TY - JOUR
T1 - Conformational Heterogeneity and Interchain Percolation Revealed in an Amorphous Conjugated Polymer
AU - Ziolek, Robert M.
AU - Santana-bonilla, Alejandro
AU - López-ríos De Castro, Raquel
AU - Kühn, Reimer
AU - Green, Mark
AU - Lorenz, Christian D.
N1 - Funding Information:
We thank Peter Quinn (King’s College London) for his advice in preparing the manuscript. R.M.Z., M.G., and C.D.L. acknowledge the Engineering and Physical Sciences Research Council (EPSRC) for funding (EP/V049771/1). We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). For the purpose of open access, the author has applied a Creative Commons Attribution (CC BY) licence (where permitted by UKRI, “Open Government Licence” or ‘Creative Commons Attribution No-derivatives (CC BY-ND) public copyright licence’ may be stated instead) to any Author Accepted Manuscript version arising.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/9/27
Y1 - 2022/9/27
N2 - Conjugated polymers are employed in a variety of application areas due to their bright fluorescence and strong biocompatibility. However, understanding the structure of amorphous conjugated polymers on the nanoscale is extremely challenging compared to their related crystalline phases. Using a bespoke classical force field, we study amorphous poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) with molecular dynamics simulations to investigate the role that its nanoscale structure plays in controlling its emergent (and all-important) optical properties. Notably, we show that a giant percolating cluster exists within amorphous F8BT, which has ramifications in understanding the nature of interchain species that drive the quantum yield reduction and bathochromic shift observed in conjugated polymer-based devices and nanostructures. We also show that distinct conformations can be unravelled from within the disordered structure of amorphous F8BT using a two-stage machine learning protocol, highlighting a link between molecular conformation and ring stacking propensity. This work provides predictive understanding by which to enhance the optical properties of next-generation conjugated polymer-based devices and materials by rational, simulation-led design principles.
AB - Conjugated polymers are employed in a variety of application areas due to their bright fluorescence and strong biocompatibility. However, understanding the structure of amorphous conjugated polymers on the nanoscale is extremely challenging compared to their related crystalline phases. Using a bespoke classical force field, we study amorphous poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) with molecular dynamics simulations to investigate the role that its nanoscale structure plays in controlling its emergent (and all-important) optical properties. Notably, we show that a giant percolating cluster exists within amorphous F8BT, which has ramifications in understanding the nature of interchain species that drive the quantum yield reduction and bathochromic shift observed in conjugated polymer-based devices and nanostructures. We also show that distinct conformations can be unravelled from within the disordered structure of amorphous F8BT using a two-stage machine learning protocol, highlighting a link between molecular conformation and ring stacking propensity. This work provides predictive understanding by which to enhance the optical properties of next-generation conjugated polymer-based devices and materials by rational, simulation-led design principles.
UR - http://www.scopus.com/inward/record.url?scp=85138811297&partnerID=8YFLogxK
U2 - 10.1021/acsnano.2c04794
DO - 10.1021/acsnano.2c04794
M3 - Article
SN - 1936-0851
VL - 16
SP - 14432
EP - 14442
JO - ACS Nano
JF - ACS Nano
IS - 9
ER -