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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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Comparison between the powder X-ray diffractograms predicted for Zn[Au(CN)2]2(DMSO)2 (Zn, green) and the blue Cu[Au(CN)2]2(DMSO)2 polymorph (Cu, blue), with the diffractogram obtained experimentally for Ni[Au(CN)2]2(DMSO)2 (Ni, orange), prepared via solution methods.
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f3-sensors-12-03669: Comparison between the powder X-ray diffractograms predicted for Zn[Au(CN)2]2(DMSO)2 (Zn, green) and the blue Cu[Au(CN)2]2(DMSO)2 polymorph (Cu, blue), with the diffractogram obtained experimentally for Ni[Au(CN)2]2(DMSO)2 (Ni, orange), prepared via solution methods.

Mentions: Although no single crystal of Ni[Au(CN)2]2(DMSO)2 suitable for X-ray crystallography could be obtained, its powder X-ray diffractogram showed similar features to the diffractograms of the Zn[Au(CN)2]2(DMSO)2 and Cu[Au(CN)2]2(DMSO)2 (blue polymorph) coordination polymers (Figure 3) [35]. The diffractogram of Ni[Au(CN)2]2(DMSO)2 could be indexed to a monoclinic unit cell, with parameters very similar to those of the Zn analogue (Table 4). Thus, the structure of Ni[Au(CN)2]2(DMSO)2 likely consists of octahedral Ni(II) ions coordinated by two DMSO molecules in a cis fashion and connected to four other Ni(II) centres via [Au(CN)2]− units, generating corrugated 2-D sheets; due to the poor quality of the diffractogram, no effort was made to structurally model the data any further. Note that the νCN data and powder X-ray diffractograms for Ni[Au(CN)2]2(DMSO)2 do not perfectly match those obtained via vapour absorption of DMSO by Ni(μ-OH2)2[Au(CN)2]2, indicating that a related, but different structure is likely accessed by vapour absorption.


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)

Comparison between the powder X-ray diffractograms predicted for Zn[Au(CN)2]2(DMSO)2 (Zn, green) and the blue Cu[Au(CN)2]2(DMSO)2 polymorph (Cu, blue), with the diffractogram obtained experimentally for Ni[Au(CN)2]2(DMSO)2 (Ni, orange), prepared via solution methods.
© Copyright Policy
Related In: Results  -  Collection

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

f3-sensors-12-03669: Comparison between the powder X-ray diffractograms predicted for Zn[Au(CN)2]2(DMSO)2 (Zn, green) and the blue Cu[Au(CN)2]2(DMSO)2 polymorph (Cu, blue), with the diffractogram obtained experimentally for Ni[Au(CN)2]2(DMSO)2 (Ni, orange), prepared via solution methods.
Mentions: Although no single crystal of Ni[Au(CN)2]2(DMSO)2 suitable for X-ray crystallography could be obtained, its powder X-ray diffractogram showed similar features to the diffractograms of the Zn[Au(CN)2]2(DMSO)2 and Cu[Au(CN)2]2(DMSO)2 (blue polymorph) coordination polymers (Figure 3) [35]. The diffractogram of Ni[Au(CN)2]2(DMSO)2 could be indexed to a monoclinic unit cell, with parameters very similar to those of the Zn analogue (Table 4). Thus, the structure of Ni[Au(CN)2]2(DMSO)2 likely consists of octahedral Ni(II) ions coordinated by two DMSO molecules in a cis fashion and connected to four other Ni(II) centres via [Au(CN)2]− units, generating corrugated 2-D sheets; due to the poor quality of the diffractogram, no effort was made to structurally model the data any further. Note that the νCN data and powder X-ray diffractograms for Ni[Au(CN)2]2(DMSO)2 do not perfectly match those obtained via vapour absorption of DMSO by Ni(μ-OH2)2[Au(CN)2]2, indicating that a related, but different structure is likely accessed by vapour absorption.

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