Temperature-Dependent in Situ Reduction of 4,4鈥?Azobispyridine via Solvothermal Reaction

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• 作者：Yan-Li Gai ; Fei-Long Jiang ; Ke-Cai Xiong ; Lian Chen ; Da-Qiang Yuan ; Lin-Jie Zhang ; Kang Zhou ; Mao-Chun Hong
• 刊名：Crystal Growth & Design
• 出版年：2012
• 出版时间：April 4, 2012
• 年：2012
• 卷：12
• 期：4
• 页码：2079-2088
• 全文大小：664K
• 年卷期：v.12,no.4(April 4, 2012)
• ISSN：1528-7505

文摘

Solvothermal reactions of 2,2鈥?biphenyldicarboxylate (H₂dpa) and 4,4鈥?azobispyridine (azpy) in the presence of transition metal ions produce six new complexes, namely, [Co(dpa)(bphy)]_n (1), [Co(dpa)(azpy)(H₂O)]_n路0.5nH₂O (2), [Zn(dpa)(bphy)]_n (3), [Zn(dpa)(azpy)(H₂O)]_n (4), [Mn(dpa)(azpy)(H₂O)]_n路0.5nH₂O (5), and [Mn(dpa)(azpy)]_n路nH₂O路nMeOH (6) (bphy = 1,2-bis(4-pyridyl)hydrazine). The crystal structure analyses reveal that complexes 1 and 3 are isostructural which features a plywood-like structure, while complex 4 exhibits a parallel chains array. Complexes 2 and 5 afford a two-dimensional chiral (4,4) network, and complex 6 shows a (4,4) network. It was noteworthy that the in situ reduction of azpy to bphy was found in complexes 1 and 3, which were confirmed by single-crystal structures and LC-MS analyses. However, this in situ reduction was not found at a low reaction temperature in the syntheses of complexes 2, 4, and 5. The second-harmonic-generation (SHG) properties of 1 and 3 and the solid circular dichroism (CD) properties of 2 and 5 were investigated. In addition, luminescent properties of complexes 3 and 4 as well as magnetic properties of complexes 1, 2, 5, and 6 were also studied.