NDLI: Ferrocenyl helquats: unusual chiral organometallic nonlinear optical chromophores

Content Provider	Royal Society of Chemistry (RSC)
Author	Buckley, Laura E. R. Jirásek, Michael Brunschwig, Bruce S. Rusanova, Daniela Joshi, Vishwas D. Clays, Koen Sánchez, Sergio Teplý, Filip Steerteghem, Nick Van Vávra, Jan Khobragade, Dushant Pospíšil, Lubomír Císařová, Ivana Coe, Benjamin J. Ramešová, Šárka Šaman, David Pohl, Radek
Copyright Year	2017
Abstract	Three new dipolar cations have been synthesised, containing ferrocenyl (Fc) electron donor groups attached to helquat (Hq) acceptors. These organometallic Hq derivatives have been characterised as their TfO− salts by using various techniques including NMR and electronic absorption spectroscopies and electrochemical measurements. UV–vis spectra show multiple intense low energy absorptions attributable to intramolecular charge-transfer (ICT) excitations. Each compound displays a reversible Fc+/0 redox process, together with two reversible one-electron reductions of the Hq fragment. Molecular quadratic nonlinear optical (NLO) responses have been determined by using hyper-Rayleigh scattering at 1064 nm, and Stark (electroabsorption) spectroscopic studies on the visible absorption bands. The obtained first hyperpolarizabilities β are moderate, consistent with the relatively short π-conjugation lengths between the Fc and attached pyridinium group. A single-crystal X-ray structure has been solved for one of the complexes as its PF6− salt, revealing a centrosymmetric packing in the triclinic space group P. Density functional theory (DFT) and time-dependent DFT calculations indicate that the lowest energy absorption bands have mainly metal-to-ligand charge-transfer character. The donor orbitals involved in the electronic transitions forming the next lowest energy ICT band also have substantial contributions from the Fe atom. Good agreement between the simulated and experimental UV–vis absorption spectra is achieved by using the PBE0 functional with the 6-311++G(d)/LANL2DZ mixed basis set, and the theoretical β values are reasonably large. Oxidation of the Fc unit is predicted to cause the βtot value to decrease by more than 80% in one of the complexes.
Starting Page	1052
Ending Page	1064
Page Count	13
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	46
Issue Number	4
Journal	Dalton Transactions
DOI	10.1039/c6dt04347j
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	NLO ICT Fc Redox Organometallic chemistry Nuclear magnetic resonance Electrochemistry Nonlinear optics Pyridinium X-ray crystallography Hexafluorophosphate Triclinic crystal system Space group Density functional theory Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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