Intramolecular non-covalent interactions as a strategy towards controlled photoluminescence in copper(<scp>i</scp>) complexes

Filonenko, Georgy A.; Fayzullin, Robert R.; Khusnutdinova, Julia R.

doi:10.1039/c6tc04989c

Cited by 19 publications

(32 citation statements)

References 57 publications

(63 reference statements)

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“…Thep reparation of the new mechanophore and its selective incorporation in PUs was the first objective of our study.W eb ased our mechanophore design on an ew class of recently developed phosphorescent complexes that were shown to reversibly respond to mechanical stress (CuN 4 , Figure 1b). [8,9] Themechanism governing their force-induced response,depicted in Figure 1b,isconceptually different from those found in common organic mechanophores. [9] Instead of bond scission and related irreversible transformations,t hese copper halide complexes vary their photoluminescence (PL) via aforce-induced restriction of their intramolecular isomerization that represents an on-radiative relaxation process.…”

mentioning

confidence: 87%

Tracking Local Mechanical Impact in Heterogeneous Polymers with Direct Optical Imaging

et al. 2018

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Structural heterogeneity defines the properties of many functional polymers and it is often crucial for their performance and ability to withstand mechanical impact. Such heterogeneity, however, poses a tremendous challenge for characterization of these materials and limits our ability to design them rationally. Herein we present a practical methodology capable of resolving the complex mechanical behavior and tracking mechanical impact in discrete phases of segmented polyurethane-a typical example of a structurally complex polymer. Using direct optical imaging of photoluminescence produced by a small-molecule organometallic mechano-responsive sensor we observe in real time how polymer phases dissipate energy, restructure, and breakdown upon mechanical impact. Owing to its simplicity and robustness, this method has potential in describing the evolution of complex soft-matter systems for which global characterization techniques fall short of providing molecular-level insight.

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mentioning

confidence: 87%

Tracking Local Mechanical Impact in Heterogeneous Polymers with Direct Optical Imaging

et al. 2018

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“…The starting point of our investigation was marked by the recent development of a family of Cu(I) phosphorescent complexes that have showed a remarkable sensitivity of the PL properties to the local environment . Namely, the subtle variations of the substituent bulk in the macrocyclic cyclophane‐inspired ligand resulted in dramatic changes of the quantum yield in the solid state.…”

Section: Properties and Composition Of Polymer Samples Prepared For Tmentioning

confidence: 99%

Dynamic Phosphorescent Probe for Facile and Reversible Stress Sensing

Filonenko

Khusnutdinova

2017

Advanced Materials

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Dynamic phosphorescent copper complex incorporated into the main chain of polyurethanes produces a facile and reversible response to tensile stress. In contrast to common deformation sensors, the applied stress does not lead to bond scission, or alters the phosphor structure. The suppression of dynamics responsible for the nonradiative relaxation is found to be the major pathway governing stress response. As a result, the response of dynamic phosphor described in this work is stress specific. Compared to initial unloaded state, a nearly twofold increase of photoluminescence intensity occurs in response to a 5-35 MPa stress applied to pristine metalated polymers or their blends with various polyurethanes. Finally, the dynamic sensor proves useful for mapping stress distribution patterns and tracking dynamic phenomena in polyurethanes using simple optical imaging techniques.

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“…(a) Reproduced with permission. [ 174 ] Copyright 2017, The Royal Society of Chemistry; (b–d) Reproduced with permission under the terms of the Creative Commons CC BY license. [ 176 ] Copyright 2018, the Authors.…”

Section: Mechanical Stimulation Of Directional Supramolecular Interacmentioning

confidence: 99%

“…[173] Analogous to these investigations with NHC complexes, Khusnutdinova and co-workers developed a series of photoluminescent iodo-copper pyridinophane (CuN 4 -I) complexes (Figure 12a). [174] The emission color of the CuN 4 -I complexes could be tuned by varying either the counterion or the bulkiness of the pendant groups attached to the pyridinophane, since these parameters influence the unique excited state geometries. The CuN 4 -I complex was covalently incorporated into the hard segments of a PU and the authors observed an increase in the photoluminescence (PL) intensity of the complex when the material was subjected to tensile deformation.…”

Section: Organometallic Complexes As Mechanoresponsive Moietiesmentioning

confidence: 99%

From Molecules to Polymers—Harnessing Inter‐ and Intramolecular Interactions to Create Mechanochromic Materials

Traeger

Kiebala

Weder

et al. 2020

Macromol. Rapid Commun.

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tion occurs to avoid catastrophic materials failure and to possibly redirect degradation processes into useful responses. Consequently, research efforts directed toward the investigation and development of mechanoresponsive materials has drawn ever increasing attention. [2,3,5-8] Polymers that translate mechanical stresses into a defined response are thought to be useful for many different applications, including as tamper-proof packaging materials, [9] as degradable plastics, [10,11] or for structural health monitoring. [12] One possibility to render polymers mechanoresponsive is the integration of so-called mechanophores. The latter generally feature a weak covalent bond that undergoes either homo-or heterolytic cleavage upon experiencing a force that exceeds a certain threshold. [1,5,7,13,14] These motifs are covalently incorporated into a polymer and serve as predefined weak links that preferentially break or transform in response to an applied mechanical force. [1,6,14-16] Widely investigated mechanophores include spiropyrans, 1,2-dioxetanes, and Diels-Alder adducts. [16-18] The rate constants, threshold forces, and transition state bond-lengths and energies of many mechanophores have been well-characterized via techniques such as single-molecule force spectroscopy (SMFS), [19-22] force-modified potential energy surface modeling, [23] and in situ activation using sonication. [2,22,24] The insights gained in such studies have driven advancements in the field of mechanoresponsive materials and the mechanical activation has, for example, been harnessed to promote thermodynamically unfavorable reactions, [19] affect the intra-or intermolecular transfer of protons, [20,25,26] release small molecules, [27] initiate the depolymerization of the surrounding material, [10,28] or elicit changes in the material's color or fluorescence. [16,17,29] The fact that the active bond or functional group of a mechanophore is typically cleaved irreversibly can limit its utility. Some mechanophores can be returned to their original state through an additional stimulus such as light or heat, but unless the mechanophore undergoes a nonscissile cleavage (e.g., a ring-opening reaction, such as in spiropyrans), the reversal is generally hampered by kinetic factors that leave the mechanophore in its cleaved state. [30] An irreversible response can be desirable for some

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Intramolecular non-covalent interactions as a strategy towards controlled photoluminescence in copper(i) complexes

Abstract: Easily accessible N-donor ligands enable tunable photoluminescence via steric modifications.

Cited by 19 publications

References 57 publications

Tracking Local Mechanical Impact in Heterogeneous Polymers with Direct Optical Imaging

Tracking Local Mechanical Impact in Heterogeneous Polymers with Direct Optical Imaging

Dynamic Phosphorescent Probe for Facile and Reversible Stress Sensing

From Molecules to Polymers—Harnessing Inter‐ and Intramolecular Interactions to Create Mechanochromic Materials

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