TY - JOUR
T1 - New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization
AU - Shah, Hakikulla H.
AU - Al-Balushi, Rayya A.
AU - Al-Suti, Mohammed K.
AU - Khan, Muhammad S.
AU - Woodall, Christopher H.
AU - Sudlow, Anna L.
AU - Raithby, Paul R.
AU - Kociok-Köhn, Gabriele
AU - Molloy, Kieran C.
AU - Marken, Frank
PY - 2013/10/21
Y1 - 2013/10/21
N2 - Three new tetra-ferrocenylethynylpyridinyl copper complexes, L 4(CuI)4 (3), L4(CuBr)2 (4), and L4(CuCl)2 (5) have been prepared from the reaction of ferrocenylethynylpyridine (L)(2) with copper halides CuX (with X = I -, Br-, Cl-).The ligand 2 and the complexes 3-5 have been fully characterized by spectroscopic methods. The structures of 2-4 have been confirmed by single-crystal X-ray crystallography. 2 forms a dimer in the crystalline-state through C-H··N hydrogen bonds. 4 and 5 are dimers and 3 a tetramer, in all cases linked through Cu-X··Cu bridging interactions. Cyclic voltammetry in dichloroethane showed chemically reversible multiferrocenyl oxidation signals with evidence for product electro-crystallization. The oxidation products were isolated by electrodeposition onto a Pt disc electrode and investigated by scanning electron microscopy which confirmed the spontaneous formation of crystalline oxidation products with distinctive morphologies. Energy dispersive X-ray elemental analysis shows the presence of hexafluorophosphate (counterion) with the P:Fe ratio of 1:1, 0.5:1, and 1:1 for the electrocrystallized products 3, 4, and 5, respectively, suggesting the formulas [3]4+(PF6 -)4, [4]2+(PF6-) 2, and [5]4+(PF6-)4 for the electro-crystallized products.
AB - Three new tetra-ferrocenylethynylpyridinyl copper complexes, L 4(CuI)4 (3), L4(CuBr)2 (4), and L4(CuCl)2 (5) have been prepared from the reaction of ferrocenylethynylpyridine (L)(2) with copper halides CuX (with X = I -, Br-, Cl-).The ligand 2 and the complexes 3-5 have been fully characterized by spectroscopic methods. The structures of 2-4 have been confirmed by single-crystal X-ray crystallography. 2 forms a dimer in the crystalline-state through C-H··N hydrogen bonds. 4 and 5 are dimers and 3 a tetramer, in all cases linked through Cu-X··Cu bridging interactions. Cyclic voltammetry in dichloroethane showed chemically reversible multiferrocenyl oxidation signals with evidence for product electro-crystallization. The oxidation products were isolated by electrodeposition onto a Pt disc electrode and investigated by scanning electron microscopy which confirmed the spontaneous formation of crystalline oxidation products with distinctive morphologies. Energy dispersive X-ray elemental analysis shows the presence of hexafluorophosphate (counterion) with the P:Fe ratio of 1:1, 0.5:1, and 1:1 for the electrocrystallized products 3, 4, and 5, respectively, suggesting the formulas [3]4+(PF6 -)4, [4]2+(PF6-) 2, and [5]4+(PF6-)4 for the electro-crystallized products.
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U2 - 10.1021/ic401803p
DO - 10.1021/ic401803p
M3 - Article
C2 - 24107148
AN - SCOPUS:84886659757
SN - 0020-1669
VL - 52
SP - 12012
EP - 12022
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 20
ER -