TY - JOUR
T1 - Long-range intramolecular electronic communication in bis(ferrocenylethynyl) complexes incorporating conjugated heterocyclic spacers
T2 - Synthesis, crystallography, and electrochemistry
AU - Shah, Hakikulla H.
AU - Al-Balushi, Rayya A.
AU - Al-Suti, Mohammed K.
AU - Khan, Muhammad S.
AU - Woodall, Christopher H.
AU - Molloy, Kieran C.
AU - Raithby, Paul R.
AU - Robinson, Thomas P.
AU - Dale, Sara E.C.
AU - Marken, Frank
PY - 2013/5/6
Y1 - 2013/5/6
N2 - A new series of bis(ferrocenylethynyl) complexes, 3-7, and a mono(ferrocenylethynyl) complex, 8, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV-vis spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltammetry and spectroelectrochemistry. Although there is a large separation of ∼14 Å between the two redox centers, ΔE 1/2 values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV-vis-near-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc-C≡C-C≡C-Fc (Fc = C 5H5FeC5H4) highest occupied molecular orbital.
AB - A new series of bis(ferrocenylethynyl) complexes, 3-7, and a mono(ferrocenylethynyl) complex, 8, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV-vis spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltammetry and spectroelectrochemistry. Although there is a large separation of ∼14 Å between the two redox centers, ΔE 1/2 values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV-vis-near-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc-C≡C-C≡C-Fc (Fc = C 5H5FeC5H4) highest occupied molecular orbital.
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U2 - 10.1021/ic3024887
DO - 10.1021/ic3024887
M3 - Article
C2 - 23593988
AN - SCOPUS:84877280690
SN - 0020-1669
VL - 52
SP - 4898
EP - 4908
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 9
ER -