Paradigm shift from self-assembly to commanded assembly of functional materials: recent examples in porphyrin/fullerene supramolecular systems

Abstract

Current nanotechnology based on top-down nanofabrication may encounter a variety of drawbacks in the near future so that development of alternative methods, including the so-called bottom-up approach, has attracted considerable attention. However, the bottom-up strategy, which often relies on spontaneous self-assembly, might be inefficient in the development of the requisite functional materials and systems. Therefore, assembly processes controlled by external stimuli might be a plausible strategy for the development of bottom-up nanotechnology. In this review, we demonstrate a paradigm shift from self-assembly to commanded assembly by describing several examples of assemblies of typical functional molecules, i.e. porphyrins and fullerenes. In the first section, we describe recent progress in the design and study of self-assembled and co-assembled supramolecular architectures of porphyrins and fullerenes. Then, we show examples of assembly induced by external stimuli. We emphasize the paradigm shift from self-assembly to commanded assembly by describing the recently developed electrochemical-coupling layer-by-layer (ECC-LbL) methodology.

Fabrication of Epoxy Vesicles using Self-Assembling Polystyrene–Montmorillonite Nanocomposite Reusable Template

“…The physical, chemical and biological properties of polymer vesicles can be tailored by varying the structure and block lengths of the polymer making them potentially interesting systems for applications as advanced functional materials. [1][2][3][4][5][6][7][8] Amphiphilic block copolymers, 9 rod-coil diblock copolymers 10 and dendrimers 11 were reported to form vesicular structures through solventassisted self-assembly. Only very few reports are there on the synthesis of rigid polymer vesicles based on block copolymers.…”

Layer-by-layer Nanoarchitectonics: Invention, Innovation, and Evolution

“…254,255 Electrochemical stimuli from an electrode surface beneath the films initiates and permits LbL assembly to proceed, and the use of additional reactants is not necessary. The resulting di-Nalkylcarbazole, unlike other electropolymerizable precursors such as aniline and thiophene, is transparent in the visible light region.…”

New Donor-Acceptor Porphyrin-Fullerene Dyades

“…Последние уже сейчас активно используются в качестве фотоактивного материала в органических солнечных батареях. [18][19][20][21] Прогресс в синтезе координационных порфирин-фуллереновых супрамолекул явно опережает развитие их физикохимии и поэтому чаще обусловлен хаотическим выбором составов комплексов и методов их сборки или синтеза. Несколько лет назад [22,23] авторы данной статьи, имея богатый опыт в области молекулярного комплексообразования MP с неорганическими и сложными органическими основаниями, [24][25][26][27] приступили к изучению природы, состава и количественных характеристик устойчивости донорно-акцепторных порфирин-фуллереновых комплексов, при образовании которых координационно ненасыщенный MP выступает в качестве акцептора, а пиридильный заместитель в молекуле пирролидинил-[60]фуллерена -в качестве донора электронной плотности.…”