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Cross‐Conjugated π‐Scaffolding with Pendant N‐Heterocyclic Metal‐Binding Sites
Author(s) -
Nauroozi Djawed,
Bruhn Clemens,
Faust Rüdiger
Publication year - 2017
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201700294
Subject(s) - enediyne , chemistry , geminal , conjugated system , cyclic voltammetry , ligand (biochemistry) , stereochemistry , metal , combinatorial chemistry , electrochemistry , organic chemistry , polymer , biochemistry , receptor , electrode
The synthesis of geminal enediyne scaffolds with pendant N‐heterocyclic metal‐coordination sites based on dipyridylmethylidene or diazafluorenylidene moieties are reported. The Pd‐catalysed cross‐coupling reactions of the corresponding heterocyclic dibromoolefins and terminal alkynes provide convenient access to the new ligand systems. Their photophysical and electrochemical properties are investigated by UV/Vis spectroscopy and cyclic voltammetry and reveal a more efficient π delocalisation in the cross‐conjugated diazafluorenylidene systems. The coordination of a PdCl 2 fragment to each of the different ligand types along with a comprehensive X‐ray crystallographic analysis of the ligands and complexes is reported. The structural data confirm the almost coplanar arrangement of the N‐heterocyclic metal binding site and the cross‐conjugated π‐delocalised enediyne scaffold as a prerequisite for efficient electronic communication between the two molecular constituents.