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Synthesis and Properties of Salicylaldehydes Fine‐Tuned by Modular Assembly using “Plug‐and‐Socket”‐Type Extendibility
Author(s) -
Houjou Hirohiko,
Suzuki Yoshikazu,
Shen QianWen,
Yoshikawa Isao,
Mutai Toshiki
Publication year - 2017
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.201701141
Subject(s) - salicylaldehyde , chemistry , zinc , chirality (physics) , amine gas treating , nickel , schiff base , diastereomer , pyridine , ethylamine , electrochemistry , stereochemistry , crystallography , combinatorial chemistry , polymer chemistry , inorganic chemistry , medicinal chemistry , organic chemistry , chiral symmetry breaking , physics , electrode , quantum mechanics , nambu–jona lasinio model , quark
A salicylaldehyde derivative bearing four pyridine arms, 3,5‐bis( N , N ‐bis(2‐pyridylmethyl)aminomethyl)‐2,4‐dihydroxybenzaldehyde (Hbpsal) as a “socket”, was prepared and used to derive a series of zinc complexes with various extra anions “plugged” into their vacant site. The crystal structure and 1 H NMR spectra were noticeably influenced by the extra anions, allowing fine‐tuning of the properties by “plug‐and‐socket”‐type modification. Similar to unsubstituted salicylaldehyde, the zinc complexes reacted with primary amines to afford Schiff‐base compounds. Because of the potential chirality around the coordination sphere, reaction with a chiral amine resulted in an equilibrium system between diastereomers, the potential of which as chiral sources tunable by the extra anions is discussed. Some of the complexes were further converted into zinc‐ or nickel‐salphen (= N , N ‐bis(salicylidene)‐1,2‐phenylenediamine) complexes. The electrochemical properties of the nickel complex were slightly modified by the extra anions, whereas the photophysical properties of the zinc complex appeared unchanged.