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Uncovering Backbone Conformation for Rigid DPP-Based Donor–Acceptor Conjugated Polymer Using Deuterium Labeling and Neutron Scattering

Journal Article · · Macromolecules
 [1];  [2];  [3];  [4];  [4];  [3];  [2];  [1]
  1. University of Southern Mississippi, Hattiesburg, MS (United States)
  2. Iowa State University, Ames, IA (United States)
  3. University of Windsor, Ontario (Canada)
  4. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
The conjugated polymer’s backbone conformation dictates the delocalization of electrons, ultimately affecting its optoelectronic properties. Most conjugated polymers can be viewed as semirigid rods with their backbone embedded among long alkyl side chains. Thus, it is challenging to experimentally quantify the conformation of a conjugated backbone. Here, we performed contrast variation neutron scattering on rigid conjugated donor–acceptor (D–A) diketopyrrolopyrrole (DPP) polymers with selectively deuterated side chains to measure the conjugated backbone conformation. We first synthesized DPPbased polymers with deuterated side chains, confirmed by NMR and FTIR. Using contrast variation neutron scattering, we found that the DPP-based conjugated polymers are much more rigid than poly(3-alkylthiophenes), with persistence length (Lp) at 16–18 nm versus 2–3 nm. More importantly, in contrast to the relatively flexible poly(3-alkylthiophenes) whose backbone is more flexible than the whole polymer, we found that the backbone of DPP-based polymers has the same Lp value compared to the whole polymer chain. This indicates that side chain interference on backbone conformation is not present for the semirigid polymer, which is further confirmed by coarse-grained molecular dynamics (CG-MD) simulations. Our work provides a novel protocol to probe polymer’s backbone conformation and paradigm-shifting understanding of the backbone conformation of semirigid conjugated polymers.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); University of Southern Mississippi, Hattiesburg, MS (United States)
Sponsoring Organization:
Natural Sciences and Engineering Research Council of Canada (NSERC); U.S. National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
AC05-00OR22725; SC0022050
OSTI ID:
2472973
Alternate ID(s):
OSTI ID: 2478330
OSTI ID: 2476928
Journal Information:
Macromolecules, Journal Name: Macromolecules Journal Issue: 21 Vol. 57; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (39)

Toward the Prediction and Control of Glass Transition Temperature for Donor–Acceptor Polymers journal May 2020
Highly Deformable Rigid Glassy Conjugated Polymeric Thin Films journal August 2023
Tough Self-Healing Elastomers by Molecular Enforced Integration of Covalent and Reversible Networks journal August 2017
Wafer‐Scale Fabrication of High‐Performance n‐Type Polymer Monolayer Transistors Using a Multi‐Level Self‐Assembly Strategy journal December 2018
The Effects of Side Chains on the Charge Mobilities and Functionalities of Semiconducting Conjugated Polymers beyond Solubilities journal September 2019
Molecular Structure and Conformational Design of Donor‐Acceptor Conjugated Polymers to Enable Predictable Optoelectronic Property journal July 2023
The Renaissance of H/D Exchange journal October 2007
Design of Near‐Infrared Nonfullerene Acceptor with Ultralow Nonradiative Voltage Loss for High‐Performance Semitransparent Ternary Organic Solar Cells journal January 2022
Pd- and Pt-catalyzed H/D exchange methods and their application for internal MS standard preparation from a Sanofi-Aventis perspective journal September 2010
Manipulating Conjugated Polymer Backbone Dynamics through Controlled Thermal Cleavage of Alkyl Side Chains journal August 2022
Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε‐Caprolactone) journal April 2019
Comparison of neutron and X-ray scattering of dilute myoglobin solutions journal April 1975
Processible and environmentally stable conducting polymers journal July 1986
Decoupling Poly(3-alkylthiophenes)’ Backbone and Side-Chain Conformation by Selective Deuteration and Neutron Scattering journal December 2020
Evolution of Chain Dynamics and Oxidation States with Increasing Chain Length for a Donor–Acceptor-Conjugated Oligomer Series journal August 2021
Chain Stiffness of Donor–Acceptor Conjugated Polymers in Solution journal January 2022
Selectively Deuterated Poly(ε-caprolactone)s: Synthesis and Isotope Effects on the Crystal Structures and Properties journal November 2018
Comb and Bottlebrush Graft Copolymers in a Melt journal May 2019
Attaining Melt Processing of Complementary Semiconducting Polymer Blends at 130 °C via Side-Chain Engineering journal January 2018
Variable-Temperature Scattering and Spectroscopy Characterizations for Temperature-Dependent Solution Assembly of PffBT4T-Based Conjugated Polymers journal February 2022
Troponin I Encompasses an Extended Troponin C in the Ca2+-Bound Complex: A Small-Angle X-ray and Neutron Scattering Study journal July 1994
Scalable Synthesis of Fused Thiophene-Diketopyrrolopyrrole Semiconducting Polymers Processed from Nonchlorinated Solvents into High Performance Thin Film Transistors journal February 2013
Bulk Heterojunction Solar Cells: Morphology and Performance Relationships journal May 2014
Aggregation in a High-Mobility n-Type Low-Bandgap Copolymer with Implications on Semicrystalline Morphology journal October 2012
Late-Stage β-C(sp3)–H Deuteration of Carboxylic Acids journal July 2021
Structure of a grafted polymer brush: a molecular dynamics simulation journal October 1989
Polymer Chain Shape of Poly(3-alkylthiophenes) in Solution Using Small-Angle Neutron Scattering journal February 2013
Efficient C−H/C−D Exchange Reaction on the Alkyl Side Chain of Aromatic Compounds Using Heterogeneous Pd/C in D 2 O journal April 2004
Non-fullerene acceptors for organic solar cells journal February 2018
Exploring the origin of high optical absorption in conjugated polymers journal May 2016
Polymer solar cells journal February 2012
Status and prospects for ternary organic photovoltaics journal July 2015
Poly(3-hexylthiophene) (P3HT): fruit fly or outlier in organic solar cell research? journal January 2017
Super-soft, firm, and strong elastomers toward replication of tissue viscoelastic response journal January 2022
Probing single-chain conformation and its impact on the optoelectronic properties of donor–accepter conjugated polymers journal January 2023
Effect of solvent quality and sidechain architecture on conjugated polymer chain conformation in solution journal January 2024
In-Situ growth of cadmium telluride nanocrystals in poly(3-hexylthiophene) matrix for photovoltaic application journal August 2011
Molecular dynamics simulation of a polymer chain in solution journal November 1993
Toughening hydrogels through force-triggered chemical reactions that lengthen polymer strands journal October 2021

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