Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes

Meera Mohankumar; Michel Holler; Eric Meichsner; Jean François Nierengarten; Frédéric Niess; Jean Pierre Sauvage; Béatrice Delavaux-Nicot; Enrico Leoni; Filippo Monti; Joanna M. Malicka; Massimo Cocchi; Elisa Bandini; Nicola Armaroli

doi:10.1021/jacs.7b12671

Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes

Meera Mohankumar, Michel Holler, Eric Meichsner, Jean François Nierengarten, Frédéric Niess, Jean Pierre Sauvage, Béatrice Delavaux-Nicot, Enrico Leoni, Filippo Monti, Joanna M. Malicka, Massimo Cocchi, Elisa Bandini, Nicola Armaroli

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Abstract

A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)]⁺ (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH₂Cl₂. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)]⁺ shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (∼40≈45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)]⁺ (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)]⁺) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)]⁺, which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.

Original language	English
Pages (from-to)	2336-2347
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	140
Issue number	6
DOIs	https://doi.org/10.1021/jacs.7b12671
State	Published - 14 Feb 2018
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

Funding

Financial support by the CNR (PHEEL; Progetto Bandiera NCHEM), the CNRS (PICS no. 6840), the University of Strasbourg, the International Center for Frontier Research in Chemistry, and the LabEx Chimie des Systemes Complexes is gratefully acknowledged. Financial support by the CNR (PHEEL; Progetto Bandiera NCHEM), the CNRS (PICS no. 6840), the University of Strasbourg, the International Center for Frontier Research in Chemistry, and the LabEx “Chimie des System̀ es Complexes” is gratefully acknowledged. We further thank M. Schmitt for high-field NMR measurements, J.-M. Strub for the mass spectra, and A. Sournia-Saquet (LCC) for electrochemical measurements.

Funders	Funder number
Center for Neuroscience Research
Pacific Institute for Climate Solutions
Université de Strasbourg
Labex
Consiglio Nazionale delle Ricerche
Centre National de la Recherche Scientifique	6840

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Cite this

Mohankumar, M., Holler, M., Meichsner, E., Nierengarten, J. F., Niess, F., Sauvage, J. P., Delavaux-Nicot, B., Leoni, E., Monti, F., Malicka, J. M., Cocchi, M., Bandini, E., & Armaroli, N. (2018). Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes. Journal of the American Chemical Society, 140(6), 2336-2347. https://doi.org/10.1021/jacs.7b12671

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title = "Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes",

abstract = "A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)]+ (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH2Cl2. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)]+ shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (∼40≈45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)]+) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)]+, which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.",

author = "Meera Mohankumar and Michel Holler and Eric Meichsner and Nierengarten, {Jean Fran{\c c}ois} and Fr{\'e}d{\'e}ric Niess and Sauvage, {Jean Pierre} and B{\'e}atrice Delavaux-Nicot and Enrico Leoni and Filippo Monti and Malicka, {Joanna M.} and Massimo Cocchi and Elisa Bandini and Nicola Armaroli",

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Mohankumar, M, Holler, M, Meichsner, E, Nierengarten, JF, Niess, F, Sauvage, JP, Delavaux-Nicot, B, Leoni, E, Monti, F, Malicka, JM, Cocchi, M, Bandini, E & Armaroli, N 2018, 'Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes', Journal of the American Chemical Society, vol. 140, no. 6, pp. 2336-2347. https://doi.org/10.1021/jacs.7b12671

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T1 - Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes

AU - Mohankumar, Meera

AU - Holler, Michel

AU - Meichsner, Eric

AU - Nierengarten, Jean François

AU - Niess, Frédéric

AU - Sauvage, Jean Pierre

AU - Delavaux-Nicot, Béatrice

AU - Leoni, Enrico

AU - Monti, Filippo

AU - Malicka, Joanna M.

AU - Cocchi, Massimo

AU - Bandini, Elisa

AU - Armaroli, Nicola

PY - 2018/2/14

Y1 - 2018/2/14

N2 - A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)]+ (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH2Cl2. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)]+ shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (∼40≈45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)]+) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)]+, which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.

AB - A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)]+ (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH2Cl2. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)]+ shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (∼40≈45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)]+) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)]+, which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.

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Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes

Abstract

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