Architectonics: Design of Molecular Architecture for Functional Applications

Abstract

The term architectonics has its roots in the architectural and philosophical (as early as 1600s) literature that refers to "the theory of structure" and "the structure of theory", respectively. The concept of architectonics has been adapted to advance the field of molecular self-assembly and termed as molecular architectonics. In essence, the methodology of organizing molecular units in the required and controlled configurations to develop advanced functional systems for materials and biological applications comprises the field of molecular architectonics. This concept of designing noncovalent systems enables to focus on different functional aspects of designer molecules for biological and nonbiological applications and also strengthens our efforts toward the mastery over the art of controlled molecular self-assemblies. Programming complex molecular interactions and assemblies for specific functions has been one of the most challenging tasks in the modern era. Meticulously ordered molecular assemblies can impart remarkable developments in several areas spanning energy, health, and environment. For example, the well-defined nano-, micro-, and macroarchitectures of functional molecules with specific molecular ordering possess potential applications in flexible electronics, photovoltaics, photonic crystals, microreactors, sensors, drug delivery, biomedicine, and superhydrophobic coatings, among others. The functional molecular architectures having unparalleled properties are widely evident in various designs of Nature. By drawing inspirations from Nature, intended molecular architectures can be designed and developed to harvest various functions, as there is an inexhaustible resource and scope. In this Account, we present exquisite designer molecules developed by our group and others with an objective to master the art of molecular recognition and self-assembly for functional applications. We demonstrate the tailor-ability of molecular self-assemblies by employing biomolecules like amino acids and nucleobases as auxiliaries. Naphthalenediimide (NDI), perylenediimide (PDI), and few other molecular systems serve as functional modules. The effects of stereochemistry and minute structural modifications in the molecular designs on the supramolecular interactions, and construction of self-assembled zero-dimensional (OD), one-dimensional (1D), and two-dimensional (2D) nano- and microarchitectures like particles, spheres, cups, bowls, fibers, belts, helical belts, supercoiled helices, sheets, fractals, and honeycomb-like arrays are discussed in extensive detail. Additionally, we present molecular systems that showcase the elegant designs of coassembly, templated assembly, hierarchical assembly, transient self-assembly, chiral denaturation, retentive helical memory, self-replication, supramolecular regulation, supramolecular speciation, supernon linearity, dynamic pathway complexity, supramolecular heterojunction, living supramolecular polymerization, and molecular machines. Finally, we describe the molecular engineering pri...

Synthetic Evolution of the Multifarene Cavity from Planar Predecessors

“…We used the Eyring equation to derive the free energy of activation, DG # ,f or the interconversion of the two conformers ( Table 4). [32] These values, 16.55 kcal mol À1 for C 2 D 2 Cl 4 and 16.6 kcal mol À1 for [D 7 ]DMF,a re comparable with those reported for conformational inversion of calix [4]arenes. [33] These results indicatet hat, in contrast to the significant solvente ffect on the conformational ratio, the activation energy barrier is quite insensitive to solvent polarity.S imilar tendencies were reported for rotamers of acyclic tertiary carbamates.…”

“…The design and construction of 3D objects from 2D building blocks is a common approach in the macroscopic world and is a most common strategy in architecture, mechanical engineering, visual arts, and almost any field that involves creation of tangible objects. This approach is much less intuitive in the microscopic world, and in organic synthesis in particular, although the close analogy between chemistry and architecture has been increasingly recognized . Scott has successfully demonstrated this strategy in the total synthesis of carbon nanotubes .…”

“…This approachism uch less intuitive in the microscopicw orld, and in organic synthesis in particular, [1] althought he close analogy between chemistry and architecture has been increasingly recognized. [2][3][4][5] Scott has successfully demonstrated this strategy in the total synthesis of carbon nanotubes. [6] The landmark discovery of stable closed-cage nanostructures derived from graphitic carbon [7] sparkedm uch interesti nt he origin of their stability.K roto proposed that the large chemical energys tored in the rim atoms of small graphene sheets forces the carbona toms to spontaneously reorganize into hollow-cage structures, [8] and Te nne has highlighted this general thermodynamic driving force in the formation of inorganic nanotubes and fullerene-like nanoparticles.…”

First in situ vesicular self-assembly of ‘binols’ generated by a two-component aerobic oxidation reaction

“…These studies have helped scientists to improve the understanding of the structure property relationships that resulted in such supramolecular structures in liquid medium. [1][2][3][4][5][6][7][8][9][10] Spontaneous self-assembly of molecules, yielding vesicles, is of special signicance due to its tremendous application in the areas of targeted drug delivery, medical implants, nanoscale reactors, tissue engineering, gene therapy, theranostics, enzyme entrapment, magnetic resonance imaging, etc. [11][12][13][14][15][16][17][18] Literature studies reveal that vesicular self-assemblies have been reported from a wide range of amphiphilic compounds.…”

“…[19][20][21][22][23][24][25][26][27][28][29] Though, the formation of nano-sized spherical assemblies and vesicles in water from long alkyl-chained compounds having different head groups are known, according to our knowledge, aerobic coupling of two components leading to the formation of vesicular self-assemblies and supramolecular nano-architectures in organic media is unprecedented. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Binols, obtained by coupling reaction of two b-naphthol precursors, have found application in the design of asymmetric catalysts for a wide range of chemical transformations. [30][31][32][33][34][35][36] The demonstration of self-replication on non-enzymatic model systems in its minimal form require: (1) suitable complementary recognition sites in the template molecule to complex the precursor molecules by non-covalent interactions and (2) a suitable chemical reaction for the formation of a chemical bond.…”