محمود زكريا على بسيونى
مدرس مساعد
Living ROMP of poly(m,p-phenylenevinylene) and functionalized norbornene-dicarboximides copolymers: guided synthesis toward enhanced optoelectronic and thermal properties with DFT insights
Polymer Chemistry • 2025
معلومات البحث
المؤلفون
Mohamed E. Abdu, Mohammed F. Radwan, Abdulrahman E. Mesbah, Ye J.hao, Abdelrahman Zkria, Mahmoud Z. Basyouni and Andrew M. Spring
الكلمات المفتاحية
Not Available
المجلة العلمية
Polymer Chemistry
الناشر
The Royal Society of Chemistry 2025
المجلد
16
العدد
Not Available
الصفحات
4444-4469
publication.type
International
رابط البحث
Not Available
المواد المرفقة
Not Available
الملخص
A series of functionalized copolymers is synthesized via ring-opening metathesis polymerization (ROMP).
Dioctyloxy-substituted [2.2]metaparacyclophane-1,9-diene (DO-mp-CPDE) (M1), was synthesized and
fully characterized by IR, 1D-NMR, and 2D-NMR. A novel fully conjugated polymer, poly(m,p-phenylenevinylene),
along with rod–coil copolymers (P2–P5) incorporating DO-mp-CPDE and non-conjugated units
Norbornene Dicarboximides (NDI), was synthesized utilizing ROMP with second-generation Grubbs catalyst
(G2). Kinetics studies examined using GPC confirmed controlled living polymerization in homopolymer
and block designs, evidenced by PDI 1.10–1.17 and a close agreement between experimental and
calculated Mn values. In contrast, random copolymers exhibited broader distributions due to ring strain
mismatch. Optical measurements revealed tunable band gaps, Eop
g 2.53–2.56 eV, and electrochemical
gaps, Eelc
g 2.01–2.37 eV, with enhanced conjugation in the homopolymer leading to narrower gaps.
Morphological investigations using SEM showed distinct self-assembly behaviours influenced by the
polymer chain and the micellization protocol, which explains the enhancement in the optical properties
of these polymers with Eop
g 2.27–2.41 eV. TGA analysis demonstrated high thermal stability across all polymers,
Dioctyloxy-substituted [2.2]metaparacyclophane-1,9-diene (DO-mp-CPDE) (M1), was synthesized and
fully characterized by IR, 1D-NMR, and 2D-NMR. A novel fully conjugated polymer, poly(m,p-phenylenevinylene),
along with rod–coil copolymers (P2–P5) incorporating DO-mp-CPDE and non-conjugated units
Norbornene Dicarboximides (NDI), was synthesized utilizing ROMP with second-generation Grubbs catalyst
(G2). Kinetics studies examined using GPC confirmed controlled living polymerization in homopolymer
and block designs, evidenced by PDI 1.10–1.17 and a close agreement between experimental and
calculated Mn values. In contrast, random copolymers exhibited broader distributions due to ring strain
mismatch. Optical measurements revealed tunable band gaps, Eop
g 2.53–2.56 eV, and electrochemical
gaps, Eelc
g 2.01–2.37 eV, with enhanced conjugation in the homopolymer leading to narrower gaps.
Morphological investigations using SEM showed distinct self-assembly behaviours influenced by the
polymer chain and the micellization protocol, which explains the enhancement in the optical properties
of these polymers with Eop
g 2.27–2.41 eV. TGA analysis demonstrated high thermal stability across all polymers,
