Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Programmed twisting of phenylene–ethynylene linkages from aromatic stacking interactions

Journal Article · · Journal of Materials Chemistry C
DOI:https://doi.org/10.1039/c8tc05612a· OSTI ID:1612546
 [1];  [1];  [1];  [2];  [1]
  1. Tufts Univ., Medford, MA (United States). Dept. of Chemistry
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
+ Show Author Affiliations
Control over the conformation and packing of conjugated materials is an unsolved problem that prevents the rational design of organic optoelectronics, such as preventing self-quenching of luminescent molecules. Exacerbating this challenge is a general lack of widely applicable strategies for controlling packing with discrete, directional non-covalent interactions. Here, we present a series of conjugated molecules with diverse backbones of three or four arenes that feature pentafluorobenzyl ester substituents. Nearly all the compounds reveal intramolecular stacking interactions between the fluoroarene (ArF) side-chains and non-fluorinated arenes (ArH) in the middle of the chromophores; a twisted PE linkage accompanies each example of this intramolecular ArF–ArH stacking. Furthermore, these molecules can resist dramatic changes to emission upon transition from organic solution to thin film when ArF rings prevent interchromophore interactions. By broadening the structural space of conjugated backbones over which ArF–ArH stacking can twist PE linkages reliably and prevent self-quenching of solids with simple synthetic approaches, this work suggests fluorinated benzyl ester substituents adjacent to phenylene ethynylene linkages as supramolecular synthons for the crystal engineering of organic optoelectronic materials.
Research Organization:
Tufts Univ., Medford, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0016423
OSTI ID:
1612546
Alternate ID(s):
OSTI ID: 1490553
Journal Information:
Journal of Materials Chemistry C, Journal Name: Journal of Materials Chemistry C Journal Issue: 5 Vol. 7; ISSN 2050-7526
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (46)

Phenyl/Pentafluorophenyl Interactions and the Generation of Ordered Mixed Crystals:sym-Triphenethynylbenzene andsym-Tris(perfluorophenethynyl)benzene journal July 2000
Phenyl/Pentafluorophenyl Interactions and the Generation of Ordered Mixed Crystals:sym-Triphenethynylbenzene andsym-Tris(perfluorophenethynyl)benzene journal July 2000
Building Blocks for n-Type Organic Electronics: Regiochemically Modulated Inversion of Majority Carrier Sign in Perfluoroarene-Modified Polythiophene Semiconductors journal August 2003
Structure of the Lowest Temperature Phase of the Solid Benzene–Hexafluorobenzene Adduct journal December 1992
Building Blocks for n-Type Organic Electronics: Regiochemically Modulated Inversion of Majority Carrier Sign in Perfluoroarene-Modified Polythiophene Semiconductors journal August 2003
Interactions with Aromatic Rings in Chemical and Biological Recognition journal March 2003
Conjugated Polyelectrolytes: Synthesis, Photophysics, and Applications journal June 2009
Sugar-Poly(para-phenylene ethynylene) Conjugates as Sensory Materials: Efficient Quenching by Hg2+ and Pb2+ Ions journal December 2004
Perfluorophenyl-Phenyl Interactions in the Crystallization and Topochemical Polymerization of Triacetylene Monomers journal September 2009
Programmed Synthesis of Molecular Wires with Fixed Insulation and Defined Length Based on Oligo(phenylene ethynylene) and Permethylated α-Cyclodextrins journal July 2017
Interactions with Aromatic Rings in Chemical and Biological Recognition. journal June 2003
Synthesis of Rotationally Restricted and Modular Biphenyl Building Blocks journal November 2009
Effect of Varying Thiophene Units on Charge-Transport and Photovoltaic Properties of Poly(phenylene ethynylene)- alt -poly(phenylene vinylene) Polymers journal June 2014
Big macrocyclic assemblies of carboranes (big MACs): synthesis and crystal structure of a macrocyclic assembly of four carboranes containing alternate ortho- and meta-carborane icosahedra linked by para-phenylene units journal August 2003
Electrochemically assisted mechanically controllable break junction studies on the stacking configurations of oligo(phenylene ethynylene)s molecular junctions journal May 2016
Gold-catalyzed C–S bond formation from thiols journal January 2010
Building upon Supramolecular Synthons: Some Aspects of Crystal Engineering journal May 2015
Organic Optoelectronic Materials: Mechanisms and Applications journal October 2016
Perfluorinated and Half-Fluorinated Rubrenes: Synthesis and Crystal Packing Arrangements journal July 2017
Self-Sterilizing, Self-Cleaning Mixed Polymeric Multifunctional Antimicrobial Surfaces journal December 2015
QUANTUM EFFICIENCIES OF FLUORESCENCE OF ORGANIC SUBSTANCES: EFFECT OF SOLVENT AND CONCENTRATION OF THE FLUORESCENT SOLUTE 1 journal February 1961
Electronic spectra of tolan in a supersonic free jet: large-amplitude torsional motion journal April 1984
Solid-State Packing of Conjugated Oligomers:  From π-Stacks to the Herringbone Structure journal April 2004
Perfluoropentacene:  High-Performance p−n Junctions and Complementary Circuits with Pentacene journal July 2004
Fluorocarbon-Modified Organic Semiconductors:  Molecular Architecture, Electronic, and Crystal Structure Tuning of Arene- versus Fluoroarene-Thiophene Oligomer Thin-Film Properties journal May 2006
Probing the Intrachain and Interchain Effects on the Fluorescence Behavior of Pentiptycene-Derived Oligo( p -phenyleneethynylene)s journal November 2006
Twisted Tethered Tolanes: Unanticipated Long-Lived Phosphorescence at 77 K journal January 2013
Theoretical Interpretation of Conductivity Measurements of a Thiotolane Sandwich. A Molecular Scale Electronic Controller journal April 1998
Substituent Effects That Control Conjugated Oligomer Conformation through Non-covalent Interactions journal March 2017
Replacing Phenyl Ring with Thiophene: An Approach to Longer Wavelength Aza-dipyrromethene Boron Difluoride (Aza-BODIPY) Dyes journal December 2011
Role of Molecular Packing in Determining Solid-State Optical Properties of π-Conjugated Materials journal March 2011
Photovoltaic Cells Based on Sequentially Adsorbed Multilayers of Conjugated Poly( p -phenylene ethynylene)s and a Water-Soluble Fullerene Derivative † journal October 2005
Light-Induced Antibacterial Activity of Symmetrical and Asymmetrical Oligophenylene Ethynylenes journal April 2011
When Worlds Collide: Interactions at the Interface between Biological Systems and Synthetic Cationic Conjugated Polyelectrolytes and Oligomers journal June 2013
Anthracene Based Conjugated Polymers: Correlation between π−π-Stacking Ability, Photophysical Properties, Charge Carrier Mobility, and Photovoltaic Performance journal February 2010
From Tunneling to Hopping: A Comprehensive Investigation of Charge Transport Mechanism in Molecular Junctions Based on Oligo( p -phenylene ethynylene)s journal November 2009
Conformational and Electronic Engineering of Twisted Diphenylacetylenes journal September 2003
Partial Fluorination Overcomes Herringbone Crystal Packing in Small Polycyclic Aromatics † journal March 2005
Oligo( p -phenyleneethynylene)s with Hydrogen-Bonded Coplanar Conformation journal July 2008
Molecular crystalline materials with tunable luminescent properties: from polymorphs to multi-component solids journal January 2014
Strategies to create hierarchical self-assembled structures via cooperative non-covalent interactions journal January 2015
Twisting and piezochromism of phenylene-ethynylenes with aromatic interactions between side chains and main chains journal January 2014
Turn-on fluorescent sensor for the detection of cyanide based on a novel dicyanovinyl phenylacetylene journal January 2017
Synergy between experimental and computational studies of aromatic stacking interactions journal January 2017
Reversible mechanofluorochromism of aniline-terminated phenylene ethynylenes journal January 2018
Engineering a twist in 9,10-diethynylanthracenes by steric interactions journal January 2007

Cited By (1)

Turning on solid-state phosphorescence of platinum acetylides with aromatic stacking journal January 2020

Similar Records

Small Changes With Big Consequences: Swapping Two Atoms In Side Chains Changes Phenylene‐Ethynylene Packing And Fluorescence
Journal Article · Thu Oct 25 20:00:00 EDT 2018 · Chemistry - A European Journal · OSTI ID:1479157

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY