Various π-conjugated copolymers constituted of π-excessive
thiophene, selenophene, or furan units
(Ar) and π-deficient pyridine or quinoxaline (Ar‘) units have been
prepared in high yields by the following
organometallic polycondensation methods: (i) n
X−Ar−Ar‘−X + n Ni(0)Lm →
(-Ar−Ar‘)-
n
(X = halogen, Ni(0)Lm = zerovalent nickel complex), (ii) n X−Ar−X +
n Me3Sn−Ar‘−SnMe3 →
(-Ar−Ar‘)-
n
(palladium catalyzed),
and (iii) a X−Ar−X + b X−Ar‘−X +
(a + b)Ni(0)Lm →
(-Ar)
x
(Ar‘)-
y
.
Powder X-ray diffraction analysis confirms
an alternative structure of a polymer prepared by the method ii.
The copolymers have a molecular weight of 5.4 ×
103 to 3.3 × 105 and an [η] value of 0.37
to 4.4 dL g-1. π−π* absorption bands of the
copolymers generally show
red shifts from those of the corresponding homopolymers,
(-Ar)-
n
and
(-Ar‘)-
n
,
and the red shifts are accounted for by
charge-transferred CT structures of the copolymers. For example,
an alternative copolymer of thiophene and 2,3-diphenylquinoxaline gives rise to an absorption band at
λmax = 603 nm, whereas homopolymers of thiophene
and
2,3-diphenylquinoxaline exhibit absorption peaks at about 460 and 440
nm, respectively. The CT copolymers are
electrochemically active in both oxidation and reduction regions,
showing oxidation (or p-doping) peaks in a range
of 0.39 to 1.32 V vs Ag/Ag+ and reduction (or
n-doping) peaks in a range of −1.80 to −2.22 V vs
Ag/Ag+,
respectively. Copolymers of pyridine give unique cyclic
voltammograms exhibiting p-undoping peaks at potentials
much different (about 2−3 V lower) from the corresponding p-doping
potentials, and this large difference between
p-doping and p-undoping potentials is explained by an EC mechanism.
They are converted into semiconductors by
chemical and electrochemical oxidation and reduction. Copolymers
of thiophene with pyridine and quinoxaline
show the third-order nonlinear optical susceptibility
χ(3) of about 5 × 10-11 esu at the
three-photon resonant wavelength,
which is 5−7 times larger than those of the corresponding
homopolymers and related to the CT structure in the
copolymers.
Thermoresponsive block copolymer brush with cell affinity peptides was prepared via two steps of ATRP and subsequent click reaction. The prepared polymer brush can purify cells with high selectivity by simply changing temperature.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.