Review
Chemistry, Multidisciplinary
Riccardo Marin, Gabriel Brunet, Muralee Murugesu
Summary: Single-molecule magnets play a crucial role in quantum information processing and spintronics. The harmonious combination of magnetism and luminescence within single molecules provides insights for emerging next-generation spintronics devices.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Vijay S. Parmar, David P. Mills, Richard E. P. Winpenny
Summary: Recent studies have shown that mononuclear lanthanide (Ln) complexes can be high-performing single-molecule magnets (SMMs). The focus is on mononuclear Dy-III alkoxide and aryloxide SMMs with coordination numbers up to eight, covering synthesis, solid-state structures and magnetic attributes. Brief overviews are also provided of mononuclear Tb-III, Ho-III, Er-III and Yb-III alkoxide and aryloxide SMMs.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Paul Richardson, Riccardo Marin, Yixin Zhang, Bulat Gabidullin, Jeffrey Ovens, Jani O. Moilanen, Muralee Murugesu
Summary: A novel tetranuclear lanthanide cluster has been reported, with its structure and properties elucidated through single-crystal X-ray crystallography and magnetic spectroscopy. Computational studies validated its magnetization dynamics and relaxation pathways, demonstrating its behavior as a single-molecule magnet.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Chaoqing Yang, Dimitrije Mara, Joydeb Goura, Flavia Artizzu, Rik Van Deun
Summary: Lanthanide hydrogen-bonded organic frameworks (LnHOFs) are a versatile class of multicomponent luminescent materials with potential applications in optics and photonics. PHTF:Eu, a trivalent europium (Eu3+) incorporated polymeric hydrogen-bonded triazine frameworks, exhibits intense red luminescence with high color purity. PHTF:Eu also functions as a self-referencing thermometer in the cryogenic temperature range.
Article
Chemistry, Inorganic & Nuclear
Arpan Mondal, Sanjit Konar
Summary: A dinuclear ytterbium complex has been designed with a strong ligand field in equatorial positions, showing easy-axis anisotropy and field induced slow relaxation of magnetization in magnetic studies, with a remarkable energy barrier. Ab initio calculations reveal the importance of a weak axial ligand field in designing high-performance Yb-based SMMs.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Peng-Bo Jin, Ke-Xin Yu, Yuan-Qi Zhai, Qian-Cheng Luo, Yi-Dian Wang, Xu-Feng Zhang, Yi Lv, Yan-Zhen Zheng
Summary: Two dysprosium(III) complexes have been confirmed as single-molecule magnets, with the dimer showing enhanced magnetic relaxation barrier. Dilution experiments with the yttrium(III) analogue indicate the single-ion nature of the magnetic behavior.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jules Moutet, Jules Schleinitz, Leo La Droitte, Maxime Tricoire, Fabrice Pointillart, Frederic Gendron, Thomas Simler, Carine Clavaguera, Boris Le Guennic, Olivier Cador, Gregory Nocton
Summary: Divalent lanthanide organometallics are highly reducing compounds known for single electron transfer reactivity and small molecule activation. This study presents a rare organometallic sandwich compound of divalent thulium with the cyclooctatetraenyl ligand, introducing it as an additional strategy for designing high-performing Single Molecule Magnets. The first divalent thulium sandwich complex with f(13) configuration behaves as a single-molecule magnet even in the absence of a DC field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sofia Zanella, Maxime Aragon-Alberti, Carlos D. S. Brite, Fabrice Salles, Luis D. Carlos, Jerome Long
Summary: Luminescent thermometry enables remote temperature detection and has great potential in future technological applications. We demonstrate for the first time that luminescence thermometry can be combined with a complementary temperature readout related to a different property. By taking advantage of the temperature dependence of magnetic and luminescence features in Single-Molecule Magnets (SMM), we develop original dual magneto-optical molecular thermometers that offer a 10-fold improvement in relative thermal sensitivity over the whole temperature range.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Rute A. S. Ferreira, Ekaterina Mamontova, Alexandre M. P. Botas, Mikhail Shestakov, Johan Vanacken, Victor Moshchalkov, Yannick Guari, Liviu F. Chibotaru, Dominique Luneau, Paulo S. Andre, Joulia Larionova, Jerome Long, Luis D. Carlos
Summary: Sensors are becoming more prevalent in various technological applications, with the challenge of engineering smart systems capable of detecting multiple physical quantities simultaneously. Using molecular chemistry, it has been shown that a luminescent single-molecule magnet can act as a dual thermometric/magnetic optical sensor, holding promise for detecting variations in future devices.
ADVANCED OPTICAL MATERIALS
(2021)
Article
Chemistry, Physical
Mikhail B. Vialtsev, Liubov O. Tcelykh, Alexey Yu. Bobrovsky, Valentina V. Utochnikova
Summary: The mixture of monometallic compounds showed superiority over bimetallic ones in terms of temperature sensitivity in luminescence thermometers.
JOURNAL OF ALLOYS AND COMPOUNDS
(2022)
Review
Chemistry, Inorganic & Nuclear
Yury A. Belousov, Andrei A. Drozdov, Ilya Taydakov, Fabio Marchetti, Riccardo Pettinari, Claudio Pettinari
Summary: The azole carboxylic acids provide a unique platform for driving the complex structures of lanthanide compounds, leading to materials with various desired properties. Understanding the coordination modes and synthesis of these compounds plays a crucial role in producing efficient advanced materials.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Junhao Wang, Jakub J. J. Zakrzewski, Mikolaj Zychowicz, Yue Xin, Hiroko Tokoro, Szymon Chorazy, Shin-ichi Ohkoshi
Summary: A new approach combining the behavior of Single-Molecule Magnets (SMMs) and luminescence thermometry has been studied for the contactless temperature readout of future SMM-based devices. It was found that the structural transformation of Tb-III-based emissive SMMs formed in a cyanido-bridged framework can enhance the SMM effect, resulting in SMM features up to 42 K. Both systems exhibit emission related to f-f electronic transitions, allowing for optical thermometry below 100 K. Dehydration expands the temperature overlap between SMM behavior and thermometry, from 6 K to 42 K.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Inorganic & Nuclear
Yun-Xia Qu, Pei-Yu Liao, Yan-Cong Chen, Ming-Liang Tong
Summary: This article reviews the coordination chemistry, single-molecule magnetism, and optical properties of lanthanide complexes based on the hexadentate mixed ligand H2bbpen, aiming to find relevant correlations between magnetic and optical structures to promote further developments in this family and related systems.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Junyu Hong, Feilong Liu, Miroslav D. Dramicanin, Lei Zhou, Mingmei Wu
Summary: A series of Yb3+- and Er3+-doped Ca3Sc2Si3O12 (CSS) upconversion (UC) phosphors were synthesized by the sol-gel combustion method to develop novel luminescent materials for optical temperature measurement. The addition of Yb3+ greatly enhanced the emission of Er3+ by effective energy transfer. The prepared CSS:Yb3+,Er3+ phosphors exhibited green and red emissions corresponding to specific transitions of Er3+, and showed excellent temperature-dependent behavior with high sensitivity.
Article
Chemistry, Physical
Qincan Ma, Ning Guo, Jing Wang, Baiqi Shao, Yanmei Xin, Ruizhuo Ouyang
Summary: This study discusses the relationship between thermal quenching performance and energy gap, and adjusts the thermal quenching activation energy by controlling the ion ratio and ligand structure. It proposes a new method for designing fluorescent powder materials with adjustable thermal quenching activation energy.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Editorial Material
Materials Science, Ceramics
Kyle Brinkman, Armin Feldhoff, Eva Hemmer, Krista Carlson
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Soham Mukherjee, Sarmad Naim Katea, Emille M. Rodrigues, Carlo. U. Segre, Eva Hemmer, Peter Broqvist, Hakan Rensmo, Gunnar Westin
Summary: Nanocrystalline ZnO sponges doped with EuO1.5 were successfully prepared by heating metal-salt complex based precursor pastes. Phase separation between ZnO and c-Eu2O3 was observed at temperatures above 700 degrees C. The clean oxide made at 600 degrees C showed a slight volume increase compared to undoped ZnO, and the Eu-doping had little effect on the local structure of ZnO.
Article
Chemistry, Multidisciplinary
Tamara Munoz-Ortiz, Idoia Alayeto, Jose Lifante, Dirk H. Ortgies, Riccardo Marin, Emma Martin Rodriguez, Maria del Carmen Iglesias de la Cruz, Gines Lifante-Pedrola, Jorge Rubio-Retama, Daniel Jaque
Summary: Nanothermometry utilizes nanoparticles as thermal probes, enabling remote and minimally invasive sensing. It has emerged as a powerful tool in biomedicine. However, the lack of 3D thermal imaging capability and readily available tools in clinic hinders its translation to the bedside.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
J. Mikko Rautiainen, Maryna Green, Minna Mahonen, Jani O. Moilane, Manu Lahtinen, Arto Valkonen
Summary: Halogen bonding interactions were studied in 15 crystalline 3-iodopyridinium systems. Experimental results showed that halogen bonding acts as a secondary intermolecular force in these charged systems, while still maintaining high directionality of interaction. Computational studies validated the experimental data and showed that halogen bond strengths were exaggerated in smaller model systems, but improved agreement between experimental and calculated structures was seen in larger systems. The strength of halogen bonds was found to come second to electrostatic interactions in stabilizing structures, but played a major role in directing the packing of solid-state structures.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Nanoscience & Nanotechnology
Khouloud Hamraoui, Vivian Andrea Torres-Vera, Irene Zabala Gutierrez, Alejandro Casillas-Rubio, Mohammed Alqudwa Fattouh, Antonio Benayas, Riccardo Marin, Marta Maria Natile, Miguel Manso Silvan, Juan Rubio-Zuazo, Daniel Jaque, Sonia Melle, Oscar G. Calderoin, Jorge Rubio-Retama
Summary: Rare-earth doped nanoparticles (RENPs) have attracted increasing interest in materials science due to their optical, magnetic, and chemical properties. RENPs can emit and absorb radiation in the second biological window (NIR-II, 1000-1400 nm), making them ideal optical probes for in vivo imaging. The optimization of thermal sensitivity in RENPs depends on the core chemical composition and size, active-shell, and outer-inert-shell thicknesses.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Nanoscience & Nanotechnology
Claudia M. S. Calado, Diogo A. Galico, Muralee Murugesu
Summary: Composition control is a powerful tool for adjusting the optical outputs of high-performance lanthanide luminescent materials. Although commonly used in hierarchically structured nanoparticles, this strategy is seldom applied to molecular compounds due to the limited number of metal centers within a single unit. In this study, we investigate the composition control in a series of molecular cluster-aggregates with an icosanuclear core, aiming to adjust the optical output similarly to nanoparticles. Through exploring the impact of the addition of a third doping ion, we gain insights into the luminescent processes and qualitative trends in each molecular cluster-aggregate.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Liyan Ming, Irene Zabala-Gutierrez, Paloma Rodriguez-Sevilla, Jorge Rubio Retama, Daniel Jaque, Riccardo Marin, Erving Ximendes
Summary: This article introduces a luminescence lifetime estimation method based on U-NET to improve the estimation accuracy under extremely low signal-to-noise ratio conditions. The effectiveness of U-NET is demonstrated in luminescence lifetime thermometry and its sensing performance improvement is verified through two experiments under extreme measurement conditions.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Carlos D. S. Brites, Riccardo Marin, Markus Suta, Albano N. Carneiro Neto, Erving Ximendes, Daniel Jaque, Luis D. Carlos
Summary: Luminescence (nano)thermometry is a remote sensing technique that utilizes the temperature dependency of luminescence features to measure temperature. It has potential applications in various fields and requires the establishment of a theoretical background, standardized practices, and improved readouts through multiparametric analysis and artificial intelligence algorithms. Challenges in luminescence thermometry and the need for continuous innovation are also discussed.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Diogo Alves Galico, Muralee Murugesu
Summary: Remote temperature probing at cryogenic range is crucial for the advancement of future quantum technologies. In this study, a novel magneto-optical thermometric approach based on magnetic-circular dichroism(MCD) technique is proposed, which offers unprecedented capabilities for meticulous temperature variation analysis at cryogenic temperatures. The use of MCD C-term's temperature sensitivity, combined with both positive and negative signals, enables highly sensitive magneto-optical temperature probing. Additionally, a groundbreaking high relative thermal sensitivity value of 95.3 % K-1 at 2.54 K can be achieved using a mononuclear lanthanide complex, [[Ho(acac)(3)(phen)], in the presence of a 0.25 T applied magnetic field and using a combination of multiparametric thermal read-out with multiple regression. These results unequivocally demonstrate the viability and effectiveness of the proposed methodology for cryogenic temperature sensing.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Liyan Ming, Irene Zabala-Gutierrez, Oscar G. Calderon, Sonia Melle, Erving Ximendes, Jorge Rubio-Retama, Riccardo Marin
Summary: Silver chalcogenide semiconductor nanocrystals (Ag2E SNCs) play an important role in the biomedical field due to their near-infrared excitation and low cytotoxicity. However, their low photoluminescence quantum yield poses a challenge for bioimaging and biosensing applications. This article provides an overview of strategies to improve the brightness of Ag2E SNCs by addressing defects, metallic silver, and composition issues. Future research directions to further enhance the brightness and effectiveness of Ag2E SNCs in biomedical applications are also discussed.
Article
Chemistry, Inorganic & Nuclear
Niki Mavragani, Alexandros A. Kitos, Jakub Hruby, Stephen Hill, Akseli Mansikkamaki, Jani O. Moilanen, Muralee Murugesu
Summary: A new series of radical-bridged dinuclear lanthanide metallocenes were synthesized by combining high-performing lanthanide metallocenes and tetrazine-based radical ligands. The formation of radical species was confirmed by various techniques. The choice of ancillary ligands and the steric effects played a crucial role in promoting stronger magnetic exchange coupling and achieving slow relaxation of the magnetization.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Materials Science, Multidisciplinary
Wojciech M. Piotrowski, Maja Szymczak, Emma Martin Rodriguez, Riccardo Marin, Marta Henklewska, Blazej Pozniak, Miroslav Dramicanin, Lukasz Marciniak
Summary: The increasing popularity of luminescent nanothermometry in recent years is due to its potential application in biomedicine. This study introduces a biocompatible bimodal luminescent thermometer that operates in ratiometric and luminescence lifetime modes, offering high sensitivity and low cytotoxicity, making it suitable for bioapplications.
MATERIALS CHEMISTRY AND PHYSICS
(2024)
Article
Chemistry, Multidisciplinary
Nan Liu, Christian Homann, Samuel Morfin, Meghana S. Kesanakurti, Nicholas D. Calvert, Adam J. Shuhendler, Tom Al, Eva Hemmer
Summary: Multimodal bioimaging probes with optical, MRI, and CT capabilities offer promising biomedical applications. Researchers prepared nanoparticles with multimodal capabilities and addressed issues such as UC emission loss and the effect of outer shell thickness on magnetic and CT performance.
Article
Chemistry, Multidisciplinary
Claudia Manuela Santos Calado, Diogo Alves Galico, Muralee Murugesu
Summary: The impact of composition control and energy transfer on luminescence thermometry in a TbIII/EuIII dual-emitting molecular cluster-aggregate, known as {Ln20}, was investigated. The study of lifetime dynamics provides new insights into enhancing thermometric performance through rational planning and understanding intriguing optical properties.
CHEMICAL COMMUNICATIONS
(2023)
Article
Nanoscience & Nanotechnology
Claudia M. S. Calado, Diogo A. Galico, Muralee Murugesu
Summary: This work presents a study on molecular cluster-aggregates with a 20-metal core, exploring the use of composition control to modulate optical outputs. The impact of a third lanthanide ion on energy transfer and optical thermometry performance is investigated.
ACS APPLIED MATERIALS & INTERFACES
(2023)