Dendrimer Ligand Directed Nanoplate Assembly
Dendrimer Ligand Directed Nanoplate Assembly
复制标题
树枝状大分子配体导向的纳米片组装
DOI：
10.1021/acsnano.9b07348
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发表时间：
2019-12-01
期刊：
影响因子：
17.1
通讯作者：
Murray, Christopher B.
中科院分区：
文献类型：
--
作者：
Elbert, Katherine C.;Thi Vo;Murray, Christopher B.
许多关于纳米粒子自组装成有序超晶格的研究主要集中在纳米粒子之间的吸引力上，而有机配体对各向异性纳米粒子的作用还处于起步阶段。在这里，我们报告了使用一系列的树枝状聚合物配体，以指导组装成2D和3D几何形状的纳米片。发现树枝状聚合物纳米片在3D膜中一致地形成定向偏移结构。我们提出了一个理论来预测配体表面分布和Monte Carlo模拟结果，表征配体壳周围的纳米片。庞大的树枝状聚合物配体在板周围产生随配体结构变化的非平凡的冠。当这种有机-无机有效形状与热力学微扰理论结合使用以预测NC之间的晶格形态和平衡相对取向时，发现3D组装的锁和钥匙类型的机制。我们观察到我们的实验结果和理论模型之间的2D和3D几何形状，包括NC层之间的偏移百分比的良好协议。这种理论理解和建模水平将有助于指导未来的设计框架，以实现NC的目标组装。
Many studies on nanocrystal (NC) self-assembly into ordered superlattices have focused mainly on attractive forces between the NCs, whereas the role of organic ligands on anisotropic NCs is only in its infancy. Herein, we report the use of a series of dendrimer ligands to direct the assembly of nanoplates into 2D and 3D geometries. It was found that the dendrimer-nanoplates consistently form a directionally offset architecture in 3D films. We present a theory to predict ligand surface distribution and Monte Carlo simulation results that characterize the ligand shell around the nanoplates. Bulky dendrimer ligands create a nontrivial corona around the plates that changes with ligand architecture. When this organic -inorganic effective shape is used in conjunction with thermodynamic perturbation theory to predict both lattice morphology and equilibrium relative orientations between NCs, a lock-and-key type of mechanism is found for the 3D assembly. We observe excellent agreement between our experimental results and theoretical model for 2D and 3D geometries, including the percent of offset between the layers of NCs. Such level of theoretical understanding and modeling will help guide future design frameworks to achieve targeted assemblies of NCs.