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Syntheses, Structures and Nonlinear Optical Properties of Ferrocenyl Complexes with Arylethenyl Substituents
Author(s) -
Mata José A.,
Peris Eduardo,
Llusar Rosa,
Uriel Santiago,
Cifuentes Marie P.,
Humphrey Mark G.,
Samoc Marek,
LutherDavies Barry
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200108)2001:8<2113::aid-ejic2113>3.0.co;2-i
Subject(s) - chemistry , crystallography , nonlinear optical , electrochemistry , stereochemistry , acceptor , electrode , physics , nonlinear system , condensed matter physics , quantum mechanics
The complexes ( E )‐ and ( Z )‐Fe(η 5 ‐C 5 H 4 CHO)(η 5 ‐C 5 H 4 CH=CH−C 6 H 4 ‐4‐NO 2 ) [ 2 ‐ (E ) and 2 ‐( Z ), respectively], ( E )‐ and ( Z )‐Fe(η 5 ‐C 5 H 4 CHO)(η 5 ‐C 5 H 4 CH=CH−C 6 H 4 ‐4‐CN) [ 3 ‐( E ) and 3 ‐( Z ), respectively], ( E,E )‐, ( E,Z )‐, and ( Z,Z )‐Fe(η 5 ‐C 5 H 4 CH=CHC 6 H 4 ‐4‐NO 2 ) 2 [ 4 ‐( E,E ), 4 ‐( E,Z ), and 4 ‐( Z,Z ), respectively], ( E,E )‐, ( E,Z )‐, and ( Z,Z )‐Fe(η 5 ‐C 5 H 4 CH=CHC 6 H 4 ‐4‐CN) 2 [ 5 ‐( E,E ), 5 ‐( E,Z ), and 5 ‐( Z,Z ), respectively], and Fe(η 5 ‐C 5 H 5 )(η 5 C 5 H 4 −( E )‐CH=CH−4‐{(η 6 ‐C 6 H 4 )Cr(CO) 3 }−( E )‐CH=CH−η 5 C 5 H 4 )Fe(η 5 ‐C 5 H 5 ) ( 7 ) have been synthesized. Structural studies on 2 ‐( E ), 4 ‐( E,Z ), 5 ‐( E,E ), Fe(η 5 ‐C 5 H 5 ){η 5 ‐C 5 H 4 −( E )‐CH=CH−4‐C 6 H 4 −( E )‐CH=CH−η 5 ‐C 5 H 4 }Fe(η 5 ‐C 5 H 5 ) ( 6 ) and 7 have been performed. Electrochemical studies of 2−5 reveal trends in the oxidation potentials which are consistent with the more effective conjugation of the ( E ) isomers, and the better electron‐accepting character of NO 2 than CN and of CHO than H. Powder SHG measurements by the Kurtz technique using fs pulses at the telecommunications wavelength of 1.3 μm reveal low responses for 4 ‐( E,E ), 5 ‐( E,E ), and 7 . Third‐order NLO measurements by Z‐scan using fs pulses at 800 nm suggest an increase in |γ| on increasing the electron‐acceptor strength [when proceeding from 5 ‐( E,Z ) to 4 ‐( E,Z ), CN is replaced by NO 2 ], and on introduction of the Cr(CO) 3 unit, when proceeding from 6 to 7 .