新型萘/苝酰亚胺取代丁二炔衍生物的合成及拓扑聚合

Synthesis and Topochemical Polymerization Study of Naphthalene/perylene Imides Substituted Diacetylene Derivatives

经5步反应制备了萘/苝酰亚胺取代的端炔和碘炔单体,通过Sonagashira偶联反应合成了2个新型对称丁二炔单体浅黄色粉末2-[4-(4-{4-[7-(庚-3-基)-1,3,6,8-四氧亚基-1,2,3,6,7,8-六氢异喹啉并[6,5,4-def]异喹啉-2-基]苯基}丁-1,3-二炔基)苯基]-7-(辛-4-基)-1,2,3,6,7,8-六氢异喹啉并[6,5,4-def]异喹啉-1,3,6,8-四酮(diNDI)和暗红色粉末2-[4-(4-{4-[1,3,8,10-四氧亚基-9-(二十三烷-12-基)-1,2,3,8,9,10-六氢异喹啉并[6',5',4':9,1,2]蒽并[6,5,10-def]异喹啉-2-基]苯基}丁-1,3-二炔基)苯基]-9-(二十三烷-12-基)-1,2,3,8,9,10-六氢异喹啉并[6',5',4':9,1,2]蒽并[6,5,10-def]异喹啉-1,3,8,10-四酮(diPDI),产率分别达60%和70%.由于NDI和PDI基元的强吸电子作用,diNDI和diPDI表现较低的最低未占分子轨道(LUMO)能级,分别为‒3.80和‒3.70 eV.单晶数据表明,萘酰亚胺基元的分子间氢键及π-π作用对diNDI分子堆积结构起主导作用,diNDI呈层状堆积模式.由差示扫描量热(DSC)实验结果可知,diNDI丁二炔经加热可发生固态聚合.加热条件下diNDI的紫外-可见吸收光谱及原位拉曼光谱特征峰以及在波长532 nm激光强度为10%的辐照条件下原位拉曼光谱特征峰的变化均表明diNDI微纳晶发生了非常规的1,4-加成聚合,并且新生成的共轭主链是无序的,同时发现激光辐照条件下更易促进聚合反应.

Naphthalene/perylene imide substituted terminal alkyne and iodide monomers were prepared by a five-step reaction.Two new symmetric diacetylene monomers,pale yellow powder 2-(2-ethylhexyl)-7-{4-[7-(2-ethylhex⁃yl)-1,3,6,8-tetraoxo-1,2,3,3a,5a,6,7,8-octahydroisoquinolino[6,5,4-def]isoquinolin-2-yl]buta-1,3-diynyl}-1,2,3,6,7,8-hexahydroisoquinolino[6,5,4-def]isoquinoline-1,3,6,8-tetraone(diNDI)and deep red powder 9-{4-[1,3,8,10-tetraoxo-9-(tricos-12-yl)-1,2,3,8,9,10-hexahydroisoquinolino[6',5',4':9,1,2]anthra[6,5,10-def]isoquinolin-2-yl]buta-1,3-diynyl}-2-(tricos-12-yl)-1,2,3,8,9,10-hexahydroisoquinolino[6',5',4':9,1,2]anthra[6,5,10-def]isoquinoline-1,3,8,10-tetraone(diPDI),were synthesized by the Sonagashira coupling reaction with yields up to 60%and 70%,respectively.Due to the strong electron-withdrawing of NDI and PDI side groups,they exhibited deeper lowest unoccupied molecular orbital energy levels of−3.80 and−3.70 eV,respectively.The single crystal data of diNDI showed that the intermolecular hydrogen bonding andπ-πinteraction of naphthalene imide units mediated the intermolecular assembly of diNDI,showing a layer packing model.The differential scanning calo⁃rimetry results indicated that diNDI polymerized in solid-state under heating.The changes in the UV-Vis absorption and in situ Raman spectra of diNDI under heating and 532 nm-10%laser irradiation condition indicated that diNDI microcrystals might react to form a distorted structure instead of a fully conjugated backbone that usually resulted from the regular 1,4-addition.The laser irradiation conditions were found to facilitate the polymerization reaction.