Diacetylene Mixed Langmuir Monolayers for Interfacial Polymerization

Abstract

Polydiacetylene (PDA) and its derivatives are promising materials for applications in a vast number of fields, from organic electronics to biosensing. PDA is obtained through polymerization of diacetylene (DA) monomers, typically using UV irradiation. DA polymerization is a 1-4 addition reaction with both initiation and growth steps with topochemical control, leading to the "blue" polymer form as primary reaction product in bulk and at interfaces. Herein, the diacetylene monomer 10,12-pentacosadiynoic acid (DA) and the amphiphilic cationic N,N'-dioctadecylthiapentacarbocyanine (OTCC) have been used to build a mixed Langmuir monolayer. The presence of OTCC imposes a monolayer supramolecular structure instead of the typical trilayer of pure DA. Surface pressure, Brewster angle microscopy, and UV-vis reflection spectroscopy measurements, as well as computer simulations, have been used to assess in detail the supramolecular structure of the DA:OTCC Langmuir monolayer. Our experimental results indicate that the DA and OTCC molecules are sequentially arranged, with the two OTCC alkyl chains acting as spacing diacetylene units. Despite this configuration is expected to prevent photopolymerization of DA, the polymerization takes place without phase segregation, thus exclusively leading to the red polydiacetylene form. We propose a simple model for the initial formation of the "blue" or "red" PDA forms as a function of the relative orientation of the DA units. The structural insights and the proposed model concerning the supramolecular structure of the "blue" and "red" forms of the PDA are aimed at the understanding of the relation between the molecular and macroscopical features of PDAs.

Transfer and Amplification of Iodine-Based Diacetylene Amphiphiles to Anisotropic Optical Properties by Uniaxial Orientation in Thin Films

“…To successfully complete topochemical polymerization, DAs must be self-assembled to meet specific geometrical parameters. − Since the volume of the hydrophilic groups for the MIDA/TIDA mixture is larger than that of the hydrophobic DA moiety, it is not sufficient to meet the requirements for uniaxial molecular alignment as well as polymerization. Unlike TIDA, MIDA itself can be topochemically polymerized in the crystalline phase.…”

Synthesis of Responsive Two‐Dimensional Polymers via Self‐Assembled DNA Networks

“…To further explore the potential of this fascinating class of materials, alternative synthetic strategies are in demand. Supramolecular polymerization provides an elegant access to the assembly of 2D materials . Moreover, the DNA double helix serves as a well‐established and widely used scaffold for the self‐assembly of sophisticated objects .…”

Synthesis of Responsive Two‐Dimensional Polymers via Self‐Assembled DNA Networks

“…[3][4][5][6][7][8][9][10][11] Graphene,w hich forms under extreme thermolytic conditions, serves as the prototype of this class of macromolecules. [11,[25][26][27][28][29][30][31][32][33][34][35][36][37] Moreover,the DNAdouble helix serves as awell-established and widely used scaffold for the self-assembly of sophisticated objects. Furthermore,t he 2D polymers obtained so far by these approaches are not water-soluble,w hich might restrict some of their applications.T of urther explore the potential of this fascinating class of materials,a lternative synthetic strategies are in demand.…”

“…Furthermore,t he 2D polymers obtained so far by these approaches are not water-soluble,w hich might restrict some of their applications.T of urther explore the potential of this fascinating class of materials,a lternative synthetic strategies are in demand. [11,[25][26][27][28][29][30][31][32][33][34][35][36][37] Moreover,the DNAdouble helix serves as awell-established and widely used scaffold for the self-assembly of sophisticated objects. [11,[25][26][27][28][29][30][31][32][33][34][35][36][37] Moreover,the DNAdouble helix serves as awell-established and widely used scaffold for the self-assembly of sophisticated objects.…”

“…Supramolecular polymerization [21][22][23][24] provides an elegant access to the assembly of 2D materials. [11,[25][26][27][28][29][30][31][32][33][34][35][36][37] Moreover,the DNAdouble helix serves as awell-established and widely used scaffold for the self-assembly of sophisticated objects. [38][39][40][41][42][43][44][45][46][47][48] DNA-based nanoarchitectures have ap otential for applications in molecular biology and medicine,aswell as for the construction of electronic and mechanical devices.…”