Melt-State Ligand Addition Generates a Near-Infrared-Emissive Coordination Polymer Glass
8 affiliations
- 1Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Str. 6, Dortmund, Germany, 44227
- 2Department of Chemistry, Graduate School of Science
- 3Kyoto University
- 4Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering
- 5Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Yoshida-Honmachi, Sakyo-ku, Kyoto, Japan, 606-8501
- 6School of Molecular Science and Engineering
- 7Vidyasirimedhi Institute of Science and Technology
- 8Dortmund Center for Advanced Exploration of Dynamics Across Limits Using Spectroscopy (DAEDALUS), Technische Universität Dortmund, Otto-Hahn-Str. 4a, Dortmund, Germany, 44227
Abstract
Meltable coordination polymers (CPs) combine liquid-phase processability with the structural and functional diversity of crystalline coordination compounds, but methods to install targeted local coordination environments and photophysical functions in CP glasses remain limited. Here, we demonstrate that 1,10-phenanthroline (phen) reacts with the 1D-extended Cu I -CP Cu(ipim) (Cuip; ipim − = 2-isopropylimidazolate) in the melt, converting half of the linearly coordinated Cu I sites into pseudo-tetrahedral [Cu(phen)(ipim) 2 ] − units while preserving chain topology and the interchain-separation melting mechanism. Depending on thermal history, the resulting phen 0.5 Cuip forms either a melt-quenched glass or crystalline polymorphs, whereas pristine Cuip invariably recrystallizes on cooling. X-ray total scattering and spectroscopic analyses show that the local Cu I -phen motif is retained across the phases, while the coordination geometry, interchain order, and phen···phen π-stacking interactions differ. Ligand addition transforms the photophysics from green phosphorescence in Cuip to broad near-infrared emission centered at approximately 850 nm in both crystalline and glassy phen 0.5 Cuip. The pronounced temperature dependence of this emission is consistent with a thermally activated delayed fluorescence mechanism. Calculations indicate that the extended CP environment restricts flattening of the pseudo-tetrahedral [Cu(phen)(ipim) 2 ] − units after metal-to-ligand charge-transfer (MLCT) excitation, thereby limiting access to non-radiative decay pathways. Melt-state ligand addition thus provides a route to construct molecular-complex-like functional units during processing, linking reactive CP melt chemistry to targeted photophysical design in CP glasses.
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BibTeX
@misc{weiß2026meltstate,
title = {{Melt-State Ligand Addition Generates a Near-Infrared-Emissive Coordination Polymer Glass}},
author = {Jan-Benedikt Weiß and Michael Nuss and Taichi Nishiguchi and Zichong Yu and Giulia Rosano and Ellan K. Berdichevsky and Nao Horike and Andreas Steffen and Yong-Sheng Wei and Satoshi Horike and Sebastian Henke},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008599/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008599/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Melt-State Ligand Addition Generates a Near-Infrared-Emissive Coordination Polymer Glass
AU - Jan-Benedikt Weiß
AU - Michael Nuss
AU - Taichi Nishiguchi
AU - Zichong Yu
AU - Giulia Rosano
AU - Ellan K. Berdichevsky
AU - Nao Horike
AU - Andreas Steffen
AU - Yong-Sheng Wei
AU - Satoshi Horike
AU - Sebastian Henke
PY - 2026
DA - 2026/09/09
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008599/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008599/v1
AB - Meltable coordination polymers (CPs) combine liquid-phase processability with the structural and functional diversity of crystalline coordination compounds, but methods to install targeted local coordination environments and photophysical functions in CP glasses remain limited. Here, we demonstrate that 1,10-phenanthroline (phen) reacts with the 1D-extended Cu I -CP Cu(ipim) (Cuip; ipim − = 2-isopropylimidazolate) in the melt, converting half of the linearly coordinated Cu I sites into pseudo-tetrahedral [Cu(phen)(ipim) 2 ] − units while preserving chain topology and the interchain-separation melting mechanism. Depending on thermal history, the resulting phen 0.5 Cuip forms either a melt-quenched glass or crystalline polymorphs, whereas pristine Cuip invariably recrystallizes on cooling. X-ray total scattering and spectroscopic analyses show that the local Cu I -phen motif is retained across the phases, while the coordination geometry, interchain order, and phen···phen π-stacking interactions differ. Ligand addition transforms the photophysics from green phosphorescence in Cuip to broad near-infrared emission centered at approximately 850 nm in both crystalline and glassy phen 0.5 Cuip. The pronounced temperature dependence of this emission is consistent with a thermally activated delayed fluorescence mechanism. Calculations indicate that the extended CP environment restricts flattening of the pseudo-tetrahedral [Cu(phen)(ipim) 2 ] − units after metal-to-ligand charge-transfer (MLCT) excitation, thereby limiting access to non-radiative decay pathways. Melt-state ligand addition thus provides a route to construct molecular-complex-like functional units during processing, linking reactive CP melt chemistry to targeted photophysical design in CP glasses.
ER -