Correlating structural changes with the photophysics of terrylenediimide films during spontaneous annealing

Natalia E. Powers-Riggs; Itai Schlesinger; Michael R. Wasielewski

doi:10.1039/d0tc02814b

Correlating structural changes with the photophysics of terrylenediimide films during spontaneous annealing

Natalia E. Powers-Riggs, Itai Schlesinger, Michael R. Wasielewski^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Interchromophore distance and geometry determine the nature of intermolecular coupling and therefore the photophysical behavior of the system. Here we demonstrate the close relationship between molecular orientation and coupling by characterizing the initial and final states of a N,N-bis(tricosan-12-yl)terrylene-3,4:11,12-bis(dicarboximide) (C23TDI) film undergoing spontaneous annealing at room temperature. Appending long aliphatic tails to the large TDI π-surface produces an initially liquid crystal-like structure that reorganizes to the thermodynamically stable structure at room temperature. Monitoring the structural changes using UV-vis absorption and X-ray diffraction techniques reveals metastable intermediates we can identify and characterize, and the slow timescale of this change allows for a clear comparison between interchromophore structures and photophysical behavior at various points along the reaction coordinate, providing important insights into the relationship between chromophore packing and function. Initially upon film preparation, C23TDI exhibits no long-range order but shows strong charge-transfer (CT) interactions, as observed through steady-state and transient absorption measurements. Within 60 hours under ambient conditions, the TDI units in the film reorganize to an orientation with higher crystallinity and diminished CT interaction, highlighting the dominance of long alkyl chain interactions over π-stacking interactions. This journal is

Original language	English (US)
Pages (from-to)	15189-15198
Number of pages	10
Journal	Journal of Materials Chemistry C
Volume	8
Issue number	43
DOIs	https://doi.org/10.1039/d0tc02814b
State	Published - Nov 21 2020

Funding

This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M. R. W.). N. E. P.-R. was supported by NSF Graduate Research Fellowship (DGE-1324585). I. S. would like to thank Yad Hanadiv Foundation for the Rothschild Postdoctoral Fellowship. Thanks to Ryan M. Young for discussion and support. Use was made of the IMSERC X-ray Facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN). Thanks to Dr Christos Malliakas for guidance in analyzing powder diffraction data. Thanks to Joaquin M. Alzola for collection of GIWAXS data and discussion. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract no. DE-AC02-06CH11357.

ASJC Scopus subject areas

General Chemistry
Materials Chemistry

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title = "Correlating structural changes with the photophysics of terrylenediimide films during spontaneous annealing",

abstract = "Interchromophore distance and geometry determine the nature of intermolecular coupling and therefore the photophysical behavior of the system. Here we demonstrate the close relationship between molecular orientation and coupling by characterizing the initial and final states of a N,N-bis(tricosan-12-yl)terrylene-3,4:11,12-bis(dicarboximide) (C23TDI) film undergoing spontaneous annealing at room temperature. Appending long aliphatic tails to the large TDI π-surface produces an initially liquid crystal-like structure that reorganizes to the thermodynamically stable structure at room temperature. Monitoring the structural changes using UV-vis absorption and X-ray diffraction techniques reveals metastable intermediates we can identify and characterize, and the slow timescale of this change allows for a clear comparison between interchromophore structures and photophysical behavior at various points along the reaction coordinate, providing important insights into the relationship between chromophore packing and function. Initially upon film preparation, C23TDI exhibits no long-range order but shows strong charge-transfer (CT) interactions, as observed through steady-state and transient absorption measurements. Within 60 hours under ambient conditions, the TDI units in the film reorganize to an orientation with higher crystallinity and diminished CT interaction, highlighting the dominance of long alkyl chain interactions over π-stacking interactions. This journal is ",

author = "Powers-Riggs, {Natalia E.} and Itai Schlesinger and Wasielewski, {Michael R.}",

note = "Funding Information: This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M. R. W.). N. E. P.-R. was supported by NSF Graduate Research Fellowship (DGE-1324585). I. S. would like to thank Yad Hanadiv Foundation for the Rothschild Postdoctoral Fellowship. Thanks to Ryan M. Young for discussion and support. Use was made of the IMSERC X-ray Facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN). Thanks to Dr Christos Malliakas for guidance in analyzing powder diffraction data. Thanks to Joaquin M. Alzola for collection of GIWAXS data and discussion. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract no. DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

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doi = "10.1039/d0tc02814b",

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N1 - Funding Information: This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M. R. W.). N. E. P.-R. was supported by NSF Graduate Research Fellowship (DGE-1324585). I. S. would like to thank Yad Hanadiv Foundation for the Rothschild Postdoctoral Fellowship. Thanks to Ryan M. Young for discussion and support. Use was made of the IMSERC X-ray Facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN). Thanks to Dr Christos Malliakas for guidance in analyzing powder diffraction data. Thanks to Joaquin M. Alzola for collection of GIWAXS data and discussion. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract no. DE-AC02-06CH11357. Publisher Copyright: © The Royal Society of Chemistry.

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N2 - Interchromophore distance and geometry determine the nature of intermolecular coupling and therefore the photophysical behavior of the system. Here we demonstrate the close relationship between molecular orientation and coupling by characterizing the initial and final states of a N,N-bis(tricosan-12-yl)terrylene-3,4:11,12-bis(dicarboximide) (C23TDI) film undergoing spontaneous annealing at room temperature. Appending long aliphatic tails to the large TDI π-surface produces an initially liquid crystal-like structure that reorganizes to the thermodynamically stable structure at room temperature. Monitoring the structural changes using UV-vis absorption and X-ray diffraction techniques reveals metastable intermediates we can identify and characterize, and the slow timescale of this change allows for a clear comparison between interchromophore structures and photophysical behavior at various points along the reaction coordinate, providing important insights into the relationship between chromophore packing and function. Initially upon film preparation, C23TDI exhibits no long-range order but shows strong charge-transfer (CT) interactions, as observed through steady-state and transient absorption measurements. Within 60 hours under ambient conditions, the TDI units in the film reorganize to an orientation with higher crystallinity and diminished CT interaction, highlighting the dominance of long alkyl chain interactions over π-stacking interactions. This journal is

AB - Interchromophore distance and geometry determine the nature of intermolecular coupling and therefore the photophysical behavior of the system. Here we demonstrate the close relationship between molecular orientation and coupling by characterizing the initial and final states of a N,N-bis(tricosan-12-yl)terrylene-3,4:11,12-bis(dicarboximide) (C23TDI) film undergoing spontaneous annealing at room temperature. Appending long aliphatic tails to the large TDI π-surface produces an initially liquid crystal-like structure that reorganizes to the thermodynamically stable structure at room temperature. Monitoring the structural changes using UV-vis absorption and X-ray diffraction techniques reveals metastable intermediates we can identify and characterize, and the slow timescale of this change allows for a clear comparison between interchromophore structures and photophysical behavior at various points along the reaction coordinate, providing important insights into the relationship between chromophore packing and function. Initially upon film preparation, C23TDI exhibits no long-range order but shows strong charge-transfer (CT) interactions, as observed through steady-state and transient absorption measurements. Within 60 hours under ambient conditions, the TDI units in the film reorganize to an orientation with higher crystallinity and diminished CT interaction, highlighting the dominance of long alkyl chain interactions over π-stacking interactions. This journal is

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Correlating structural changes with the photophysics of terrylenediimide films during spontaneous annealing

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