Ni[Au(CN)(2)](2)(DMSO)(2) product. Co[Au(CN)(2)](2)(DMSO)(2) and M[Au(CN)(2)](2)(DMF)(2) (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH(2))[Au(CN)(2)](2) and from DMSO or DMF solution synthesis. Co[Au(CN)(2)](2)(pyridine)(4) is generated via vapour absorption by Co(μ-OH(2))[Au(CN)(2)](2); the analogous Ni complex is synthesized by immersion of Ni(μ-OH(2))[Au(CN)(2)](2) in 4% aqueous pyridine. Similar immersion of Co(μ-OH(2))[Au(CN)(2)](2) yielded Co[Au(CN)(2)](2)(pyridine)(2), which has a flat 2-D square-grid structure with trans-pyridine units. Absorption of pyridine vapour by solid Ni(μ-OH(2))[Au(CN)(2)](2) was incomplete, generating a mixture of pyridine-bound complexes. Analyte-free Co[Au(CN)(2)](2) was prepared by dehydration of Co(μ-OH(2))[Au(CN)(2)](2) at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate.

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Structural model proposed for Co[Au(CN)2]2(pyridine)2: (A) 2-D square-grid array with pyridine molecules on both sides of the grid; (B) Side-view of a 2-D layer, showing the position of the [Au(CN)2]− units with respect to the Co(II) centres.
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f8-sensors-12-03669: Structural model proposed for Co[Au(CN)2]2(pyridine)2: (A) 2-D square-grid array with pyridine molecules on both sides of the grid; (B) Side-view of a 2-D layer, showing the position of the [Au(CN)2]− units with respect to the Co(II) centres.

Mentions: Using a combination of the Cu[Au(CN)2]2(pyridine)2 and Co[Au(CN)2]2(DMF)2 structures as a starting point, a structural model is proposed for Co[Au(CN)2]2(pyridine)2 (the corresponding atomic coordinates are reported in Table S2). The structure consists of 2-D square grids of Co[Au(CN)2]2 with pyridine molecules N-bound to the Co(II) centres on both sides of the layer (Figure 8(A)). The structure differs from the Cu(II) analogue as all the cyanide groups are equidistant from the Co(II) centres and no Jahn-Teller distortion is observed. Also, the Co[Au(CN)2]2 layers are not completely flat as in the Cu[Au(CN)2]2 system, but the [Au(CN)2]− units are buckled in an alternate way on each side of the layer (Figure 8(B)), as is observed in the related Co[Au(CN)2]2(DMF)2 polymer [50]. This arrangement allows π–π interactions between the pyridine rings, but no aurophilic interactions are present as the closest contact between two Au atoms is approx. 3.7 Å. The powder diffractogram predicted by this model is compared to the experimental diffractogram of Co[Au(CN)2]2(pyridine)2 in Figure 7.


Vapochromic behaviour of M[Au(CN)2]2-based coordination polymers (M = Co, Ni).

Lefebvre J, Korčok JL, Katz MJ, Leznoff DB - Sensors (Basel) (2012)

Structural model proposed for Co[Au(CN)2]2(pyridine)2: (A) 2-D square-grid array with pyridine molecules on both sides of the grid; (B) Side-view of a 2-D layer, showing the position of the [Au(CN)2]− units with respect to the Co(II) centres.
© Copyright Policy
Related In: Results  -  Collection

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Show All Figures
getmorefigures.php?uid=PMC3376558&req=5

f8-sensors-12-03669: Structural model proposed for Co[Au(CN)2]2(pyridine)2: (A) 2-D square-grid array with pyridine molecules on both sides of the grid; (B) Side-view of a 2-D layer, showing the position of the [Au(CN)2]− units with respect to the Co(II) centres.
Mentions: Using a combination of the Cu[Au(CN)2]2(pyridine)2 and Co[Au(CN)2]2(DMF)2 structures as a starting point, a structural model is proposed for Co[Au(CN)2]2(pyridine)2 (the corresponding atomic coordinates are reported in Table S2). The structure consists of 2-D square grids of Co[Au(CN)2]2 with pyridine molecules N-bound to the Co(II) centres on both sides of the layer (Figure 8(A)). The structure differs from the Cu(II) analogue as all the cyanide groups are equidistant from the Co(II) centres and no Jahn-Teller distortion is observed. Also, the Co[Au(CN)2]2 layers are not completely flat as in the Cu[Au(CN)2]2 system, but the [Au(CN)2]− units are buckled in an alternate way on each side of the layer (Figure 8(B)), as is observed in the related Co[Au(CN)2]2(DMF)2 polymer [50]. This arrangement allows π–π interactions between the pyridine rings, but no aurophilic interactions are present as the closest contact between two Au atoms is approx. 3.7 Å. The powder diffractogram predicted by this model is compared to the experimental diffractogram of Co[Au(CN)2]2(pyridine)2 in Figure 7.

Bottom Line: Co[Au(CN)(2)](2)(DMSO)(2) and M[Au(CN)(2)](2)(DMF)(2) (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH(2))[Au(CN)(2)](2) and from DMSO or DMF solution synthesis.Absorption of pyridine vapour by solid Ni(μ-OH(2))[Au(CN)(2)](2) was incomplete, generating a mixture of pyridine-bound complexes.Analyte-free Co[Au(CN)(2)](2) was prepared by dehydration of Co(μ-OH(2))[Au(CN)(2)](2) at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Simon Fraser University, Burnaby, BC, Canada. jlefebvr@ucalgary.ca

ABSTRACT
A series of M[Au(CN)(2)](2)(analyte)(x) coordination polymers (M = Co, Ni; analyte = dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), pyridine; x = 2 or 4) was prepared and characterized. Addition of analyte vapours to solid M(μ-OH(2))[Au(CN)(2)](2) yielded visible vapochromic responses for M = Co but not M = Ni; the IR ν(CN) spectral region changed in every case. A single crystal structure of Zn[Au(CN)(2)](2)(DMSO)(2) revealed a corrugated 2-D layer structure with cis-DMSO units. Reacting a Ni(II) salt and K[Au(CN)(2)] in DMSO yielded the isostructural Ni[Au(CN)(2)](2)(DMSO)(2) product. Co[Au(CN)(2)](2)(DMSO)(2) and M[Au(CN)(2)](2)(DMF)(2) (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH(2))[Au(CN)(2)](2) and from DMSO or DMF solution synthesis. Co[Au(CN)(2)](2)(pyridine)(4) is generated via vapour absorption by Co(μ-OH(2))[Au(CN)(2)](2); the analogous Ni complex is synthesized by immersion of Ni(μ-OH(2))[Au(CN)(2)](2) in 4% aqueous pyridine. Similar immersion of Co(μ-OH(2))[Au(CN)(2)](2) yielded Co[Au(CN)(2)](2)(pyridine)(2), which has a flat 2-D square-grid structure with trans-pyridine units. Absorption of pyridine vapour by solid Ni(μ-OH(2))[Au(CN)(2)](2) was incomplete, generating a mixture of pyridine-bound complexes. Analyte-free Co[Au(CN)(2)](2) was prepared by dehydration of Co(μ-OH(2))[Au(CN)(2)](2) at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate.

No MeSH data available.


Related in: MedlinePlus