The Fabrication of Multicomponent Oxide Films by Computer- Controlled Dual Ion Beam Sputter Deposition

有机化学和高分子化学项目的这笔赠款为普林斯顿大学的小罗伯特·帕斯卡博士的研究提供了支持。这项工作的重点是分子结构，在这些分子结构中，两个相对不活跃的分子实体被迫非常接近。以这种方式被迫占据有限空间的原子团在化学反应和物理性质方面都有不寻常的行为。在一类目标分子中，甲胺、胺和氨基将被压在芳环的圆周率电子云的外围；在第二类目标分子中，这些相同的基团将被投射到环的中心。在第一种情况下，“目标”苯基上的取代基将发生变化，以产生相对富含电子或缺电子的芳香环。官能团与环的相互作用程度应随这种电子取代而变化。在第二类化合物中，相互作用的增加不是通过芳环取代基的变化来实现的，而是通过合成一系列的化合物来实现的，其中官能团与环之间的距离被系统地减小了。通过平衡这些化合物中分子内应变引起的力与环的亲核性或亲电性的程度，可以观察到这些基团之间部分成键的结构。在芳香族化合物的亲核和亲电取代反应中，这种结构应该被解释为过渡态的类似物(本身并不是可观察到的)。

This grant in the Organic and Macromolecular Chemistry Program provides support for the research of Dr. Robert Pascal, Jr., Princeton University. The work is focused on the structures of molecules in which two relatively unreactive molecular entities are forced to be very close together. Groups of atoms which are forced in this way to occupy a limited space have unusual behavior, both in terms of their chemical reactivity and their physical properties. In one class of target molecules, methine, amine, and ammonium groups will be pressed near the periphery of the pi electron clouds of aromatic rings; in a second class these same groups will be projected toward the center of the rings. In the first case, the substituents on the "target" phenyl groups will be varied to produce aromatic rings which are relatively electron-rich or electron-deficient. The extent of interaction of the functional groups with the ring should vary with this electronic substitution. In the second class of compounds, increased interactions will be achieved not by the variation of aromatic ring substituents, but by synthesizing a series of compounds in which the distance between the functional group and ring is systematically reduced. By balancing the forces due to intramolecular strain in these compounds with the degree of nucleophilicity or electrophilicity of the ring, structures may be observed with partial bonding between these groups. Such structures should be interpretable as analogs of transition states (which are not themselves observable) in the nucleophilic and electrophilic substitution reactions of aromatic compounds.