Programming intramolecular charge transfer in NDI–pyrene paracyclophanes through distance and linker design
- 1Department of Chemistry, Biochemistry and Pharmaceutical Sciences, W. Inäbnit Laboratory for Molecular Quantum Materials and WSS-Research Center for Molecular Quantum Systems, University of Bern Freiestrasse 3 Bern 3012 Switzerland [email protected].
- 2Laboratory of Computational Chemistry and Biochemistry, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne Lausanne 1015 Switzerland [email protected].
- 3Institute of Applied Physics, University of Bern Sidlerstrasse 5 Bern 3012 Switzerland.
Abstract
Through-space charge transfer (TSCT) in electron donor-acceptor (D-A) molecules is a powerful strategy for controlling excited-state processes. However, the influence of molecular architecture on TSCT dynamics remains poorly understood. Herein, we report a series of naphthalene diimide (NDI)-pyrene (Py) D-A paracyclophanes (PCPs) with systematically varied interchromophore distance and spatial arrangement via different linkers: phenylene (NDI-Ph-Py), benzylamine (NDI-BnNH-Py), and adamantylamine (NDI-AdaNH-Py). All PCPs exhibit low-energy CT absorption bands absent in the corresponding reference compounds, confirming efficient intramolecular TSCT interactions. Combined spectroscopic, electrochemical, and computational studies reveal that the TSCT strength and energies are highly sensitive to linker structure, rigidity, and NDI-Py separation. Furthermore, femtosecond transient absorption spectroscopy shows multiple CT states and distinct relaxation pathways governed by linker properties. NDI-AdaNH-Py exhibits CT-state formation on the sub-picosecond timescale, facilitated by the short NDI-Py separation distance and substantial orbital overlap. NDI-Ph-Py, with the shortest interchromophore distance, strongest electronic coupling, and rigid structure, further promotes the formation of an exciplex state. These findings demonstrate that linker engineering is an effective means of modulating TSCT interactions, providing valuable design principles for the development of next-generation functional organic materials.
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BibTeX
@article{negretevergara2026programming,
title = {{Programming intramolecular charge transfer in NDI–pyrene paracyclophanes through distance and linker design}},
author = {Camila Negrete-Vergara and Vladislav Slama and Elnaz Zyaee and Hans-Martin Frey and Silvio Decurtins and Thomas Feurer and Ursula Röthlisberger and Shi-Xia Liu},
journal = {Journal of materials chemistry. C},
year = {2026},
month = oct,
doi = {10.1039/d6tc02775j},
url = {https://europepmc.org/article/PMC/PMC13718283},
note = {CC BY},
}
RIS
TY - JOUR
TI - Programming intramolecular charge transfer in NDI–pyrene paracyclophanes through distance and linker design
AU - Camila Negrete-Vergara
AU - Vladislav Slama
AU - Elnaz Zyaee
AU - Hans-Martin Frey
AU - Silvio Decurtins
AU - Thomas Feurer
AU - Ursula Röthlisberger
AU - Shi-Xia Liu
PY - 2026
DA - 2026/10/21
JO - Journal of materials chemistry. C
DO - 10.1039/d6tc02775j
UR - https://europepmc.org/article/PMC/PMC13718283
AB - Through-space charge transfer (TSCT) in electron donor-acceptor (D-A) molecules is a powerful strategy for controlling excited-state processes. However, the influence of molecular architecture on TSCT dynamics remains poorly understood. Herein, we report a series of naphthalene diimide (NDI)-pyrene (Py) D-A paracyclophanes (PCPs) with systematically varied interchromophore distance and spatial arrangement via different linkers: phenylene (NDI-Ph-Py), benzylamine (NDI-BnNH-Py), and adamantylamine (NDI-AdaNH-Py). All PCPs exhibit low-energy CT absorption bands absent in the corresponding reference compounds, confirming efficient intramolecular TSCT interactions. Combined spectroscopic, electrochemical, and computational studies reveal that the TSCT strength and energies are highly sensitive to linker structure, rigidity, and NDI-Py separation. Furthermore, femtosecond transient absorption spectroscopy shows multiple CT states and distinct relaxation pathways governed by linker properties. NDI-AdaNH-Py exhibits CT-state formation on the sub-picosecond timescale, facilitated by the short NDI-Py separation distance and substantial orbital overlap. NDI-Ph-Py, with the shortest interchromophore distance, strongest electronic coupling, and rigid structure, further promotes the formation of an exciplex state. These findings demonstrate that linker engineering is an effective means of modulating TSCT interactions, providing valuable design principles for the development of next-generation functional organic materials.
SN - 2050-7526
SN - 2050-7534
ER -