Systematic Investigation of Molecular Arrangements and Solid-State Fluorescence Properties on Salts of Anthracene-2,6-disulfonic Acid with Aliphatic Primary Amines

• Published in: Chemistry : a European journal 2009-08, Vol.15 (33), p.8175-8184
• Main Authors: Mizobe, Yuji, Hinoue, Tomoaki, Yamamoto, Atsushi, Hisaki, Ichiro, Miyata, Mikiji, Hasegawa, Yasuchika, Tohnai, Norimitsu
• Format: Article
• Language: English
• Subjects: anthracene; crystal engineering; fluorescence; hydrogen bonds; solid-state structures
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200900773

Organic salts of anthracene‐2,6‐disulfonic acid (ADS) with a wide variety of primary amines have been fabricated, and their arrangements of anthracene molecules and solid‐state fluorescence properties investigated. Single‐crystal X‐ray studies reveal that the salts show seven types of crystal forms and corresponding molecular arrangements of anthracene moieties depending on the amine, while anthracene shows only one form and arrangement in the solid state. Depending on the molecular arrangements, the ADS salts exhibit various solid‐state fluorescence properties: spectral shift (30 nm) and suppression and enhancement of the fluorescence intensity. Especially the ADS salt with n‐heptylamine (nHepA), which shows discrete anthracene moieties in the crystal, exhibits the highest quantum yield (ΦF=46.1±0.2 %) in the series of ADS salts, which exceeds that of anthracene crystal (ΦF=42.9±0.2 %). From these systematic investigations on the arrangements and the solid‐state properties, the following factors are essential for high fluorescence quantum yield in the solid state: prevention of contact between π planes of anthracene moieties and immobilization of anthracene rings. In addition, such organic salts have potential as a system for modulating the molecular arrangements of fluorophores and the concomitant solid‐state properties. Thus, systematic investigation of this system constructs a library of arrangements and properties, and the library leads to remarkable strategies for the development of organic solid materials. Magnificent seven: Seven types of arrangements of anthracene molecules were found in crystals of salts of anthracene 2,6‐disulfonic acid with aliphatic amines, depending on the size and shape of the amine alkyl groups. A systematic investigation of the relationships between molecular arrangement and solid‐state fluorescence properties (see picture) showed a significant influence of the number of adjacent fluorophores and immobilization of fluorophores.