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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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Related in: MedlinePlus

Extended 3-D structure of Co[Au(CN)2]2, looking down the c axis. Dashed lines represent Au-Au interactions.
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f9-sensors-12-03669: Extended 3-D structure of Co[Au(CN)2]2, looking down the c axis. Dashed lines represent Au-Au interactions.

Mentions: The structure of Co[Au(CN)2]2 was deduced by matching the powder X-ray diffractogram to that of the isostructural compound [37], γ-Zn[Au(CN)2]2 (Figure S1), indexing the data accordingly (spacegroup P-4b2, a = 6.7968(17) Å, c = 8.4651(3) Å) and refining atomic positions (Tables S3 and S4). The cobalt(II) centres are tetrahedrally coordinated through the nitrogen end of four [Au(CN)2]− units, creating a tetragonal diamond-type lattice (Figure 9). There are four interpenetrated networks that are linked together via aurophilic interactions (3.33 and 3.56 Å). Note that a previously reported synthesis of Co[Au(CN)2]2 (by a simple addition of salt [55]) generated a different polymorph (equivalent to quartz-type α-Zn[Au(CN)2]2) [37,38], while using another route, via solvent-free grinding of Co(OH2)2[Au(CN)2]2, the structure was not determined [42].


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)

Extended 3-D structure of Co[Au(CN)2]2, looking down the c axis. Dashed lines represent Au-Au interactions.
© Copyright Policy
Related In: Results  -  Collection

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

f9-sensors-12-03669: Extended 3-D structure of Co[Au(CN)2]2, looking down the c axis. Dashed lines represent Au-Au interactions.
Mentions: The structure of Co[Au(CN)2]2 was deduced by matching the powder X-ray diffractogram to that of the isostructural compound [37], γ-Zn[Au(CN)2]2 (Figure S1), indexing the data accordingly (spacegroup P-4b2, a = 6.7968(17) Å, c = 8.4651(3) Å) and refining atomic positions (Tables S3 and S4). The cobalt(II) centres are tetrahedrally coordinated through the nitrogen end of four [Au(CN)2]− units, creating a tetragonal diamond-type lattice (Figure 9). There are four interpenetrated networks that are linked together via aurophilic interactions (3.33 and 3.56 Å). Note that a previously reported synthesis of Co[Au(CN)2]2 (by a simple addition of salt [55]) generated a different polymorph (equivalent to quartz-type α-Zn[Au(CN)2]2) [37,38], while using another route, via solvent-free grinding of Co(OH2)2[Au(CN)2]2, the structure was not determined [42].

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