TY - JOUR
T1 - Synthesis and Absorption/Emission Properties of Novel Poly(silylenearylenevinylene)s
AU - Kwak, Giseop
AU - Sumiya, Ken Ichi
AU - Sanda, Fumio
AU - Masuda, Toshio
PY - 2003/11/15
Y1 - 2003/11/15
N2 - Polymerization of p-(dimethylsilyl)phenylacetylene in toluene at 25 and 80 °C with RhI(PPh3)3 catalyst afforded highly regio- and stereoregular poly(dimethylsilylene-1,4-phenylenevinylene)s [cis- and trans-poly(1a)s] containing 98% cis- and 99% trans-vinylene moieties, respectively. The trans-type polymers exhibited redshifts and hyper-chromic effects in the ultraviolet-visible spectrum as compared with the cis-type counterparts. Photoirradiation of cis- and trans-poly(1a)s gave cis-rich mixtures at equilibrium - states. The trans and cis polymers exhibited different emission properties, for example - trans polymer, emissn λ max = 400 nm, quantum yield: 3.4 × 10-3 and cis polymer, emissn λmax = 380 nm, quantum yield: 1.5 × 10-3. Besides poly(1a), poly(dimethylsilylenearyl-enevinylene)s containing biphenylene and phenylenesilylenephenylene units [poly(3)] were prepared. The extent of conjugation in these polymers decreased in the orders of biphenylene > phenylene > phenylenesilylenephenylene as well as trans-vinylene > cis-vinylene. The quantum yield of the trans-rich polymer with biphenylene moiety was fairly large and 0.15. Polyaddition of 1,4-bis(dimethylsilyl)benzene and three types of diethynylarenes (4,4′-diethynylbiphenyl, 2,7-diethynylfluorene, and 2,6-diethynylnaphthalene) catalyzed by RhI(PPh3)3 provided novel regio- and stereoregular polymers [poly(6)]. These polymers displayed blue light emission with high quantum yields (4-81%).
AB - Polymerization of p-(dimethylsilyl)phenylacetylene in toluene at 25 and 80 °C with RhI(PPh3)3 catalyst afforded highly regio- and stereoregular poly(dimethylsilylene-1,4-phenylenevinylene)s [cis- and trans-poly(1a)s] containing 98% cis- and 99% trans-vinylene moieties, respectively. The trans-type polymers exhibited redshifts and hyper-chromic effects in the ultraviolet-visible spectrum as compared with the cis-type counterparts. Photoirradiation of cis- and trans-poly(1a)s gave cis-rich mixtures at equilibrium - states. The trans and cis polymers exhibited different emission properties, for example - trans polymer, emissn λ max = 400 nm, quantum yield: 3.4 × 10-3 and cis polymer, emissn λmax = 380 nm, quantum yield: 1.5 × 10-3. Besides poly(1a), poly(dimethylsilylenearyl-enevinylene)s containing biphenylene and phenylenesilylenephenylene units [poly(3)] were prepared. The extent of conjugation in these polymers decreased in the orders of biphenylene > phenylene > phenylenesilylenephenylene as well as trans-vinylene > cis-vinylene. The quantum yield of the trans-rich polymer with biphenylene moiety was fairly large and 0.15. Polyaddition of 1,4-bis(dimethylsilyl)benzene and three types of diethynylarenes (4,4′-diethynylbiphenyl, 2,7-diethynylfluorene, and 2,6-diethynylnaphthalene) catalyzed by RhI(PPh3)3 provided novel regio- and stereoregular polymers [poly(6)]. These polymers displayed blue light emission with high quantum yields (4-81%).
KW - Absorption
KW - Conjugated polymers
KW - Geometric structure
KW - Heteroatom-containing polymers
KW - Luminescence
KW - Poly(silylenearylenevinylene)
KW - Quantum yield
UR - http://www.scopus.com/inward/record.url?scp=0242693285&partnerID=8YFLogxK
U2 - 10.1002/pola.10829
DO - 10.1002/pola.10829
M3 - Article
AN - SCOPUS:0242693285
SN - 0887-624X
VL - 41
SP - 3615
EP - 3624
JO - Journal of Polymer Science, Part A: Polymer Chemistry
JF - Journal of Polymer Science, Part A: Polymer Chemistry
IS - 22
ER -