The efficiency of triplet-sensitized photon upconversion in ionic liquids was previously found to be dependent on the type of ionic liquid employed. The properties of the intermolecular energy transfer need to be understood in order to improve the upconversion efficiency. Here, we investigate the kinetics of the triplet energy transfer from the triplet sensitizing molecule to the emitter molecule where the latter is responsible for delayed upconversion fluorescence emission. The collision kinetics between the sensitizer and emitter molecules in imidazolium ionic liquids are investigated by systematically changing the alkyl chain length of the ionic liquid cation. Stern-Volmer analysis reveals unique diffusion behavior of the solute molecules in ionic liquids, and this observation is attributed to the microheterogeneity of the ionic liquids. Through time-resolved transient absorption measurements and determination of the triplet-triplet absorption coefficient of the sensitizer molecule used, we find that the quantum efficiency of the triplet energy transfer in the present system is sufficiently high (ca. 0.75) and independent of the type of ionic liquid. These findings show that the ionic liquid dependence of the upconversion efficiency arises from the later processes pertaining to the emitter molecule rather than the triplet energy transfer process.
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http://dx.doi.org/10.1021/jp3124082 | DOI Listing |
ChemSusChem
January 2025
Bedimensional Spa, Lungotorrente Secca, 3d, 16163, Genova, ITALY.
The design of interfaces between nanostructured electrodes and advanced electrolytes is critical for realizing advanced electrochemical double-layer capacitors (EDLCs) that combine high charge-storage capacity, high-rate capability, and enhanced safety. Toward this goal, this work presents a novel and sustainable approach for fabricating ionogel-based electrodes using a renewed slurry casting method, in which the solvent is replaced by the ionic liquid (IL), namely 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIFSI). This method avoids time-consuming and costly electrolyte-filling steps by integrating the IL directly into the electrode during slurry preparation, while improving the rate capability of EDLCs based on non-flammable ILs.
View Article and Find Full Text PDFDes Monomers Polym
January 2025
Leibniz-Institut für Polymerforschung Dresden e.V, Dresden, Germany.
Enhancing both ionic conductivity and mechanical robustness remains a major challenge in designing solid-state electrolytes for lithium batteries. This work presents a novel approach in designing mechanically robust and highly conductive solid-state electrolytes, which involves ionic liquid-based cross-linked polymer networks incorporating polymeric ionic liquids (PILs). First, linear PILs with different side groups were synthesized for optimizing the structure.
View Article and Find Full Text PDFACS Mater Au
January 2025
Department of Electrical and Electronic Engineering, Kyushu Institute of Technology, 1-1 Sensuicho, Tobataku, Kitakyushu, Fukuoka 804-8550, Japan.
Ionic gels (IGs), ionic liquids (ILs) dispersed in polymers, exhibit extremely low vapor pressure, electrochemical and thermal stability, and excellent mechanical characteristics; therefore, they are used for fabricating stretchable sensors, electrochemical transistors, and energy storage devices. Although such characteristics are promising for flexible and stretchable electronics, the mechanical stress-induced ruptured covalent bonds forming polymer networks cannot recover owing to the irreversible interaction between the bonds. Physical cross-linking via noncovalent bonds enables the interaction of polymers and ILs to form supramolecular IGs (SIGs), which exhibit favorable characteristics for wearable devices that conventional IGs with noncovalent bonds cannot achieve.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Department of Physics, The Graduate Center of CUNY, New York, NY, USA.
There is increasing interest in studying molecular motions in ionic liquids to gain better insights into their transport properties and to expand their applications. In this study, we have employed the fast field cycling relaxometry and pulsed field gradient nuclear magnetic resonance techniques to investigate the rotational and translational dynamics of fluorinated imide-based ionic liquids (ILs) at different temperatures. We have studied a total of six ILs composed of the 1-butyl-3-methylimidazolium cation ([BMIM]) combined with chemically modified analogs of the bis((trifluoromethyl)sulfonyl)imide anion ([NTf] or [TFSI]).
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, J. D. Block, Sec.III, Salt Lake, Kolkata, West Bengal 700 098, India.
We investigated the temperature dependence of the intermolecular dynamics, including intermolecular vibrations and collective orientational relaxation, of one of the most typical deep eutectic solvents, reline, using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES), subpicosecond optical Kerr effect spectroscopy (ps-OKES), and molecular dynamics (MD) simulations. According to fs-RIKES results, the temperature-dependent intermolecular vibrational band peak at ∼90 cm exhibited a redshift with increasing temperature. The density-of-state (DOS) spectrum of reline by MD simulations reproduced this fs-RIKES spectral feature.
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