Conventional spiro-linked conjugated materials are attractive for organic optoelectronic applications due to the unique combination of their optical and electronic properties. However, spiro-linked conjugated materials with conjugation extension directed along the main axis of the molecule are still only rare examples among the vast number of spiro-linked conjugated materials. Herein, the synthesis, leading to π-extended spiro-linked conjugated materials-spiro[4.4]nonane-1,6-diones and spiro[5.5]undecane-1,7-diones-has been developed and optimized. The proposed design concept starts from readily available malonic esters and contains several steps: double alkylation of malonic ester with bromomethylaryl(hetaryl)s; conversion of a malonic ester into the corresponding malonic acid; electrophilic spirocyclization of the latter into the annulated spiro[4.4]nonane-1,6-dione or spiro[5.5]undecane-1,7-dione in the presence of phosphorus pentoxide. On the basis of these insights, the developed method yielded spiro-linked conjugated cores fused with benzene, thiophene, and naphthalene, decorated with active halogen atoms. The structures of the synthesized spirocycles were determined by single-crystal X-ray diffraction analysis. Benzene fused spiro[4.4]nonane-1,6-dione decorated with bromine atoms was transformed into V-shape phenylene-thiophene co-oligomer type spirodimers via Stille coupling. The spiro-bis(4-n-dodecylphenyl)-2,2′-bithiophene derivative possessed high photoluminescence properties in both solution and solid state with a photoluminescence quantum yield (PL QY) of 38%.

Язык оригиналаанглийский
Страницы (с-по)2456-2469
Число страниц14
ЖурналJournal of Organic Chemistry
Номер выпуска5
Ранняя дата в режиме онлайн15 февр. 2022
СостояниеОпубликовано - 4 мар. 2022

Предметные области OECD FOS+WOS



Подробные сведения о темах исследования «P2O5-Promoted Cyclization of Di[aryl(hetaryl)methyl] Malonic Acids as a Pathway to Fused Spiro[4.4]nonane-1,6-Diones». Вместе они формируют уникальный семантический отпечаток (fingerprint).