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Unexpected High Second‐Order Nonlinear Optical Activity of Metal Complexes with Three‐Branched Hexadentate 2,2′‐Bipyridine Ligands
Author(s) -
Wolff Marie C.,
van Steerteghem Nick,
Clays Koen,
Heck Jürgen
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801189
Subject(s) - hyperpolarizability , chemistry , crystallography , bipyridine , metal , fluorescence , nonlinear optical , diamagnetism , stereochemistry , molecule , nonlinear system , physics , optics , organic chemistry , crystal structure , quantum mechanics , polarizability , magnetic field
Two hexadentate bipyridine ligands and their Ru II and Ni II complexes were prepared. The helical alignment of the three electron‐donor–π‐bridge–electron‐acceptor ( d ‐π‐A) single‐strands with bundle architecture in cooperation with the metal center can strongly enhance the nonlinear optical (NLO) properties. The complexation of the novel cage‐type hexadentate ligands with a paramagnetic Ni II ‐core almost doubles the β HRS values compared with the corresponding diamagnetic Ru II complexes. The hyper‐Rayleigh scattering (HRS) was performed with a highly sensitive setup for simultaneous discrimination between multi‐photon fluorescence and the molecular first hyperpolarizability.