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- Title
Structure and spectroscopic properties of porphyrinato group 14 derivatives: Part I -- Phenylacetylido ligands.
- Authors
Stadlbauer, Stefan; Fischer, Roland; Flock, Michaela; Zach, Peter W.; Borisov, Sergey M.; Torvisco, Ana; Uhlig, Frank
- Abstract
A series of bis(phenylacetylido)(porphyrinato) E(IV) (E = Si, Ge, Sn) derivatives were obtained by reacting lithium phenylacetylide with the corresponding bis(chlorido)(porphyrinato) E(IV) precursors. Crystal structure determinations demonstrated that the transcoordinated acetylide ligands deviate from their expected ideal geometry. Density functional theory calculations and comparison of the packing of the molecules among the homologous series of Si(IV), Ge(IV) and Sn(IV) revealed causes for the deviation from the simple valence shell electron pair repulsion model. Fluorescence and phosphorescence of these organometallic group 14 derivatives were studied and the results are compared to the literature-known properties of the related bis(chlorido) (porphyrinato) E(IV) compounds (E = Si, Ge, Sn). The first crystal structure of a porphyrinato Ge(IV) compound with σ-bonded acetylide ligands is reported.
- Subjects
CRYSTAL structure; CHEMICAL derivatives; LIGANDS (Chemistry); DENSITY functional theory; ELECTRON pairs; FLUORESCENCE
- Publication
Zeitschrift für Naturforschung B: A Journal of Chemical Sciences, 2017, Vol 72, Issue 11, p801
- ISSN
0932-0776
- Publication type
Article
- DOI
10.1515/znb-2017-0090