Progress in Molecular Nanoarchitectonics and Materials Nanoarchitectonics

Abstract

Although various synthetic methodologies including organic synthesis, polymer chemistry, and materials science are the main contributors to the production of functional materials, the importance of regulation of nanoscale structures for better performance has become clear with recent science and technology developments. Therefore, a new research paradigm to produce functional material systems from nanoscale units has to be created as an advancement of nanoscale science. This task is assigned to an emerging concept, nanoarchitectonics, which aims to produce functional materials and functional structures from nanoscale unit components. This can be done through combining nanotechnology with the other research fields such as organic chemistry, supramolecular chemistry, materials science, and bio-related science. In this review article, the basic-level of nanoarchitectonics is first presented with atom/molecular-level structure formations and conversions from molecular units to functional materials. Then, two typical application-oriented nanoarchitectonics efforts in energy-oriented applications and bio-related applications are discussed. Finally, future directions of the molecular and materials nanoarchitectonics concepts for advancement of functional nanomaterials are briefly discussed.

Keywords: bio-related application; energy-oriented application; nanoarchitectonics; nanotechnology.

Figure 1

The nanoarchitectonics methodology to produce functional materials and functional structures from nanoscale unit components.

Figure 2

Nanoarchitectonics designs (models) of entrapment of fullerene molecules (C₆₀ molecules) within a carbon tube for single-molecule atomic-resolution real-time electron microscopic (SMART-EM) with image recording.

Figure 3

Molecular attachment to a surface of a carbon nanohorn for a single molecular level observation.

Figure 4

Two MOF structures (MOF-2 and MOF-5) obtained from the same precursors, zinc nitrate and benzene dicarboxylic acid in dimethylformamide under different conditions.

Figure 5

Nano-Saturn through supramolecular association between anthracene macrocyclic ring and ellipsoidal C₇₀ molecule.

Figure 6

(A) Carbon nanobelt with a closed loop of fully fused edge-sharing benzene rings; (B) Cylindrical C₃₀₄H₂₆₄ molecule with 40 benzene (phenine) units bonded mutually at the 1, 3, and 5 positions.

Figure 7

Fusion of molecules with a dimethyltetracene core and two bromoanthryl units into structure defined graphene nanoribbons.

Figure 8

Three different regioisomeric junctions synthesized from 10,10’-dibromo-9,9’-bianthryl and 1,3,6,8-tetrabromopyrene on Au (111) surface.

Figure 9

Synthesis of π-extended diaza[8]circulene through on-surface syntheses on a Au(111) surface.

Figure 10

Tip-induced debromination with substitution reaction with fullerene molecule were at three-dimensional graphene nanoribbon.

Figure 11

Nanoarchitectonics strategy to control the numbers of dopant atoms within solid electrolyte nanostructures using a Pt tip.

Figure 12

Structurally defined dendrimer cores to give metal cluster with precisely controlled number (12 atoms).

Figure 13

Parallel allays of the Au nanowires with regular wire-by-wire intervals (models) with narrow interval of 2.9 nm and wide interval of 9.1 nm, corresponding to interdigitated bilayer and non-interdigitated four layer of the ascorbic acid derivatives, respectively.

Figure 14

Surface nanoarchitectonics of conventional alumina materials to regenerate bio-like wettability functions of rose petal and lotus leaf effects where single molecule in assembled structure is only depicted.

Figure 15

Faint orientational changes of double-paddled binuclear Pt^II at the air-water interface from perpendicular to parallel accompanied with drastic increase of phosphorescence, as called submarine emission.

Figure 16

Nanoarchitectonics for preparation of carbon nanosheet from carbon ring molecule (9,9’,10,10’-tetrabutoxy-cyclo-[6]-paraphenylene-[2]-3,6-phenanthrenylene) through vortex Langmuir-Blodgett (vortex LB) method and calcination at 850 °C under N₂ gas flow.

Figure 17

A novel method, 100 °C-Langmuir-Blodgett (100-LB) technique to fabricate highly oriented uniform ultrathin films with edge-on orientation of polymeric semiconductors, poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno(3,2-b)-thiophene] (PBTTT), on ethylene glycol as a solvent for subphase.

Figure 18

Nanoarchitectonics approach to fabricate hollow MOF nanobubbles and their carbonized materials by combined processes of MOF coordination self-assembly, site-selective etching, and calcination.

Figure 19

Fabrication of cathode electrode structures for flexible micro-supercapacitors through electrophoresis method nanocarbon materials prepared from ZIF-8 particles.

Figure 20

Nanoarchitectonics approach on the basis of layer-by-layer (LbL) assembly of conductive polymers and MOF complexes for better oxygen reduction reaction.

Figure 21

DNA Programmable nanoarchitectonics with DNA components to form advanced supramolecular structures such as interlocked structure, catenane.

Figure 22

A polyamide with N-methylpyrrole (P) and N-methylimidazole (I) with bending hairpin structure binds to the minor groove of DNA upon hydrogen bond formation to specific nucleobases.

Figure 23

Assembling structures of naphthalenediimides conjugated with amino acid to form exciplex, excimer, and charge transfer complex depending on α-substituent of amino acids.

Figure 24

Photothermal nanodots from peptide-porphyrin conjugates for photothermal antitumor therapy.

Figure 25

Metallohydrogels prepared from self-assembled nanofibers of Fmoc amino acids and Ag nanoparticles for antibacterial effects.

Figure 26

Formation of networked nanofibers and hydrogel with designed peptide (Ac-EYEYKYEYKY-NH₂: E, glutamic acid; Y, tyrosine; K, lysine) with the aid of Ca²⁺.

Figure 27

Nanoarchitectonics of artificial metalloenzyme on the basis of glycosylation of proteins.