Molecular Engineering of Free-Base Porphyrins as Ligands-The N-H? ? ? X Binding Motif in Tetrapyrroles
Citation:
Kielmann Marc, Senge Mathias O, Molecular Engineering of Free-Base Porphyrins as Ligands-The N-H? ? ? X Binding Motif in Tetrapyrroles, Angewandte Chemie (International ed. in English), 58, 2, 2019, 418 - 441Download Item:
Abstract:
The core N-H units of planar porphyrins are often inaccessible to
forming hydrogen-bonding complexes with acceptor molecules. This is
due to the fact that the amine moieties are “shielded” by the macrocyclic
system, impeding the formation of intermolecular H-bonds.
However, methods exist to modulate the tetrapyrrole conformations
and to reshape the vector of N@Horientation outwards, thus increasing
their availability and reactivity. Strategies include the use of porpho-
(di)methenes and phlorins (calixphyrins), as well as saddle-distorted
porphyrins. The former form cavities due to interruption of the
aromatic system. The latter are highly basic systems and capable of
binding anions and neutral molecules via N-H···X-type H-bonds. This
Review discusses the role of porphyrin(oid) ligands in various coordination-
type complexes, means to access the core for hydrogen
bonding, the concept of conformational control, and emerging applications,
such as organocatalysis and sensors.
URI:
https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201806281http://hdl.handle.net/2262/89380
Sponsor
Grant Number
Science Foundation Ireland (SFI)
SFIIvP 13/IA/1894
Author's Homepage:
http://people.tcd.ie/sengemDescription:
PUBLISHED
Author: Senge, Mathias
Other Titles:
Angew Chem Int Ed EnglType of material:
Journal ArticleURI:
https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201806281http://hdl.handle.net/2262/89380
Collections:
Series/Report no:
Angewandte Chemie (International ed. in English)58
2
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Full text availableKeywords:
Calixpyrroles, Hydrogen bonds, Molecular engineering, Porphyrinoids, PorphyrinsDOI:
http://dx.doi.org/10.1002/anie.201806281ISSN:
1433-7851Other Identifiers:
30067890Licences: