Cyclooctatetrathiophene Annulated Multicyclic Macrocycles  

作　　者：Longbin Ren Yi Han Xudong Hou Ya Zou Tianyu Jiao Jishan Wu 

机构地区：[1]Department of Chemistry,National University of Singapore,Singapore 117543

出　　处：《CCS Chemistry》2024年第11期2758-2769,共12页中国化学会会刊（英文）

基　　金：supported financially by the Singapore Ministry of Education(MOE)Academic Research Fund(AcRF)Tier 2 grant(MOE-T2EP10222-0003);the Agency for Science,Technology and Research Manufacturing,Trade,and Connectivity(A*STAR MTC)project,Singapore(M22K2c0083).

摘　　要：The aromaticity and electronic properties of monocyclic or polycyclicπ-conjugated molecules have been widely studied.However,the related research on fullyπ-conjugated multicyclic macrocycles(MMCs)remains limited mainly due to the synthetic challenges.Herein,we report a straightforward synthesis of two MMCs(T8 and T12)in which unilateral and bilateral thiophene-based macrocycles merged with a cyclooctatetrathiophene unit by employing intramolecular Yamamoto coupling reactions of the designed precursors(8 and 12)followed by oxidative dehydrogenation.The neural compounds,their dications,and even tetracations were isolated in single-crystal form.Their geometry,aromaticity,open-shell diradical character,and physical properties were investigated by experiments such as X-ray crystallographic analysis,nuclear magnetic resonance(NMR),electron spin resonance(ESR),and theoretical calculations,which revealed changes in local/global aromatic/antiaromatic characteristics at different oxidation states.

关 键 词：MACROCYCLE AROMATICITY DIRADICAL CYCLOOCTATETRAENE THIOPHENE 

分 类 号：O62[理学—有机化学]