硅杂大环芳烃是一类由硅原子作为桥连单元连接芳(杂)环所构成的新型大环分子。与传统碳桥联大环芳烃相比,硅原子的引入因其较大的原子半径、可极化的化学键等特性,显著改变了分子的构象灵活性、电子结构和配位能力。系统综述了多类硅杂大环芳烃的合成策略、结构特征与固相构象行为,并重点阐述了其在金属离子配位、主客体识别及光电功能材料等领域的应用研究进展。最后对硅杂大环芳烃的未来发展方向进行了展望。
Silicon-bridged macrocyclic arenes are a class of novel macrocyclic molecules constructed by linking (hetero) arene units via silicon bridges.Compared with traditional carbon-bridged macrocyclic arenes,the introduction of silicon significantly alters the molecular conformational flexibility,electronic structure,and coordination capabilities owing to their larger atomic radius,polarizable chemical bonds,and other distinctive properties.This review systematically summarized the synthetic strategies,structural characteristics,and conformational behaviors of several representative types of silicon-bridged macrocyclic arenes.It focused on their research progress in applications such as metal ion coordination,host-guest recognition,and optoelectronic functional materials.Finally,the future development directions of silicon-bridged macrocyclic arenes awere prospected.
[1] 张来新,陈琦.新型杯芳烃的合成自组装及应用研究[J].化工新型材料,2018,46(3):34-36.
[2] 蔡秀琴.基于杯[4]芳烃超分子凝胶组装进展[J].化工新型材料,2018,46(9):45-50.
[3] 陈煜,田晓冲,唐坤,等.柱[6]芳烃在功能材料方面的应用研究进展[J].化工新型材料,2019,47(6):18-21.
[4] Wang M X.Nitrogen and oxygen bridged calixaromatics:synthesis,structure,functionalization,and molecular recognition[J].Accounts of Chemical Research,2012,45(2):182-195.
[5] Lhotak P.Chemistry of thiacalixarenes[J].European Journal of Organic Chemistry,2004,8:1675-1692.
[6] Mendoza-Espinosa D,Hanna T A.Facile synthesis of bismuth(Ⅲ) and antimony(Ⅲ) complexes supported by silylated calix[5]arenes[J].Inorganic Chemistry,2009,48:10312-10325.
[7] 来国桥,幸松民.有机硅产品合成工艺及应用[M].北京:化学工业出版社,2009.
[8] Moores A,Mezailles N,Maigrot N,et al.Synthesis and reactivity towards cationic group 11 metal centers of an extended silacalix-[3]-phosphinine macrocycle[J].European Journal of Organic Chemistry,2002,8:2034-2039.
[9] Avarvari N,Maigrot N,Ricard L,et al.Synthesis and X-ray crystal structures of silacalix[n]phosphinines:the first sp2-based phosphorus macrocycles[J].Chemistry-A European Journal,1999,5:2109-2118.
[10] Avarvari N,Mezailles N,Ricard L,et al.Silacalix-[n]-phosphaarenes:macrocyclic ligands based on dicoordinate phosphorus centers[J].Science,1998,280:1587-1589.
[11] Konig B,Rodel M,Bubenitschek P,et al.Silicon-bridged macrocycles-synthesis of sila-calixarenes[J].Angewandte Chemie International Edition,1995,34:661-662.
[12] Yoshida M,Goto M,Nakanishi F.Silicon-bridged metacyclophanes as parent compounds of silacalix[n]arenes.synthesis,structures,and conformational analysis by semiempirical mo calculations[J].Organometallics,1999,18:1465-1470.
[13] Konig B,Rodel M,Bubenitschek P.Synthesis,structure,and coordination properties of silicon-bridged macrocycles[J].Journal of Organic Chemistry,1995,60:7406-7410.
[14] Tsutsui S,Sakamoto K.Preparation and structures of novel silamacrocyclic compounds:silacalix[4]quinone and silacalix[4]hydroquinone octamethyl ether[J].Chemical Communications,2003,18:2322-2323.
[15] Tsutsui S,Tanaka H,Sakamoto K.Preparation,structures,and theoretical calculations of novel silacalixarene derivatives:silacalix[4]quinone and silacalix[4]hydroquinone octamethyl ether[J].Organometallics,2024,23:3719-3726.
[16] Kasprzak A.Supramolecular chemistry of sumanene[J].Angewandte Chemie International Edition,2024,63:e202318437.
[17] Furukawa S,Kobayashi J,Kawashima T.Development of a sila-friedel-crafts reaction and its application to the synthesis of dibenzosilole derivatives[J].Journal of the American Chemical Society,2009,131:14192-14193.
[18] Tan Q,Zhou D,Zhang T,et al.Iodine-doped sumanene and its application for the synthesis of chalcogenasumanenes and silasumanenes[J].Chemical Communications,2017,53:10279-10282.
[19] Zhou D,Gao Y,Liu B,et al.Synthesis of silicon and germanium-containing heterosumanenes via rhodium-catalyzed cyclodehydrogenation of silicon/germanium-hydrogen and carbon-hydrogen bonds[J].Organic Letters,2017,19:4628-4631.
[20] Kumar S,Tao Y.Coronenes,benzocoronenes and beyond:modern aspects of their syntheses,properties,and applications[J].Chemistry-an Asian Journal,2021,16:621-647.
[21] Yang B,Sun Y,Hu J,et al.A silicon-doped nanographenic bowl for supramolecular assembly with fullerenes[J].Organic Letters,2025,27:11045-11051.
[22] Yang B,Sun Y,Hu J,et al.Triazasupersumanenes:bowl-shaped nanographenes with tunable properties and unexpected charge transport performance[J].Chem,2025,11:102628.
[23] Ohtani S,Akine S,Kato K,et al.Silapillar[n]arenes:their enhanced electronic conjugation and conformational versatility[J].Journal of the American Chemical Society,2024,146:4695-4703.
[24] Ogoshi T,Yamagishi T A,Nakamoto Y.Pillar-shaped macrocyclic hosts pillar[n]arenes:new key players for supramolecular chemistry[J].Chemical Reviews,2016,116:7937-8002.
[25] 翟慧娟.新型含脲基大环与硅杂大环化合物的合成及其性质研究[D].长沙:湖南大学,2022.
基金资助
四川省重大科技专项项目(2024ZDZX0038)
PDF
