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## Meet the editors

Dr. Hemali Rathnayake is an associate professor in the Department of Nanoscience, Joint School of Nanoscience and Nanoengineering (JSNN), University of North Carolina at Greensboro (UNCG), USA. She obtained her BS in Chemistry from the University of Peradeniya, Sri Lanka, in 2000 and her Ph.D. from the Department of Chemistry, University of Massachusetts Amherst (UMass), USA, in 2007. Dr. Rathnayake is a pioneer

scientist and a chemist in nanomaterials chemistry with a focus on the interfacial interaction of nanomaterials, molecules, macromolecules, and polymers in homogeneous and heterogeneous media. Her research on the design, synthesis, self-assembly, and application of well-defined superstructures in nanoelectronics, environmental remediation, and sustainable energy has impacted the scientific community with highly rated peer-reviewed journal publications, patents, and more than eighty invited talks to scientific and non-scientific communities.

Dr. Gayani Pathiraja is a postdoctoral research scholar in the Department of Nanoscience, Joint School of Nanoscience and Nanoengineering (JSNN), University of North Carolina at Greensboro (UNCG), USA. She earned her bachelor's degree in Materials Science and Technology from Uva Wellassa University, Sri Lanka, and her master's degree in Electrochemistry/ Environmental Engineering from the University of Peradeniya,

Sri Lanka. She obtained her Ph.D. in Nanoscience from UNCG in 2021 with her investigation of the crystal growth mechanism and kinetics of ultrathin copper hydroxide/oxide nanowire self-assembly. Dr. Pathiraja began her academic career as a lecturer in the Department of Engineering Technology, University of Ruhuna, Sri Lanka in 2016. She is a co-author of several peer-reviewed journal publications and a book chapter, and she has presented her work at several regional, international, and national conferences.

Dr. Eram Sharmin is an associate professor in the Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Saudi Arabia. She received a BSc in Chemistry and an MSc in Organic Chemistry from Aligarh Muslim University (AMU), India in 1998 and 2000, respectively. She obtained her Ph.D. in Chemistry from Jamia Millia Islamia (JMI) - A Central University, New Delhi, India, in 2007. She previously

worked as a senior research fellow, research associate, and senior research associate (under the Scientists' Pool Scheme, Council of Scientific and Industrial Research (CSIR), India) at the Materials Research Laboratory, Department of Chemistry, JMI. Dr. Sharmin has more than fifty publications in peer-reviewed journals and books to her credit. She has presented more than thirty research papers at national and international conferences. Her research interests include the development of "green" materials with applications as antimicrobial and corrosion-resistant films, coatings, and packaging materials.

### Contents


Preface

The bottom-up approach for the self-assembly of molecules, macromolecules, and particles into well-defined superstructures provides superior structural control of materials compared to top-down methods. Nature largely utilizes macromolecules to construct supramolecular materials, which ultimately contribute to the great array of forms and functions of life. Thus, the self-assembly of materials and the formation of superstructures have been of great interest in the fields of materials science, nanosci-

This book describes the self-assembly of materials and supramolecular chemistry design principles for a broad spectrum of materials, including bio-inspired amphiphiles, metal oxides, metal nanoparticles, and organic–inorganic hybrid materials. It provides fundamental concepts of self-assembly design approaches and supramolecular chemistry principles for research ideas in nanotechnology applications. Written by leading scientists in their fields, this book includes six chapters organized into three sections: "Introduction to Self-Assembly and Supramolecular Chemistry",

"Amphiphiles Self-Assembly", and "Nanoparticles Self-Assembly and Their

Applications". We hope that this book will provide a foundation on supramolecular chemistry principles to students and active researchers who are interested in nanosci-

**Hemali Rathnayake and Gayani Pathiraja**

University of North Carolina at Greensboro,

Department of Pharmaceutical Chemistry,

Nanoscience Department,

Greensboro, USA

**Eram Sharmin**

 College of Pharmacy, Umm Al-Qura University, Mecca, Saudi Arabia

ence, and nanoengineering.

ence and nanoengineering.

## Preface

The bottom-up approach for the self-assembly of molecules, macromolecules, and particles into well-defined superstructures provides superior structural control of materials compared to top-down methods. Nature largely utilizes macromolecules to construct supramolecular materials, which ultimately contribute to the great array of forms and functions of life. Thus, the self-assembly of materials and the formation of superstructures have been of great interest in the fields of materials science, nanoscience, and nanoengineering.

This book describes the self-assembly of materials and supramolecular chemistry design principles for a broad spectrum of materials, including bio-inspired amphiphiles, metal oxides, metal nanoparticles, and organic–inorganic hybrid materials. It provides fundamental concepts of self-assembly design approaches and supramolecular chemistry principles for research ideas in nanotechnology applications. Written by leading scientists in their fields, this book includes six chapters organized into three sections: "Introduction to Self-Assembly and Supramolecular Chemistry", "Amphiphiles Self-Assembly", and "Nanoparticles Self-Assembly and Their Applications". We hope that this book will provide a foundation on supramolecular chemistry principles to students and active researchers who are interested in nanoscience and nanoengineering.

#### **Hemali Rathnayake and Gayani Pathiraja**

Nanoscience Department, University of North Carolina at Greensboro, Greensboro, USA

#### **Eram Sharmin**

Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Mecca, Saudi Arabia

**1**

Section 1

Introduction to Self-Assembly

and Supramolecular

Chemistry

Section 1

## Introduction to Self-Assembly and Supramolecular Chemistry

#### **Chapter 1**

## Introductory Chapter: Self-Assembly of Molecules into Supramolecular Structures

*Hemali Rathnayake*

#### **1. Overview**

The bottom-up approach for the self-assembly of molecules, macromolecules, and particles into well-defined superstructures provides superior structural control of materials compared to top-down methods. Nature largely utilizes macromolecules to construct supramolecular materials, ultimately contributing to a wide range of applications. Thus, the self-assembly of materials and the formation of superstructures have been of great interest in the fields of materials science, nanoscience, and nanoengineering.

This book provides the self-assembly of materials and supramolecular chemistry design principles for a broad spectrum of materials, including bio-inspired amphiphiles, metal oxides, metal nanoparticles, and organic-inorganic hybrid materials. It describes the fundamental concepts of self-assembly design approaches and supramolecular chemistry principles for research ideas in nanotechnology-enabled applications. The book focuses on three main themes, which include: the self-assembly and supramolecular chemistry of amphiphiles, the supramolecular structures and devices of inorganic materials, and the assembly-disassembly of organic-inorganic hybrid materials.

#### **2. Self-assembly of bioinspired amphiphiles**

Assembly of amphiphilic molecular and polymeric materials into precise functional structures is being explored actively for patterning and fabricating periodic array structures from mesoscale to nanoscale. Leading examples can be found in biosystems where assemblies of different amphiphilic components yield unusual microstructures that enable the performance of highly specific cellular functions [1–3]. For example, cell membrane's lipid bilayer, which is constructed from self-assembled phospholipids (PLs), is one of nature's well-organized nanoscale machines and is vital to cell's signal transduction. The self-assembly of biologically based lipids into unusual microstructures provides superior structural control due to the amphiphilic nature of lipids that are composed of a polar head group and a nonpolar hydrocarbon tail [4]. The dimensionality of the hydrated hydrophilic head group (0.7 to 1.0 nm) and the hydrophobic core of the bilayer (2.5 to 3.5 nm) results in varied tail lengths, which provide unprecedented control over the structural complexity and function at

the nanoscale. For instance, most long-chain PLs self-assemble into spherical bilayer aggregates, known as liposomes [5]. However, by exploiting the subtle interplay between appropriately modified head groups and fatty acid chains, certain synthetic phospholipids self-assemble into novel microstructures [6]. One such example consists of synthetic PLs with photopolymerizable diacetylenic moieties in the acyl chains that self-assemble into hollow, cylindrical structures, known as tubules [7, 8], which have also been observed in other synthetic surfactants [9] and in bile [10].

Owing to these remarkable supramolecular assemblies, bio-conjugated nanomaterials, consisting of lipid bilayers and inorganic nanomaterials, such as metal nanoparticles [11–13] and nanocarbon [14, 15], have been demonstrated as new functional materials for electronic devices. In these devices, lipid bilayers are used as electrically insulating substrates that confine the nanomaterials. Particularly, the recent research advancements in this field set forth the supramolecular design principles, enabling access to many of the current examples of nanomaterials conjugated lipid bilayer architectures [11, 16–21]. These efforts toward biological mimicry of supramolecular assemblies suggest that metal-nanoparticle arrays can be self-assembled in the lipid bilayer vesicles, and one can separate an array of nanoparticles with a uniform gap distance through supramolecular principles. By controlling the separation distance between nanoparticles or arrays with nanoscale precision using selective molecular interactions of lipids, many variations in the size and shape of the assembled nanostructures are possible [22, 23]. Additionally, it has been demonstrated that lipids can alter the dielectric properties of metallic nanoparticles, providing a way to modulate the optical properties of an integrated architecture and serve as optical sensors [24]. It has also been proven that the interaction between the lipid and nanoparticle can be adjusted by altering the nature of the polar head groups [25]. Because the study of PLs assembly is used to model biological membranes [26], current studies of the hybrid structures of metallic nanoparticles and PLs have shown the potential for the development of new biosensing devices and drug delivery methods across cellular membranes.

Utilizing bioinspired molecular and polymeric systems, stimuli-responsive nanomaterials with a variety of functionalities that respond to light [27], pH [28], temperature [29], and chemical [30] stimuli have been also developed. Although a variety of synthetic strategies enables the development of responsive materials, their structures exhibit limitations in morphological deformation in response to external stimuli. Transition metal ions are a unique tool for engineering responsive character based on their various binding stoichiometries and geometries, allowing a single material to have a diverse set of responses to different metal ions.7 Utilizing the dynamic nature of transition metal coordination bonds, structural control in small molecules [31–34] and proteins, [35–37] to develop responsive films, [38, 39] self-healing soft materials, [39–42] subcomponent self-assembly of polymeric materials, [43–46] and hierarchical assemblies of nanoparticles has been demonstrated [47, 48].

#### **3. Supramolecular nanoassemblies of π-conjugated molecular systems**

Conjugated organic molecules have been the subject of continuous interest in organic electronics. Synthetic efforts aimed at π-conjugated systems having welldefined architectures are indeed driven by the desire to impart specific optical and electrical properties to materials by controlling their molecular structure. Crafting the structure and function of organic materials using the strategies of self-assembly

#### *Introductory Chapter: Self-Assembly of Molecules into Supramolecular Structures DOI: http://dx.doi.org/10.5772/intechopen.109277*

and supramolecular chemistry has progressed over the past two decades in materials chemistry. A variety of systems have been engineered where function is directly linked to non-covalent interactions, such as ionic, hydrophobic, van der Waals, hydrogen, and coordination bonds. They also influence solid-state self-organization to produce an organized structure at any scale, ranging from the nano and micrometer scales to microscopic dimensions.

Great efforts have been directed to the solution-processable self-assembly of π- conjugated small molecules, oligomers, or polymers into shape-defined nanostructures. Bridging the gap between natural and artificial systems, well-organized nanomaterials can be prepared using self-assembly approaches [49–54]. The morphologies of these self-assembled nanostructures cooperatively control by non-covalent interactions, such as H- bonding, dipole-dipole attraction, π-π stacking, van der Waals force, hydrophobic effect, electrostatic interaction, and metal-ligand coordination. Most predominantly, intermolecular π-π interactions and H-bonding have been the major driving forces, which often cooperatively drive other weak non-covalent interactions [50, 55]. Moreover, non-covalent interactions are highly dependent on the molecular structure where external environmental parameters, such as solvent, temperature, concentration, and fabrication process are responsible for the morphology of the supramolecular structure [50, 52, 56].

1D nanostructures of organic semiconductors with morphologies, including nanowires, nanobelts, nanorods, nanotubes, and helices, have merited intensive study over the past two decades. These 1D functional nanostructures hold great potential for enabling next-generation electronic and optoelectronic nanodevices [57, 58]. Consequently, the self-assembly of π-conjugated organic molecules into 1D nanostructures has been an active and rapidly developing field [52, 59–64].

In recent years, the application of Watson-Crick pairing of nucleic acids, that is, the pairing of nucleic acids, using specific hydrogen bonding to pattern selfassembling and supramolecular organic materials, has transformed how we design, engineer, and synthesize structures at all scales [65–68]. In the context of organic materials, the ability to generate ordered one-dimensional structures (1D) is fundamentally useful and functional. Thus, there remains considerable untapped potential in 1D organic materials. Successful fabrication of 1D nanostructures demands a tight correlation between the self-assembling kinetics and the molecular design and engineering. This usually requires a strong interplay between chemical synthesis, materials fabrication, and physical characterization that relate to a broad range of applications in electronic devices. Thus, understanding how to design molecules that can form 1D structures through non-covalent interactions is a key objective in organic material chemistry. So far, there is no universal principle that can predict the formation of any sort of 1D molecular self-assembly. Therefore, in order to design selfassembled 1D nanostructures, the supramolecular chemistry approaches should not only focus on the design principles of the molecular and supramolecular structure but also control the dynamic assembly-disassembly of the architecture. For example, they can be cylindrical assemblies, flat or twisted ribbons, tubes, and many other shapes but retain their morphologies in one dimension during the assembly and disassembly process.

Planar and rigid aromatic molecules are known to form one-dimensional (1D) and three-dimensional (3D) nanostructures through strong π-π interactions, evidencing that such interactions could be an effective approach for the formation of 1D nanoassemblies [69–80]. However, it still remains a difficult task to fabricate 1D nanostructures with well-defined morphology and molecular arrangement of

these systems. Although impressive research have been performed on covalent and hydrogen-bonded dyads, triads, and higher order polycyclic aromatic systems in solution and solid phase [69–80]. research on further self-assembly of these complexes utilizing other strong non-covalent interactions, in particular, a combination of σ-holes and π−π interactions, is relatively scarce. This is quite unfortunate since self-assembly may have enormous potential for organic electronics, by providing a pathway to arrange electron donating (donors) and electron-accepting (acceptors) semiconducting fused-arene moieties into higher architectures through a wide variety of functional groups. In the solution phase, these systems can utilize for studying energy transfer phenomena as well as for understanding the feasibility of making dynamic self-assembled supramolecular structures by tailoring supramolecular interactions. For example, synergistic effect of non-covalent interactions, such as π-π stacking and hydrogen bonding on the chromophore stacking can reveal from their solution phase assembly behavior. These studies eventually can lead to the transfer of shape-persistent structures from solution to the thin film of the active layer of organic devices. Regardless, it is necessary to be programmed the molecular building blocks for the successful implementation of supramolecular electronics in practice, where the design enables the organization of functional chromophores into ordered, nanosized aggregates.

### **Conflict of interest**

The authors declare no conflict of interest.

### **Author details**

Hemali Rathnayake Nanoscience Department, University of North Carolina Greensboro, Greensboro, NC, USA

\*Address all correspondence to: hprathna@uncg.edu

© 2022 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

*Introductory Chapter: Self-Assembly of Molecules into Supramolecular Structures DOI: http://dx.doi.org/10.5772/intechopen.109277*

#### **References**

[1] Butler A, Theisen RM. Iron(III)– siderophore coordination chemistry: Reactivity of marine siderophores. Coordination Chemistry Reviews. 2010;**254**(3-4):288-296. Available from: https://pubmed.ncbi.nlm.nih. gov/21442004/

[2] Knight AS, Larsson J, Ren JM, Bou Zerdan R, Seguin S, Vrahas R, et al. Control of amphiphile self-assembly via bioinspired metal ion coordination. Journal of the American Chemical Society. 2018;**140**(4):1409-1414. Available from: https://europepmc.org/ article/med/29338205

[3] Glotzer SC, Solomon MJ. Anisotropy of building blocks and their assembly into complex structures. Nature Materials. 2007;**6**(8):557-562. Available from: https://pubmed.ncbi.nlm.nih. gov/17667968/

[4] Katsaras J, Gutberlet T. Lipid Bilayers. Berlin, Heidelberg: Springer Berlin Heidelberg; 2001. DOI: 10.1007/978- 3-662-04496-4

[5] Seddon JM, Templer RH. Polymorphism of lipid-water systems. Handbook of Biological Physics. 1995;**1995**:97-160. Available from: https://linkinghub.elsevier.com/retrieve/ pii/S1383812106800205

[6] Lee YL, Lin JY, Chang CH. Thermodynamic characteristics and Langmuir–Blodgett deposition behavior of mixed DPPA/DPPC monolayers at air/ liquid interfaces. Journal of Colloid and Interface Science. 2006;**296**(2):647-654. Available from: https://pubmed.ncbi. nlm.nih.gov/16225885/

[7] Bangham AD, Hill MW, Miller NGA. Preparation and use of liposomes as

models of biological membranes. In: Methods in Membrane Biology. Boston, MA: Springer US; 1974. DOI: 10.1007/ 978-1-4615-7422-4\_1

[8] Schnur JM, Peckerar MC, Stratton HM. Synthetic Microstructures in Biological Research. Boston, MA: Springer US; 1992. p. 249. Available from: https://agris.fao.org/agris-search/search. do?recordID=US201300721622

[9] Yager P, Schoen PE. Formation of tubules by a polymerizable surfactant. Molecular Crystals and Liquid Crystals. 1984;**106**(3-4):371-381. DOI: 10.1080/ 00268948408071454

[10] Schnur JM. Lipid tubules: A paradigm for molecularly engineered structures. Science. 1993;**262**(5140):1669-1676. DOI: 10.1126/ science.262.5140.1669

[11] Nakashima N, Asakuma S, Kunitake T. Optical microscopic study of helical superstructures of chiral bilayer membranes. Journal of the American Chemical Society. 1985;**107**(2):509-510. DOI: 10.1021/ja00288a043

[12] Chung DS, Benedek GB, Konikoff FM, Donovan JM. Elastic free energy of anisotropic helical ribbons as metastable intermediates in the crystallization of cholesterol. Proceedings of the National Academy of Sciences. 1993;**90**(23):11341-11345. DOI: 10.1021/ja00288a043

[13] Song J, Cheng L, Liu A, Yin J, Kuang M, Duan H. Plasmonic vesicles of amphiphilic gold nanocrystals: Selfassembly and external-stimuli-triggered destruction. Journal of the American Chemical Society. 2011;**133**(28):10760- 10763. DOI: 10.1021/ja204387w

[14] Song J, Zhou J, Duan H. Selfassembled plasmonic vesicles of SERSencoded amphiphilic gold nanoparticles for cancer cell targeting and traceable intracellular drug delivery. Journal of the American Chemical Society. 2012;**134**(32):13458-13469. DOI: 10.1021/ ja305154a

[15] Zeng Y, Zhang D, Wu M, Liu Y, Zhang X, Li L, et al. Lipid-AuNPs@PDA nanohybrid for MRI/CT imaging and photothermal therapy of hepatocellular carcinoma. ACS Applied Materials & Interfaces. 2014;**6**(16):14266-14277. Available from: https://pubmed.ncbi. nlm.nih.gov/25090604/

[16] Huang SCJ, Artyukhin AB, Misra N, Martinez JA, Stroeve PA, Grigoropoulos CP, et al. Carbon nanotube transistor controlled by a biological ion pump gate. Nano Letters. 2010;**10**(5):1812-1816. Available from: https://pubmed.ncbi.nlm.nih. gov/20426455/

[17] Frost R, Svedhem S, Langhammer C, Kasemo B. Graphene oxide and lipid membranes: Size-dependent interactions. Langmuir. 2016;**32**(11):2708-2717. DOI: 10.1021/acs.langmuir.5b03239

[18] Kim K, Geng J, Tunuguntla R, Comolli LR, Grigoropoulos CP, Ajo-Franklin CM, et al. Osmoticallydriven transport in carbon nanotube porins. Nano Letters. 2014;**14**(12):7051- 7056. Available from: https://pubmed. ncbi.nlm.nih.gov/25372973/

[19] Rasch MR, Rossinyol E, Hueso JL, Goodfellow BW, Arbiol J, Korgel BA. Hydrophobic gold nanoparticle selfassembly with phosphatidylcholine lipid: Membrane-loaded and Janus vesicles. Nano Letters. 2010;**10**(9):3733-3739. DOI: 10.1021/nl102387n

[20] Rasch MR, Yu Y, Bosoy C, Goodfellow BW, Korgel BA.

Chloroform-enhanced incorporation of hydrophobic gold nanocrystals into dioleoylphosphatidylcholine (DOPC) vesicle membranes. Langmuir. 2012;**28**(36):12971-12981. Available from: https://www.ncbi.nlm.nih.gov/pmc/ articles/pmid/22897240/?tool=EBI

[21] Šegota S, Vojta D, Kendziora D, Ahmed I, Fruk L, Baranović G. Liganddependent nanoparticle clustering within lipid membranes induced by surrounding medium. The Journal of Physical Chemistry. B. 2015;**119**(16):5208-5219. DOI: 10.1021/acs.jpcb.5b00898

[22] Park SH, Oh SG, Mun JY, Han SS. Loading of gold nanoparticles inside the DPPC bilayers of liposome and their effects on membrane fluidities. Colloids and Surfaces. B, Biointerfaces. 2006;**48**(2):112-118. Available from: https://pubmed.ncbi.nlm.nih. gov/16520025/

[23] Sakaguchi N, Kimura Y, Hirano-Iwata A, Ogino T. Fabrication of Au-nanoparticle-embedded lipid bilayer membranes supported on solid substrates. The Journal of Physical Chemistry. B. 2017;**121**(17):4474-4481. Available from: https://pubmed.ncbi. nlm.nih.gov/28414450/

[24] Howland MC, Szmodis AW, Sanii B, Parikh AN. Characterization of physical properties of supported phospholipid membranes using imaging ellipsometry at optical wavelengths. Biophysical Journal. 2007;**92**(4):1306- 1317. Available from: https:// linkinghub.elsevier.com/retrieve/pii/ S0006349507709414

[25] Nieh MP, Raghunathan VA, Glinka CJ, Harroun TA, Pabst G, Katsaras J. Magnetically alignable phase of phospholipid "Bicelle" mixtures is a chiral nematic made up of wormlike micelles. Langmuir.

*Introductory Chapter: Self-Assembly of Molecules into Supramolecular Structures DOI: http://dx.doi.org/10.5772/intechopen.109277*

2004;**20**(19):7893-7897. Available from: https://pubmed.ncbi.nlm.nih. gov/15350048/

[26] Ma G, Allen HC. Condensing effect of palmitic acid on DPPC in mixed langmuir monolayers. Langmuir. 2007;**23**(2):589-597. Available from: https://pubmed.ncbi.nlm.nih. gov/17209610/

[27] Coleman AC, Beierle JM, Stuart MCA, Maciá B, Caroli G, Mika JT, et al. Light–induced disassembly of self-assembled vesicle-capped nanotubes observed in real time. Nature Nanotechnology. 2011;**6**(9):547-552. Available from: https://pubmed.ncbi. nlm.nih.gov/21841795/

[28] Jang SG, Audus DJ, Klinger D, Krogstad DV, Kim BJ, Cameron A, et al. Striped, ellipsoidal particles by controlled assembly of diblock copolymers. Journal of the American Chemical Society. 2013;**135**(17):6649-6657. DOI: 10.1021/ ja4019447

[29] Moughton AO, O'Reilly RK. Thermally induced micelle to vesicle morphology transition for a charged chain end diblock copolymer. Chemical Communications. 2010;**46**(7):1091-1093. Available from: https://pubs.rsc.org/en/ content/articlehtml/2010/cc/b922289h

[30] Yan Q, Zhao Y. CO2-stimulated diversiform deformations of polymer assemblies. Journal of the American Chemical Society. 2013;**135**(44):16300- 16303. DOI: 10.1021/ja408655n

[31] Philip A, Gale JWS. Supramolecular Chemistry: From Molecules to Nanomaterials. 1st ed. Chichester, West Sussex: Wiley; 2012. p. 4014. Available from: https://www.worldcat.org/ title/753634033

[32] Geng Y, Wang XJ, Chen B, Xue H, Zhao YP, Lee S, et al. Semiconducting neutral microstructures fabricated by coordinative self-assembly of intramolecular charge-transfer tetrathiafulvalene derivatives. Chemistry - A European Journal. 2009;**15**(20):5124- 5129. Available from: https://pubmed. ncbi.nlm.nih.gov/19322846/

[33] Li L, Ke CF, Zhang HY, Liu Y. Coordination-induced switchable nanoparticle formation from naphthylbridged bis(β-cyclodextrin). The Journal of Organic Chemistry. 2010;**75**(19):6673- 6676. Available from: https://pubmed. ncbi.nlm.nih.gov/20806949/

[34] Xiao ZY, Zhao X, Jiang XK, Li ZT. Tunable coordinative assembly of a disc-like molecule and metal ions: From mirospheres to microtubes and microrods. Chemistry of Materials. 2011;**23**(6):1505-1511. DOI: 10.1021/ cm103182e

[35] van Eldijk MB, Schoonen L, Cornelissen JJLM, Nolte RJM, van Hest JCM. Metal ion-induced selfassembly of a multi-responsive block copolypeptide into well-defined nanocapsules. Small. 2016;**12**(18):2476- 2483. Available from: https://pubmed. ncbi.nlm.nih.gov/27151830/

[36] Salgado EN, Radford RJ, Tezcan FA. Metal-directed protein self-assembly. Accounts of Chemical Research. 2010;**43**(5):661-672. DOI: 10.1021/ ar900273t

[37] Nepal M, Sheedlo MJ, Das C, Chmielewski J. Accessing threedimensional crystals with incorporated guests through metal-directed coiled-coil peptide assembly. Journal of the American Chemical Society. 2016;**138**(34):11051-11057. DOI: 10.1021/ jacs.6b06708

[38] Michal BT, McKenzie BM, Felder SE, Rowan SJ. Metallo-, thermo-, and photoresponsive shape memory and actuating liquid crystalline elastomers. Macromolecules. 2015;**48**(10):3239-3246. DOI: 10.1021/acs.macromol.5b00646

[39] Mozhdehi D, Ayala S, Cromwell OR, Guan Z. Self-healing multiphase polymers via dynamic metal–ligand interactions. Journal of the American Chemical Society. 2014;**136**(46):16128-16131. DOI: 10.1021/ ja5097094

[40] Grindy SC, Learsch R, Mozhdehi D, Cheng J, Barrett DG, Guan Z, et al. Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics. Nature Materials. 2015;**14**(12):1210-1216. Available from: https://pubmed.ncbi. nlm.nih.gov/26322715/

[41] Whittell GR, Hager MD, Schubert US, Manners I. Functional soft materials from metallopolymers and metallosupramolecular polymers. Nature Materials. 2011;**10**(3):176-188. Available from: https://pubmed.ncbi.nlm.nih. gov/21336298/

[42] Ott C, Hoogenboom R, Hoeppener S, Wouters D, Gohy JF, Schubert US. Tuning the morphologies of amphiphilic metallo-supramolecular triblock terpolymers: From spherical micelles to switchable vesicles. Soft Matter. 2009;**5**(1):84-91. Available from: https://pubs.rsc.org/en/content/ articlehtml/2009/sm/b813161a

[43] Gao H, Liu G, Chen X, Hao Z, Tong J, Lu L, et al. Media-modulated interchain or intrachain coordination of amphiphilic block copolymer micelles. Macromolecules. 2010;**43**(14):6156-6165. DOI: 10.1021/ma100761a

[44] Chen X, Xu N, Li N, Lu L, Cai Y, Zhao Y, et al. Programmable selectivity of metal–imine bond coordination

in subcomponent self-assembly of a primary amine based block copolymer. Soft Matter. 2013;**9**(6):1885-1894. Available from: https://pubs.rsc.org/ en/content/articlehtml/2013/sm/ c2sm26904j

[45] Wu X, Xu N, Zhu Z, Cai Y, Zhao Y, Wang D. Subcomponent self-assembly of polymer chains based on dynamic and geometrical coordination diversity of the first row transition metal ions. Polymer Chemistry. 2014;**5**(4):1202-1209. Available from: https://pubs.rsc.org/en/ content/articlehtml/2014/py/c3py01111a

[46] Xu N, Han J, Zhu Z, Song B, Lu X, Cai Y. Directional supracolloidal selfassembly via dynamic covalent bonds and metal coordination. Soft Matter. 2015;**11**(27):5546-5553. Available from: https://pubs.rsc.org/en/content/ articlehtml/2015/sm/c5sm00546a

[47] Wang Y, Hollingsworth AD, Yang SK, Patel S, Pine DJ, Weck M. Patchy particle self-assembly via metal coordination. Journal of the American Chemical Society. 2013;**135**(38):14064-14067. Available from: https://pubmed.ncbi. nlm.nih.gov/24044358/

[48] Lunn DJ, Gould OEC, Whittell GR, Armstrong DP, Mineart KP, Winnik MA, et al. Microfibres and macroscopic films from the coordination-driven hierarchical self-assembly of cylindrical micelles. Nature Communications. 2016;**7**(1):12371. Available from: https:// pubmed.ncbi.nlm.nih.gov/27538877/

[49] Whitesides GM, Simanek EE, Mathias JP, Seto CT, Chin D, Mammen M, et al. Noncovalent synthesis: Using physical-organic chemistry to make aggregates. Accounts of Chemical Research. 1995;**28**(1):37-44. DOI: 10.1021/ar00049a006

[50] Hoeben FJM, Jonkheijm P, Meijer EW, Schenning APHJ. About *Introductory Chapter: Self-Assembly of Molecules into Supramolecular Structures DOI: http://dx.doi.org/10.5772/intechopen.109277*

supramolecular assemblies of π-conjugated systems. Chemical Reviews. 2005;**105**(4):1491-1546. DOI: 10.1021/ cr030070z

[51] Zhang Z, Ma R, Shi L. Cooperative macromolecular self-assembly toward polymeric assemblies with multiple and bioactive functions. Accounts of Chemical Research. 2014;**47**(4):1426- 1437. DOI: 10.1021/ar5000264

[52] Schenning APHJ, Meijer EW. Supramolecular electronics; nanowires from self-assembled π-conjugated systems. Chemical Communications. 2005;**26**:3245. Available from: http:// xlink.rsc.org/?DOI=b501804h

[53] Wu J, Pisula W, Müllen K. Graphenes as potential material for electronics. Chemical Reviews. 2007;**107**(3):718-747. DOI: 10.1021/cr068010r

[54] Würthner F. Supramolecular polymerization: Living it up. Nature Chemistry. 2014;**6**(3):171-173. Available from: https://pubmed.ncbi.nlm.nih. gov/24557127/

[55] González-Rodríguez D, Schenning APHJ. Hydrogen-bonded supramolecular π-functional materials. Chemistry of Materials. 2011;**23**(3):310- 325. DOI: 10.1021/cm101817h

[56] Ariga K, Hill JP, Lee MV, Vinu A, Charvet R, Acharya S. Challenges and breakthroughs in recent research on self-assembly. Science and Technology of Advanced Materials. 2008;**9**(1):014109. DOI: 10.1088/ 1468-6996/9/1/014109

[57] Nguyen TQ, Martel R, Bushey M, Avouris P, Carlsen A, Nuckolls C, et al. Self-assembly of 1-D organic semiconductor nanostructures. Physiological Chemistry and Physics. 2007;**9**(13):1515. Available from:

https://pubs.rsc.org/en/content/ articlehtml/2007/cp/b609956d

[58] Kim FS, Ren G, Jenekhe SA. One-dimensional nanostructures of π-conjugated molecular systems: Assembly, properties, and applications from photovoltaics, sensors, and nanophotonics to nanoelectronics. Chemistry of Materials. 2011;**23**(3):682- 732. DOI: 10.1021/cm102772x

[59] Meijer EW, Schenning APHJ. Material marriage in electronics. Nature. 2002;**419**(6905):353-354. Available from: https://pubmed.ncbi.nlm.nih. gov/12353020/

[60] Wang X, Li Y. Solutionbased synthetic strategies for 1-D nanostructures. Inorganic Chemistry. 2006;**45**(19):7522-7534. DOI: 10.1021/ ic051885o

[61] Zang L, Che Y, Moore JS. Onedimensional self-assembly of planar π-conjugated molecules: Adaptable building blocks for organic nanodevices. Accounts of Chemical Research. 2008;**41**(12):1596-1608. DOI: 10.1021/ ar800030w

[62] Zhao YS, Fu H, Peng A, Ma Y, Liao Q, Yao J. Construction and optoelectronic properties of organic onedimensional nanostructures. Accounts of Chemical Research. 2010;**43**(3):409-418. DOI: 10.1021/ar900219n

[63] Su B, Wu Y, Jiang L. The art of aligning one-dimensional (1D) nanostructures. Chemical Society Reviews. 2012;**41**(23):7832. Available from: https://pubs.rsc.org/en/content/ articlehtml/2012/cs/c2cs35187k

[64] Dasgupta NP, Sun J, Liu C, Brittman S, Andrews SC, Lim J, et al. 25th Anniversary Article: Semiconductor nanowires - Synthesis, characterization,

and applications. Advanced Materials. 2014;**26**(14):2137-2184. DOI: 10.1002/ adma.201305929

[65] Zheng J, Constantinou PE, Micheel C, Alivisatos AP, Kiehl RA, Seeman NC. Two-dimensional nanoparticle arrays show the organizational power of robust DNA motifs. Nano Letters. 2006;**6**(7):1502-1504. Available from: https://pubmed.ncbi.nlm.nih. gov/16834438/

[66] Park SY, Lytton-Jean AKR, Lee B, Weigand S, Schatz GC, Mirkin CA. DNA-programmable nanoparticle crystallization. Nature. 2008;**451**(7178): 553-556. Available from: https://pubmed. ncbi.nlm.nih.gov/18235497/

[67] Aldaye FA, Palmer AL, Sleiman HF. Assembling materials with DNA as the guide. Science. 2008;**321**(5897):1795- 1799. Available from: https://pubmed. ncbi.nlm.nih.gov/18818351/

[68] Sayar M, Stupp SI. Selforganization of rod-coil molecules into nanoaggregates: A coarse grained model. Macromolecules. 2001;**34**:7135-7139. Available from: https://pubs.acs.org/ sharingguidelines

[69] Duzhko V, Singer KD. Self-assembled fibers of a discotic phthalocyanine derivative: Internal structure, tailoring of geometry, and alignment by a direct current electric field. Journal of Physical Chemistry C. 2007;**111**(1):27-31. DOI: 10.1021/jp066936x

[70] Hill JP, Jin W, Kosaka A, Fukushima T, Ichihara H, Shimomura T, et al. Self-assembled hexa- peri -hexabenzocoronene graphitic nanotube. Science. 2004;**304**(5676):1481-1483. DOI: 10.1126/science.1097789

[71] Briseno AL, Mannsfeld SCB, Reese C, Hancock JM, Xiong Y, Jenekhe SA, et al.

Perylenediimide nanowires and their use in fabricating field-effect transistors and complementary inverters. Nano Letters. 2007;**7**(9):2847-2853. DOI: 10.1021/ nl071495u

[72] Praefcke K, Singer D, Kohne B, Ebert M, Liebmann A, Wendorff JH. Charge transfer induced nematic columnar phase in low molecular weight disc-like systems. Liquid Crystals. 1991;**10**(2):147-159. DOI: 10.1080/ 02678299108036421

[73] Tang Q, Li H, He M, Hu W, Liu C, Chen K, et al. Low threshold voltage transistors based on individual singlecrystalline submicrometer-sized ribbons of copper phthalocyanine. Advanced Materials. 2006;**18**(1):65-68. DOI: 10.1002/adma.200501654

[74] Bendikov M, Wudl F, Perepichka DF. Tetrathiafulvalenes, oligoacenenes, and their buckminsterfullerene derivatives: The brick and mortar of organic electronics. Chemical Reviews. 2004;**104**(11):4891-4946. Available from: https://pubmed.ncbi.nlm.nih. gov/15535637/

[75] Balakrishnan K, Datar A, Oitker R, Chen H, Zuo J, Zang L. Nanobelt selfassembly from an organic n-type semiconductor: Propoxyethyl-PTCDI. Journal of the American Chemical Society. 2005;**127**(30):10496-10497. DOI: 10.1021/ja052940

[76] Balakrishnan K, Datar A, Naddo T, Huang J, Oitker R, Yen M, et al. Effect of side-chain substituents on self-assembly of perylene diimide molecules: Morphology control. Journal of the American Chemical Society. 2006;**128**(22):7390-7398. Available from: https://pubmed.ncbi.nlm. nih.gov/16734495/

[77] Sinks LE, Rybtchinski B, Iimura M, Jones BA, Goshe AJ, Zuo X, et al. Selfassembly of photofunctional cylindrical *Introductory Chapter: Self-Assembly of Molecules into Supramolecular Structures DOI: http://dx.doi.org/10.5772/intechopen.109277*

nanostructures based on perylene-3,4:9,10-bis(dicarboximide). Chemistry of Materials. 2005;**17**(25):6295-6303. DOI: 10.1021/cm051461s

[78] Gesquière A, Jonkheijm P, Hoeben FJM, Schenning APHJ, De Feyter S, De Schryver FC, et al. 2D-structures of quadruple hydrogen bonded oligo(p-phenylenevinylene)s on graphite: Self-assembly behavior and expression of chirality. Nano Letters. 2004;**4**(7):1175-1179. DOI: 10.1021/ nl049842c

[79] Schenning APHJ et al. Photoinduced electron transfer in hydrogen-bonded oligo(p -phenylene vinylene)—perylene bisimide chiral assemblies. Journal of the American Chemical Society. 2002;**124**(35):10252-10253. DOI: 10.1021/ ja020378s

[80] Gehan TS, Bag M, Renna LA, Shen X, Algaier DD, Lahti PM, et al. Multiscale active layer morphologies for organic photovoltaics through selfassembly of nanospheres. Nano Letters. 2014;**14**(9):5238-5243. DOI: 10.1021/ nl502209s

Section 2
