摘要
化合物6-苯胺基-5H-2,3-二硫杂-5,7-二氮杂环戊二烯并[c,d]茚-1,4-二甲酸二乙酯(DADDCI)是本实验室合成的新型硫氮杂环化合物。通过吸收、荧光光谱,结合理论计算,研究了该化合物在溶剂DMSO/H_2O中的结构和聚集性质。结果表明,在DMSO中,化合物的苯环与并噻吩共平面,易形成H-聚集体致使荧光强度相对较弱,在H2O含量为66%—70%时,化合物形成J-聚集体,吸收峰明显红移,从390nm到444nm,伴随着荧光峰强度迅速增强至7倍以上,此时可明显观察到体系呈凝胶状。结构优化证实,化合物与H_2O之间的氢键复合物取代与DMSO形成的复合物后,化合物的苯环与主平面之间发生扭转,二面角达86°。形成J-聚集体后,化合物的结构被固定,灵活性降低,分子中亚胺N接受质子的能力及胺N上的氢质子离域能力明显下降,化合物的吸收光谱受酸碱的影响程度明显降低。
The investigation of the significant intermolecular hydrogen bonding effects on the structure and aggregate properties of diethyl-6-anilino-5H-2,3-dithia-5,7-diaza-cyclopenta[c,d] indenes（DADDCI） in H_2O/DMSO solvent was performed in this paper through absorption and fluorescence spectroscopy,as well as theoretical calculation.DADDCI is a new kind of sulfur and nitrogen heterocyclic compound synthesized in our group.The benzene ring of DADDCI is coplanar with bithiophene in DMSO,which is benefit to form H-aggregation for DADDCI and bring down fluorescence intensity.When the H_2O content was 66%—70%in solvent,it formed J-aggregation for DADDCI,and the absorption peak had a red shift sharply from 390nm to 444nm,meanwhile the fluorescence intensity strengthened more than 7 times.The theoretical study based on DFT calculation is very helpful for the understanding on the optical properties of DADDCI.It was confirmed that the formation of intermolecular hydrogen bonds between DADDCI and H_2O could lead to a torsion angle （86°） between the benzene ring and the main plane,then J-aggregation and aggregation-induced emission were observed.It was found that the conformer of DADDCI was fixed and the flexibility was very weak in the state of J-aggregation,the ability of protonation of amine N and deprotonation of NH in compound both became more difficult.
出处
《光谱实验室》
CAS
2013年第1期246-252,共7页
Chinese Journal of Spectroscopy Laboratory
基金
湖北省自然科学基金项目(No.2010CDB10704)
