Limits...
Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.

Vitórica-Yrezábal IJ, Libri S, Loader JR, Mínguez Espallargas G, Hippler M, Fletcher AJ, Thompson SP, Warren JE, Musumeci D, Ward MD, Brammer L - Chemistry (2015)

Bottom Line: Four polymorphic forms of 1 (1-A(LT) , 1-A(HT) , 1-B(LT) and 1-B(HT) ; HT=high temperature, LT=low temperature) have been identified crystallographically.The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers.Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-A(HT) show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Sheffield, Brook Hill, Sheffield S3 7HF (UK), Fax: (+44) 114-222-9536 http://www.sheffield.ac.uk/chemistry/staff/profiles/lee_brammer.

No MeSH data available.


Related in: MedlinePlus

a) Sequence of AFM images of a 7 μm square of the (01) face of a single crystal of 1-MeOH recorded at 308 K in tapping mode at 8 min intervals during the release of MeOH. b) View of the crystal structure of 1-MeOH perpendicular to the (01) face (as for the AFM images) with (01) plane indicated as a red line. Colours as in Scheme 2. Hydrogen atoms not shown.
© Copyright Policy
Related In: Results  -  Collection


getmorefigures.php?uid=PMC4641464&req=5

fig09: a) Sequence of AFM images of a 7 μm square of the (01) face of a single crystal of 1-MeOH recorded at 308 K in tapping mode at 8 min intervals during the release of MeOH. b) View of the crystal structure of 1-MeOH perpendicular to the (01) face (as for the AFM images) with (01) plane indicated as a red line. Colours as in Scheme 2. Hydrogen atoms not shown.

Mentions: In a separate experiment a series of AFM images of a single crystal of 1-MeOH maintained at a temperature of 308 K were recorded by scanning the (01) face. Over a period of 48 min a large crack developed in a direction corresponding to the (01) planes (Figure 9) as MeOH is lost. This observation is consistent with the optical microscope images.


Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study.

Vitórica-Yrezábal IJ, Libri S, Loader JR, Mínguez Espallargas G, Hippler M, Fletcher AJ, Thompson SP, Warren JE, Musumeci D, Ward MD, Brammer L - Chemistry (2015)

a) Sequence of AFM images of a 7 μm square of the (01) face of a single crystal of 1-MeOH recorded at 308 K in tapping mode at 8 min intervals during the release of MeOH. b) View of the crystal structure of 1-MeOH perpendicular to the (01) face (as for the AFM images) with (01) plane indicated as a red line. Colours as in Scheme 2. Hydrogen atoms not shown.
© Copyright Policy
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4641464&req=5

fig09: a) Sequence of AFM images of a 7 μm square of the (01) face of a single crystal of 1-MeOH recorded at 308 K in tapping mode at 8 min intervals during the release of MeOH. b) View of the crystal structure of 1-MeOH perpendicular to the (01) face (as for the AFM images) with (01) plane indicated as a red line. Colours as in Scheme 2. Hydrogen atoms not shown.
Mentions: In a separate experiment a series of AFM images of a single crystal of 1-MeOH maintained at a temperature of 308 K were recorded by scanning the (01) face. Over a period of 48 min a large crack developed in a direction corresponding to the (01) planes (Figure 9) as MeOH is lost. This observation is consistent with the optical microscope images.

Bottom Line: Four polymorphic forms of 1 (1-A(LT) , 1-A(HT) , 1-B(LT) and 1-B(HT) ; HT=high temperature, LT=low temperature) have been identified crystallographically.The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers.Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-A(HT) show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Sheffield, Brook Hill, Sheffield S3 7HF (UK), Fax: (+44) 114-222-9536 http://www.sheffield.ac.uk/chemistry/staff/profiles/lee_brammer.

No MeSH data available.


Related in: MedlinePlus