Isostructural materials achieved by using structurally equivalent donors and acceptors in halogen-bonded cocrystals
Isostructural materials achieved by using structurally equivalent donors and acceptors in halogen-bonded cocrystals
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DOI：
10.1002/chem.200701184
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发表时间：
2008-01-01
影响因子：
4.3
通讯作者：
Jones, William
中科院分区：
文献类型：
--
作者：
Cincic, Dominik;Friscic, Tomislav;Jones, William
通过合成7种同结构的卤键共晶，包括1，4-二溴和1，4-二碘四氟苯(给体)和硫吗啉、硫代恶烷、吗啉和哌嗪(受体)，我们证明了两个卤键给体(I和Br)和三个受体(O、NH和S)在超分子和结构上的等价性。等结构共晶体的形成表明共结晶如何被用来克服控制固态中分子排列的形状和官能团的不同。七种等结构共晶之间的组成差异直接影响其组分之间卤素键的强度和性质，允许共晶物理性质的系统变化，特别是熔点，而不影响其晶体结构。将每个O或S卤键受体替换为NH基团可使熔点升高约70℃，而将I替换为溴作为卤键给体则使所得固体的熔点降低了类似的量。
We demonstrate the supramolecular and structural equivalence of two halogen-bond donors (I and Br) and three acceptors (O, NH and S) through the synthesis of seven isostructural halogen-bonded cocrystals, involving six different molecules: 1,4-dibromo- and 1,4-diiodotetrafluorobenzene (donors) and thiomorpholine, thioxane, morpholine, and piperazine (acceptors). ne formation of isostructural cocrystals indicates how cocrystallization may be used to overcome shape and functional group dissimilarities that control molecular arrangement in the solid state. The differences in composition between the seven isostructural cocrystals directly affect the strength and nature of halogen bonds between their constituents, allowing the systematic variation of cocrystal physical properties, in particular the melting point, without affecting their crystal structure. Replacement of each O or S halogen-bond acceptor with an NH group provided an approximate 70 degrees C increase in melting point, whereas the replacement of I with Br as the halogen-bond donor lowered the melting point of the resulting solid by a similar amount.