College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Jiefang Road 2519, Changchun, 130023, PR China.
Dalton Trans. 2012 Feb 28;41(8):2382-92. doi: 10.1039/c1dt11846c. Epub 2011 Dec 23.
Under the hydrothermal conditions, five new acylhydrazidate-containing compounds [Cd(EPDH)(2)(H(2)O)] 1, [Cd(MPDH)(2)] 2, [Zn(MPDH)(2)(H(2)O)(2)]·2H(2)O 3, [Pb(2)(ODPTH)(2)(phen)(2)(H(2)O)(2)] 4 and [Cd(2)(APTH)(4)(phen)(2)]·2H(2)O 5 (EPDH = 5-ethylpyridine-2,3-dicarboxylhydrazidate, MPDH = 6-methylpyridine-2,3-dicarboxylhydrazidate, ODPTH = 4,4'-oxydiphthalhydrazidate, APTH = 3-amiophthalhydrazidate, phen = 1,10-phenanthroline) were luckily obtained. Note that MPDH, EPDH and ODPTH were derived from the hydrothermal in situ acylation reactions between organic polycarboxylic acids and N(2)H(4)·H(2)O, whereas APTH originated from the hydrothermal in situ reduction reaction of NPTH (NPTH = 3-nitrophthalhydrazidate) in the presence of N(2)H(4)·H(2)O. The photoluminescence analysis indicates that all of the title compounds are fluorescent materials with maximum emissions at 530 nm for 1, 540 nm for 2, 517 nm for 3, 413 nm for 4 and 563 nm for 5, respectively. The density functional theory (DFT) calculations on the excited electronic states of compound 3 indicate that the emission is associated with the ligands, corresponding to the charge transfer from the π orbital of the acylhydrazidate ring to the π* orbital of the pyridine ring.
在水热条件下，五个新的酰腙基化合物[Cd(EPDH)(2)(H(2)O)]1、[Cd(MPDH)(2)]2、[Zn(MPDH)(2)(H(2)O)(2)]·2H(2)O3、[Pb(2)(ODPTH)(2)(phen)(2)(H(2)O)(2)]4 和[Cd(2)(APTH)(4)(phen)(2)]·2H(2)O5 被幸运地得到。需要注意的是，MPDH、EPDH 和 ODPTH 是由有机多羧酸与 N(2)H(4)·H(2)O 在水热原位酰化反应得到的，而 APTH 则是 NPTH（NPTH = 3-硝基邻苯二甲酰腙）在 N(2)H(4)·H(2)O 存在下的水热原位还原反应得到的。荧光分析表明，所有标题化合物都是荧光材料，最大发射峰分别位于 1 的 530nm、2 的 540nm、3 的 517nm、4 的 413nm 和 5 的 563nm。对化合物 3 的激发电子态的密度泛函理论（DFT）计算表明，发射与配体有关，对应于酰腙环的π轨道到吡啶环的π*轨道的电荷转移。
