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Please use this identifier to cite or link to this item: http://apo.ansto.gov.au/dspace/handle/10238/7398

Title: Intermolecular interactions in solid-state metalloporphyrins and their impacts on crystal and molecular structures
Authors: Hunter, SC
Smith, BA
Hoffmann, CM
Wang, X
Chen, Y
McIntyre, GJ
Xue, Z
Keywords: Crystal Structure
Phase Transformations
Porphyrins
Molecular Structure
Neutrons
Voids
Issue Date: 23-Oct-2014
Publisher: ACS Publications
Citation: Hunter, S. C., Smith, B. A., Hoffmann, C. M., Wang, X., Chen, Y.-S., McIntyre, G. J. & Xue, Z.-L. (2014). Intermolecular Interactions in Solid-State Metalloporphyrins and Their Impacts on Crystal and Molecular Structures. Inorganic Chemistry, 53(21), 11552-11562. doi: http://dx.doi.org/10.1021/ic5015835
Abstract: A variable-temperature (VT) crystal structure study of [Fe(TPP)Cl] (TPP2– = meso-tetraphenylporphyrinate) and Hirshfeld surface analyses of its structures and previously reported structures of [M(TPP)(NO)] (M = Fe, Co) reveal that intermolecular interactions are a significant factor in structure disorder in the three metalloporphyrins and phase changes in the nitrosyl complexes. These interactions cause, for example, an 8-fold disorder in the crystal structures of [M(TPP)(NO)] at room temperature that obscures the M–NO binding. Hirshfeld analyses of the structure of [Co(TPP)(NO)] indicate that the phase change from I4/m to P1̅ leads to an increase in void-volume percentage, permitting additional structural compression through tilting of the phenyl rings to offset the close-packing interactions at the interlayer positions in the crystal structures with temperature decrease. X-ray and neutron structure studies of [Fe(TPP)Cl] at 293, 143, and 20 K reveal a tilting of the phenyl groups away from being perpendicular to the porphyrin ring as a result of intermolecular interactions. Structural similarities and differences among the three complexes are identified and described by Hirshfeld surface and void-volume calculations.© 2014, American Chemical Society.
URI: http://dx.doi.org/10.1021/ic5015835
http://apo.ansto.gov.au/dspace/handle/10238/7398
ISSN: 1520-510X
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