RESEARCH

5. Self-assembling Systems

Self-assembly is an excellent means for preparing complex objects or materials with unusual nano- or microstructures. We apply self-assembly concepts to both conventional amphiphilic surfactants and functional molecules such as porphyrins or pyrazinacenes.Amphiphilic properties, coordination chemistry and hydrogen bonding have all been applied in the development of some highly complex assemblies or hierarchically assembled systems.

Amphiphilic assembly of trigeminal porphyrins for controllable nanowire fabrication at a surface – molecular mobility aids the preparation of complex patterns of nanowires. (a) Atomic force microscopy of the nanowire formations. (b) model structure.

Self-assembled pyrazinacene nanotubes. (a) Dark field transmission electron microscopy image of the nanotubes with fans of expelled materials. (b) Multiwalled self-assembled nanotunes.

(a) Molecular assemblies involving three different chromophores and anionic cofactors for mimicking of light harvesting processes and the influence of cofactors. (b) Oxocorrologen, a molecule with potentially ten different tautomeric forms.

Porphyrin-fullerene zebra nanowires assembled from block copolymers synthesized using living polymerization. The dimensions of the porphyrin- and fullerene-containing domains in these nanowires could be tuned minutely and the nanowires exhibited very high charge carrier mobilities due to the nanostructuring.

Lead sulphide nanowires were converted to lead sulphide 2-dimensional sheets by applying a supramolecular concept involving Langmuir-Blodgett techniques.

Related publications

S. Acharya, B. Das, U. Thupakula, K. Ariga, D. D. Sarma, J. Israelachvili, and Y. Golan. “A Bottom-up Approach Towards Fabrication of Ultrathin PbS Sheets” Nano Letters (2013) 13, 409–415. [Link ]
J. P. Hill, Y, Xie, M, Akada, Y, Wakayama, L, K, Shrestha, Q, Ji and K, Ariga. “Controlling Porphyrin Nanoarchitectures at Solid Interfaces” Langmuir (2013) 29, 7291–7299. [Link ]
T. Mori, K. Sakakibara, H. Endo, M.Akada, K. Okamoto, A. Shundo, M. V. Lee, Q. Ji, T. Fujisawa, K. Oka, M. Matsumoto, H. Sakai, M. Abe, J. P. Hill and K. Ariga. “Langmuir Nanoarchitectonics: One-Touch Fabrication of Regularly Sized Nanodisks at the Air-Water Interface” Langmuir (2013) 29, 7239–7248. [Link ]
N. M. Sanchez-Ballester, L. K. Shrestha, M. R. J. Elsegood, K. Ariga, C. E. Anson, W. Schmitt, J. P. Hill and A. K. Powell. “Ligand Displacement for Fixing Manganese: Relevance for Cellular Metal Ion Transport and Synthesis of Polymeric Coordination Complexes” Dalton Trans. (2013) 42, 2779–2785. [Link ]
K. Ariga, Q. Ji, T. Mori, M. Naito, Y. Yamauchi, H. Abe and J. P. Hill. “Enzyme Nanoarchitectonics: Organization and Device Application” Chem. Soc. Rev. (2013) 42, 6322–6345. [Link ]
A. M. Ako,M. Sahabul Alam, M. Rahman, J. P. Hill, N. M. Sanchez-Ballester, K. Ariga, C. E. Anson and A. K. Powell. “Self-assembly of a Mononuclear [FeIII(L)(EtOH)2] Complex bearing an n-Dodecyl Chain on Solid HOPG Surfaces” Chem. Eur. J. (2012) 18, 16419–16425. [Link ]
S. Ishihara, Y. Furuki, J. P. Hill, K. Ariga and S. Takeoka. “Coordinative Nanoporous Polymers Synthesized with Hydrogen-Bonded Columnar Liquid Crystals” J. Nanosci. Nanotechnol. (2012) 12, 7885–7895. [Link ]
M. Li, S. Ishihara, Q. Ji, M. Akada, J. P. Hill and Katsuhiko Ariga. “Paradigm shift from self-assembly to commanded assembly of functional materials: recent examples in porphyrin/fullerene supramolecular systems” Sci. Tech. Adv. Mater. (2012) 13, 053001. [Link ]
M. Ramanathan, S. M. Kilbey II, Q. Ji, J. P. Hill and K. Ariga. “Materials Self-assembly and Fabrication in Confined Spaces” J. Mater. Chem. (2012) 22, 10389–10405. [Link ]
F. Geng, H. Gao, Q. Meng, Z. Dong, Y. Wakayama, M. Akada, K. Ariga and J. P. Hill. “Anchoring of Self-assembled Monolayers of Unsymmetrically-substituted Chromophores with an Oxoporphyrinogen Surface Clamp” Chem. Commun. (2011) 47, 8533–8535. [Link ]
R. Charvet, K. Ariga, J. P. Hill, Q. Ji, A. H. Khan and S. Acharya. “Large Scale Assembly of Ordered Donor-Acceptor Heterojunction Molecular Wires using Langmuir-Blodgett Technique” Chem. Commun. (2011) 47, 6825–6827. [Link ]
Y. Xie, M. Akada, J. P. Hill, Q. Ji, R. Charvet and K. Ariga. “Real time Self-assembly and Reassembly of Molecular Nanowires of Trigeminal Amphiphile Porphyrins” Chem. Commun. (2011) 47, 2285–2287. [Link ]
G. J. Richards, J. P. Hill, J. Labuta, Y. Wakayama, M. Akada and K. Ariga. “Self-assembled Pyrazinacene Nanotubes” Phys. Chem. Chem. Phys. (2011) 13, 4868–4876. [Link ]
J. P. Hill, M. E. El-Khouly, R. Charvet, N. K. Subbaiyan, K. Ariga, S. Fukuzumi and F. D’Souza. “Effect of Anion Binding on Charge Stabilization in a Bis-Fullerene-Oxoporphyrinogen Conjugate” Chem. Commun. (2010) 46, 7933–7935. [Link ]
F. D’Souza, N. K. Subbaiyan, Y. Xie, J. P. Hill, K. Ariga, K. Ohkubo and S. Fukuzumi. “Anion-complexation-induced Stabilization of Charge Separation” J. Am. Chem. Soc. (2009) 131, 16138–16146. [Link ]
R. Charvet, S. Acharya, J. P. Hill, M. Akada, M. Liao, S. Seki, Y. Honsho, A. Saeki and K. Ariga. “Block-Copolymer-Nanowires with Nanosized Domain Segregation and High Charge Mobilities as Stacked p/n Heterojunction Arrays for Repeatable Photocurrent Switching” J. Am. Chem. Soc. (2009) 131, 18030–18031. [Link ]
Y. Xie, J. P. Hill, A. L. Schumacher, A. S. D. Sandanayaka, Y. Araki, P. A. Karr, J. Labuta, F. D’Souza, O. Ito, C. E. Anson, A. K. Powell and K. Ariga. “Twisted, Two-faced Porphyrins as Hosts for Bispyridyl Fullerenes: Construction and Photophysical Properties” J. Phys. Chem. C (2008) 112, 10559–10572. [Link ]
J. P. Hill, Y. Wakayama, M. Akada and K. Ariga. “Self-Assembly Structures of a Phenol-Substituted Porphyrin in the Solid State: Hydrogen Bonding, Kagomé Lattice and Defect Tolerance” J. Phys. Chem. C. (2007) 111, 16174–16180. [Link ]
J. P. Hill, Y. Wakayama, W. Schmitt, T. Tsuruoka, T. Nakanishi, P. A. Karr, M. L. Zandler, A. L. McCarty, F. D’Souza, L. R. Milgrom and K. Ariga. “Regulating the Stability of 2-Dimensional Crystal Structures using an Oxidation State dependent Molecular Conformation” Chem. Commun. (2006) 2320–2322. [Link ]
J. P. Hill, Y. Wakayama and K. Ariga. “How Molecules accommodate a 2-D Lattice Mismatch: an Unusual ‘Mixed’ Conformation of Tetraphenylporphyrin” Phys. Chem. Chem. Phys. (2006) 8, 5034–5037. [Link ]
W. Schmitt, J. P. Hill, S. Malik, C. A. Volkert, I. Ichinose, C.E. Anson and A. K. Powell. “Thermolysis of a Hybrid Organic-Inorganic Supramolecular Coordination Assembly: Templating the Formation of Nanostructured Fibrous Materials and C-based Microcapsules” Angew. Chem., Int. Ed. (2005) 44, 7048–7053. [Link ]
W. Schmitt, J. P. Hill, P. Juanico, A. Caneschi, F. Costantino, C. E. Anson and A. K. Powell. “Supramolecular Coordination Assemblies of Dinuclear FeIII Complexes” Angew. Chem., Int. Ed. (2005) 44, 4187–4192. [Link ]
J. P. Hill, W. Jin, A. Kosaka, T. Fukushima, H. Ichihara, T. Shimomura, K. Ito, T. Hashizume, N. Ishii and T. Aida. “Self-Assembled Hexa-peri-hexabenzocoronene Graphitic Nanotubes” Science (2004) 304, 1481–1483. [Link ]
W. Schmitt, C. E. Anson, J. P. Hill and A. K. Powell. “Cation-p binding of an Alkali Metal Ion by Pendant a,a-Dimethylbenzyl Groups in a Mixed Metal Coordination Complex” J. Am. Chem. Soc. (2003) 125, 11142–11143. [Link ]