Zethrene and Dibenzozethrene: Masked Biradical Molecules?†
Ya-Chu Hsieh
Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorHau-Yu Fang
Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorYi-Ting Chen
Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Search for more papers by this authorRong Yang
Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Search for more papers by this authorProf. Chen-I Yang
Department of Chemistry, Tunghai University, No. 181 Taichung-Kang Rd., Sec. 3, 40704 Taichung (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Pi-Tai Chou
Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Pi-Tai Chou, Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Ming-Yu Kuo, Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Yao-Ting Wu, Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Ming-Yu Kuo
Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Pi-Tai Chou, Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Ming-Yu Kuo, Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Yao-Ting Wu, Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Yao-Ting Wu
Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Pi-Tai Chou, Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Ming-Yu Kuo, Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Yao-Ting Wu, Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorYa-Chu Hsieh
Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorHau-Yu Fang
Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorYi-Ting Chen
Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Search for more papers by this authorRong Yang
Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Search for more papers by this authorProf. Chen-I Yang
Department of Chemistry, Tunghai University, No. 181 Taichung-Kang Rd., Sec. 3, 40704 Taichung (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Pi-Tai Chou
Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Pi-Tai Chou, Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Ming-Yu Kuo, Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Yao-Ting Wu, Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Ming-Yu Kuo
Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Pi-Tai Chou, Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Ming-Yu Kuo, Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Yao-Ting Wu, Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorCorresponding Author
Prof. Yao-Ting Wu
Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Pi-Tai Chou, Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei (Taiwan)
Ming-Yu Kuo, Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou (Taiwan)
Yao-Ting Wu, Department of Chemistry, National Cheng Kung University, No. 1 Ta-Hsueh Rd., 70101 Tainan (Taiwan)
Search for more papers by this authorMetal-Catalyzed Reactions of Alkynes. Part XVI. This work was supported by the Ministry of Science and Technology of Taiwan. We thank Prof. Sue-Lein Wang and Ms. Pei-Lin Chen (National Tsing Hua University, Taiwan) for the X-ray structure analyses. Prof. Hui-Lien Tsai (National Cheng Kung University) is acknowledged for a helpful discussion.
Abstract
The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel-catalyzed cyclodimerization of 9-ethynyl-1-iodoanthracenes. The substituents in zethrene and dibenzozethrene twisted their backbones, and remarkably influenced their properties. Unlike closed-shell disubstituted derivatives, the parent zethrene and dibenzozethrene are singlet open-shell biradicals, which were studied by variable-temperature 1H NMR, ESR, SQUID and computational methods. Since substituents were observed to affect significantly the biradical properties, the relevant mechanisms were analyzed. The nonlinear optical performance of each of these compounds depends on its π-conjugation and biradical properties. Dibenzozethrenes have larger two-photon absorption cross-sections than zethrenes, as most strongly evidenced by the parent dibenzothrene [σmax=4323 GM at 530 nm].
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