期刊
TETRAHEDRON
卷 64, 期 36, 页码 8394-8401出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.tet.2008.05.127
关键词
porphyrin; coordination; Tin(IV); molecular dynamics; rotamers; supramolecular chemistry; clock
资金
- Australian Research Council [DP0878220]
- Australian Research Council [DP0878220] Funding Source: Australian Research Council
An approach to the formation of molecular timepieces is outlined based on differentiating between rotamers in diaxial Sn(IV) porphyrin phenolates. Two models are explored in detail. The first explores how the rates Of rotation of the diaxial ligands is discriminated based on steric hindrance of the two porphyrin macrocycle faces at low temperature. The second model explores a 'stopwatch' function based on the ligation of Ag(I) ions to a 5,15-dipyridylporphyrinato tin(IV) complex bearing 3-hydroxypyridine ligands. The complexation inhibits rotation of the axial ligand, a result. which can be reversed by precipitation of Ag(I) using tetraethylammonium bromide. X-ray crystallography has also been used to characterize two Ag(I) 5,15-dipyridylporphyrinato tin(]V)complexes. The two isoforms differ in their supramolecular organization. One structure is formed through a cofacial stack linking each porphyrin by Ag(I) coordination. The other displays a sheet-like coordination polymer structure. (C) 2008 Elsevier Ltd. All rights reserved.
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