Palladium-catalyzed polycondensation between diiodoferrocenes
(1,1‘-diiodoferrocene and
1,6-diiodo-1‘,6‘-biferrocene) and diethynyl aromatic compounds
HC⋮CArC⋮CH (e.g., 2,5-diethynylpyridine and 2,5-diethynyl-3-hexylthiophene) gives
poly(aryleneethynylene) (PAE) type polymers containing the ferrocene unit in the π-conjugated main chain. The
prepared polymers include
(FcC⋮CPhC⋮C)
n
, PAE-Fc-1,
(FcC⋮CPyC⋮C)
n
, PAE-Fc-2, and
(FcC⋮ChexThC
⋮C)
n
, PAE-Fc-3 (Fc = 1,1‘-ferrocenylene;
Ph = p-phenylene; Py = pyridine-2,5-diyl; hexTh
=
3-hexylthiophene-2,5-diyl). 1H-NMR and IR spectra of
the polymers are reasonable for their structures.
The PAE type polymer containing the pyridine unit (PAE-Fc-2) is
soluble in formic acid, and the polymer
containing the hexylthiophene unit (PAE-Fc-3) is soluble in common
organic solvents such as CHCl3,
THF, and benzene. UV−visible spectra of the polymers exhibit a
main π−π* absorption peak at about
330 nm and a d−d absorption peak at about 450 nm. The cyclic
voltammogram of the polymers in a
CH3CN/CH2Cl2 solution
shows a reversible Fe(II) ⇄ Fe(III) redox cycle at about
0.25 V vs Ag/Ag+, and
the redox peaks are broadened compared with those of
low-molecular-weight ferrocenes. Exchange of
electrons along the main chain is considered to be the origin of the
broadening. The polymers themselves
are insulating, however, they are converted into semiconducting
materials with conductivity of 10-7 to
10-4 S cm-1 by formation of adducts with
iodine. Mössbauer spectra of the polymers reveal oxidation
of
Fe(II) in the ferrocene unit of PAE-Fc-1 to Fe(III), and the
ease of the oxidation reflects the electronic
properties of the polymer.
A new charge‐transfer polymer, containing a benzo[2,1,3]thiadiazole electron‐accepting group and a 2,5‐dihexyloxy‐1,4‐phenylene electron‐donating group, has been synthesized via Pd‐complex‐catalyzed polycondensation. The polymer has a π‐stacked structure in the solid state and forms spherulites. In addition, thin films of the polymer have a golden metallic luster (see Figure).
A new class of poly(aryleneethynylene)s containing an aryl heterocyclic structure were prepared in the yield of higher than 80% by polycondensation between 4,7-dibromo-2,1,3-benzothiadiazole and 2,5-dialkoxy-1,4-diethynylbenzenes with different long side chains using Pd(PPh 3)4 and CuI as the catalysts in the presence of triethylamine. All these polymers had a number-average molecular weight, Mn, higher than 12 000 and showed good solubility in chloroform. The polymers were photoluminescent in chloroform and showed metallic luster in the solid state. X-ray diffraction patterns of the powder and cast film (on a platinum plate) of the polymers revealed that the polymers assumed a π-stacked structure in the solid state, and the polymer molecules in the film were ordered on the surface of the platinum plate.
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