Chrysene-based nanographenes (ChrNGs), despite their relatively small structures, have been reported to exhibit low highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps and strong long-wavelength fluorescence, making them attractive for various applications. However, the precise synthesis of ChrNGs remains challenging, and their availability is limited compared with other classes of nanographenes. Herein, we report the synthesis of novel ChrNGs by a successive annulative π-extension (APEX) reaction. Using diphenylacetylene and benzonaphthosilole in a Pd/o-chloranil catalytic system, successive APEX afforded ChrNGs of various lengths and degrees of oxidation. Furthermore, exhaustive separation and further π-extension by cyclodehydrogenation afforded ChrNGs with more flat and rigid structures. Photophysical measurements of the obtained ChrNGs showed a variety of absorption and emission properties, including intense multicolor emission.
{"title":"Synthesis of Chrysene-Based Nanographenes by a Successive APEX Reaction.","authors":"Yuichi Nakashige, Hidefumi Nakatsuji, Kaho Matsushima, Kazuo Murakami, Hideto Ito, Kenichiro Itami","doi":"10.1021/prechem.5c00032","DOIUrl":"10.1021/prechem.5c00032","url":null,"abstract":"<p><p>Chrysene-based nanographenes (ChrNGs), despite their relatively small structures, have been reported to exhibit low highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps and strong long-wavelength fluorescence, making them attractive for various applications. However, the precise synthesis of ChrNGs remains challenging, and their availability is limited compared with other classes of nanographenes. Herein, we report the synthesis of novel ChrNGs by a successive annulative π-extension (APEX) reaction. Using diphenylacetylene and benzonaphthosilole in a Pd/<i>o</i>-chloranil catalytic system, successive APEX afforded ChrNGs of various lengths and degrees of oxidation. Furthermore, exhaustive separation and further π-extension by cyclodehydrogenation afforded ChrNGs with more flat and rigid structures. Photophysical measurements of the obtained ChrNGs showed a variety of absorption and emission properties, including intense multicolor emission.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 9","pages":"535-540"},"PeriodicalIF":6.2,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12458009/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145151174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The nonequilibrium composition and its formation process are critical aspects of nanoparticle production technology. Understanding the dynamics of nanoparticle formation under nonequilibrium conditions is essential. In this study, Cr-doped CeO2 nanoparticles are synthesized via continuous-flow hydrothermal synthesis at various temperatures (300, 350, 400 °C) with reaction times precisely controlled on the order of seconds. At the initial stage of particle formation, Cr-rich CeO2 particles form due to a low surface energy. Over time, the Cr content decreases as the particles relax toward the equilibrium structure. This process yields an unusual nonequilibrium composition through rapid heating and short residence times. Similar nonequilibrium compositions are also observed for other dopants, such as Fe and Eu. Continuous-flow hydrothermal synthesis thus presents an efficient method for fabricating nanomaterials with unique compositions that are unattainable using conventional batch methods.
{"title":"Nonequilibrium Process for Doping Under Continuous-Flow Hydrothermal Synthesis of Cerium Oxide-Based Nanoparticles","authors":"Akira Yoko*, Chunli Han, Ayame Sakonaka, Gimyeong Seong, Takaaki Tomai, Satoshi Ohara and Tadafumi Adschiri*, ","doi":"10.1021/prechem.5c00004","DOIUrl":"10.1021/prechem.5c00004","url":null,"abstract":"<p >The nonequilibrium composition and its formation process are critical aspects of nanoparticle production technology. Understanding the dynamics of nanoparticle formation under nonequilibrium conditions is essential. In this study, Cr-doped CeO<sub>2</sub> nanoparticles are synthesized via continuous-flow hydrothermal synthesis at various temperatures (300, 350, 400 °C) with reaction times precisely controlled on the order of seconds. At the initial stage of particle formation, Cr-rich CeO<sub>2</sub> particles form due to a low surface energy. Over time, the Cr content decreases as the particles relax toward the equilibrium structure. This process yields an unusual nonequilibrium composition through rapid heating and short residence times. Similar nonequilibrium compositions are also observed for other dopants, such as Fe and Eu. Continuous-flow hydrothermal synthesis thus presents an efficient method for fabricating nanomaterials with unique compositions that are unattainable using conventional batch methods.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":"3 7","pages":"372–379"},"PeriodicalIF":6.2,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12308591/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144761595","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}