Department of Chemistry, Oregon State University, Corvallis, Oregon 97331-4003, United States.
Inorg Chem. 2011 Nov 21;50(22):11676-82. doi: 10.1021/ic201661y. Epub 2011 Oct 19.
A series of ternary graphite intercalation compounds (GICs) of alkali metal cations (M = Li, Na, K) and diamines [EN (ethylenediamine), 12DAP (1,2-diaminopropane), and DMEDA (N,N-dimethylethylenediamine)] are reported. These include stage 1 and 2 M-EN-GIC (M = Li, d(i) = 0.68-0.84 nm; M = Na, d(i) = 0.68 nm), stage 2 Li-12DAP-GIC (d(i) = 0.83 nm), and stage 1 and 2 Li-DMEDA-GIC (d(i) = 0.91 nm), where d(i) is the gallery height. For M = Li, a perpendicular-to-parallel transition of EN is observed upon evacuation, whereas for M = Na, the EN remains in parallel orientation. Li-12DAP-GIC and Li-DMEDA-GIC contain chelated Li(+) and do not show the perpendicular-to-parallel transition. We also report the quaternary compounds of mixed cations (Li,Na)-12DAP-GIC and mixed amines Na-(EN,12DAP)-GIC, with d(i) values in both cases between those of the ternary end members. (Li,Na)-12DAP-GIC is a solid solution with lattice dimensions dependent on composition, whereas for Na-(EN,12DAP)-GIC, the lattice dimension does not vary with amine content.
报道了一系列碱金属阳离子（M=Li、Na、K）和二胺[EN（乙二胺）、12DAP（1,2-二氨基丙烷）和 DMEDA（N,N-二甲基乙二胺）]的三元石墨插层化合物（GIC）。这些包括阶段 1 和 2 的 M-EN-GIC（M=Li，d(i)=0.68-0.84nm；M=Na，d(i)=0.68nm）、阶段 2 的 Li-12DAP-GIC（d(i)=0.83nm）以及阶段 1 和 2 的 Li-DMEDA-GIC（d(i)=0.91nm），其中 d(i)为层间距离。对于 M=Li，在抽真空时观察到 EN 的垂直-平行转变，而对于 M=Na，EN 仍保持平行取向。Li-12DAP-GIC 和 Li-DMEDA-GIC 含有螯合的 Li(+)，并且不显示垂直-平行转变。我们还报道了混合阳离子（Li，Na）-12DAP-GIC 和混合胺 Na-(EN,12DAP)-GIC 的四元化合物，在这两种情况下，其层间距离都介于三元端成员之间。（Li，Na）-12DAP-GIC 是一种固溶体，晶格尺寸取决于组成，而对于 Na-(EN,12DAP)-GIC，晶格尺寸不随胺含量而变化。
