The
creation of matter with varying degrees of complexities and
desired functions is one of the ultimate targets of self-assembly.
The ability to regulate the complex interactions between the individual
components is essential in achieving this target. In this direction,
the initial success of controlling the pathways and final thermodynamic
states of a self-assembly process is promising. Despite the progress
made in the field, there has been a growing interest in pushing the
limits of self-assembly processes. The main inception of this interest
is that the intended self-assembled state, with varying complexities,
may not be “at equilibrium (or at global minimum)”,
rendering free energy minimization unsuitable to form the desired
product. Thus, we believe that a thorough understanding of the design
principles as well as the ability to predict the outcome of a self-assembly
process is essential to form a collection of the next generation of
complex matter. The present review highlights the potent role of finely
tuned interparticle interactions in nanomaterials to achieve the preferred
self-assembled structures with the desired properties. We believe
that bringing the design and prediction to nanoparticle self-assembly
processes will have a similar effect as retrosynthesis had on the
logic of chemical synthesis. Along with the guiding principles, the
review gives a summary of the different types of products created
from nanoparticle assemblies and the functional properties emerging
from them. Finally, we highlight the reasonable expectations from
the field and the challenges lying ahead in the creation of complex
and evolvable matter.
A novel thiocyanate bridged 2D MOF, [CdL(μ-1,3-SCN)2]n, [HL = 2-(2-(ethylamino)ethyliminomethyl)-6-ethoxyphenol] has been synthesized and characterized by X-ray crystallography. The band gap of the synthesized material in the solid state has been determined by experimental measurements and compared with the theoretical value obtained from DFT calculations. For the first time, the single crystal X-ray crystallography of a MOF has been reported along with its applicability in photosensitive devices.
The underlying power of "interplay of forces" in controlling the properties and functions at the nanoscale is highlighted in this perspective. This interplay is achieved by installing attractive and repulsive forces, via proper ligand chemistry, which will guide the nanomaterials to interact with their surroundings as per the need. Along with improving the existing properties, the balancing of attractive and repulsive forces holds the prospects of imparting newer functions as well. The concept of "ligand-directed interplay of forces" is extensively practiced by our group and others for addressing many challenges in the areas of self-assembly, catalysis, light harvesting, and nanomedicine. The journey has been rewarding so far in terms of achieving many important feats in nanoscience, such as selfassembly under equilibrium and nonequilibrium regimes, outplaying ligand poisoning in nanocatalysis, channelizing the flow of energy and electron in donor−acceptor systems, multicolor photopatterning using a single nanohybrid system, biospecific targeting and therapy, and so on. As evident from this perspective, the diversity of the areas benefited showcases the breadth and depth of the impact that surface ligands and interplay of forces can have in material science. Furthermore, the implementation of the "ligand of choice" approach is one way to realize distinct and specific functions from a limited set of nanomaterials. All the examples of "liganddirected studies" mentioned in this perspective are based on the regulation of, primarily, electrostatic forces emanating from the charged surface ligands. Thus, it will be logical to try various combinations of ligands and forces, which means that the area of "ligand-directed nanochemistry" will keep on advancing beyond our predictions. Looking forward, there is plenty of room at the NP surface.
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