Monolayer patterning using ketone dipoles.
Monolayer patterning using ketone dipoles.
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DOI：
10.1039/c3cp50808k
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发表时间：
2013-07
期刊：
影响因子：
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通讯作者：
Min Kyoung Kim;Yi Xue;Tereza Pašková;M. Zimmt
中科院分区：
文献类型：
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作者：
Min Kyoung Kim;Yi Xue;Tereza Pašková;M. Zimmt
具有设计图案的多组分单分子膜的自组装需要组分之间的分子识别。偶极相互作用被发现影响自组装单分子膜的形态，并且可以影响分子识别功能。酮基团具有大的偶极矩（2.6 D），并且容易并入分子中。通过合成两个1，5-二取代的蒽轴承单酮侧链，STM表征的单分子膜自组装从他们的单和双组分的解决方案和分子力学模拟，以确定其自组装能量的偶极图案的酮基团的潜力进行了评估。结果表明：（1）带有自排斥单酮侧链的蒽分子以非典型的单分子层形态聚集，在相邻侧链的酮分子之间建立了偶极吸引力而不是排斥力;（ii）其自排斥酮侧链是偶极互补的蒽分子对自发地组装组成图案化的单层，其中两种组分分离成相邻的，单组分柱，由侧链偶极相互作用驱动;（iii）组成图案化的单层也由采用不同偶极基团的偶极互补蒽对组装而成（酮或CF 2基团）;（iv）酮基，具有较大的偶极矩和尺寸，为图案化单层的形成提供了与较小的偶极子和较小尺寸的CF 2基团相当的驱动力。
The self-assembly of multi-component monolayers with designed patterns requires molecular recognition among components. Dipolar interactions have been found to influence morphologies of self-assembled monolayers and can affect molecular recognition functions. Ketone groups have large dipole moments (2.6 D) and are easily incorporated into molecules. The potential of ketone groups for dipolar patterning has been evaluated through synthesis of two 1,5-disubstituted anthracenes bearing mono-ketone side chains, STM characterization of monolayers self-assembled from their single and two component solutions and molecular mechanics simulations to determine their self-assembly energetics. The results reveal that (i) anthracenes bearing self-repulsive mono-ketone side chains assemble in an atypical monolayer morphology that establishes dipolar attraction, instead of repulsion, between ketones in adjacent side chains; (ii) pairs of anthracene molecules whose self-repulsive ketone side chains are dipolar complementary spontaneously assemble compositionally patterned monolayers, in which the two components segregate into neighboring, single component columns, driven by side chain dipolar interactions; (iii) compositionally patterned monolayers also assemble from dipolar complementary anthracene pairs that employ different dipolar groups (ketones or CF2 groups) in their side chains; (iv) the ketone group, with its larger dipole moment and size, provides comparable driving force for patterned monolayer formation to that of the smaller dipole, and smaller size, CF2 group.