Double Insertion of Thiophene Rings in Polyynediyl Chains to Stabilize Nanoscaled Molecular Wires with [Cp*(dppe)Fe] Termini
收藏NIAID Data Ecosystem2026-03-09 收录
下载链接：
https://figshare.com/articles/dataset/Double_Insertion_of_Thiophene_Rings_in_Polyynediyl_Chains_to_Stabilize_Nanoscaled_Molecular_Wires_with_Cp_dppe_Fe_Termini/3425822
下载链接
链接失效反馈官方服务：
资源简介：
The dinuclear iron
complexes [Cp*(dppe)Fe–CC–C4H2S-(CC)x-C4H2S–CC–Fe(dppe)Cp*] (2, x = 1; 3 x = 2) and [Cp*(dppe)Fe–CC–CC–C4H2S–CC–CC–Fe(dppe)Cp*]
(4) were prepared in one-pot procedures from known organometallic
precursors. Compound 2 was obtained from Cp*(dppe)Fe–CC–C4H2S–CC–C4H2S–CCH (6) and Cp*(dppe)FeCl (5) in 74% yield. Its relative 3, isolated in
84%, resulted from the oxidative coupling of Cp*(dppe)Fe–CC–C4H2S–CCH (7) in the
presence of Cu(OAc)2 and 1,8-diazabicyclo[5.4.0]-undec-7-ene
(DBU). Complex 4 was obtained from the bridging ligand
2,5-bis(trimethylsilylbutadiynyl)thiophene (8) and two
equiv of 5. The new complexes were characterized by ESI-mass
spectrometry, IR, multinuclear NMR, cyclic voltammetry, and Mössbauer
spectroscopy. Complex 3 was also analyzed by X-ray diffraction
on a single crystal. The data are consistent with a sizable metal–metal
interaction across the 14- and 16-carbon atoms of the bridges. The
singly and doubly oxidized forms 2(PF6)n and 3(PF6)n (n = 1, 2) were obtained by oxidation of the corresponding
18-electron iron(II) precursors with 1 and 2 equivs of ferrocenium
salt, while 4 decomposed very quickly upon oxidation.
The thermally stable salts 2(PF6)n and 3(PF6)n (n = 1, 2) were subjected to analyses by ESI-mass spectrometry,
IR, Mössbauer, ESR, UV–vis, and NIR spectroscopies.
The radical cations 2(PF6) and 3(PF6) belong to Class II of the mixed-valence Robin and Day classification
with quite sizable electronic coupling parameters for large metal–metal
separation (2(PF6), Hab = 262 cm–1, dFeFe = 17.7 Å; 3(PF6), Hab = 203
cm–1, dFeFe = 19.7 Å).
Paramagnetic 1H NMR spectroscopy was also performed on
the dicationic salts to measure the magnetic exchange between the
distant spin carriers (2(PF6)2, ΔGST = −120 cm–1). The data were analyzed
with the support of quantum chemistry calculations at the DFT level
of theory.
创建时间：
2016-08-04
