Article
Chemistry, Physical
Elvis N. Nishida, Elder C. Leopoldino, Laize Zaramello, Higor A. Centurion, Renato Goncalves, Ricardo F. Affeldt, Carlos E. M. Campos, Bruno S. Souza
Summary: A novel Pd(II)-polymeric pre-catalyst was successfully prepared and demonstrated good activity in the Suzuki-Miyaura coupling reaction. The catalyst showed recyclability and its performance was affected by the concentration of the cross-coupling partners. The presence of oxygen was found to be crucial in preventing the formation of inactive Pd(0) aggregates.
Article
Chemistry, Multidisciplinary
Sheng-Qi Qiu, Yu Chen, Xiang-Jun Peng, Shi-Jiang He, Jun Kee Cheng, Yong-Bin Wang, Shao-Hua Xiang, Jun Song, Peiyuan Yu, Junmin Zhang, Bin Tan
Summary: In this study, we achieved the arene-alkene Suzuki-Miyaura coupling reaction between hindered aryl halides and vinyl boronates by designing appropriate ligands and reaction parameters. The axially chiral acyclic aryl-alkenes obtained exhibited remarkable efficiency, enantioselectivity, and E/Z selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Matteo Albino, Thomas J. Burden, Carmen C. Piras, Adrian C. Whitwood, Ian J. S. Fairlamb, David K. Smith
Summary: The increase in demand and low abundance of palladium pose a significant threat to its future availability, making research into sustainable palladium-based technologies crucial. This study reports the development of Pd scavenging hybrid gel beads composed of agarose and a low-molecular-weight gelator based on DBS-CONHNH2. These mechanically robust gel beads exhibit potential as practical catalysts for Suzuki-Miyaura cross-coupling reactions, demonstrating good reusability, green metrics, and improved reaction times compared to previous examples. The leaching of palladium is almost completely eliminated and a detailed investigation explains how the nanoparticles are formed in situ. These ligand-free gel beads can be considered as robust nonligated heterogeneous PdNP catalysts with potential for the development of easily used chemical reaction systems.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Inorganic & Nuclear
Ceren Akpunar, Namik Ozdemir, Mert Olgun Karatas, Bulent Alici, Ismail Ozdemir
Summary: In this study, we synthesized five new coumarin-functionalised PEPPSI type Pd-NHC complexes to examine their catalyst properties. The complexes showed slightly distorted square-planar geometry and exhibited catalytic activity in the Suzuki-Miyaura reaction of phenylboronic acid and aryl bromide derivatives.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Orhan Altan
Summary: This study investigates the catalytic activity of Pd (II) complexes of phosphino-benzaldoxime ligands in Suzuki-Miyaura coupling reactions. The results show that reducing the amount of catalyst leads to an increase in catalytic activity, and it is found that palladium nanoparticles formed in the reaction medium are responsible for this activity. This study contributes to the debate over whether the catalytic activity of phosphine-palladium complexes in SMC reactions results from a homogeneous or heterogeneous pathway.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Julius Hoepfner, Marius Brehm, Pavel A. Levkin
Summary: The rising costs of pharmaceutical research are currently limiting the productivity of drug discovery and development, but can potentially be reduced through miniaturization of compound synthesis and screening. In this study, the influential palladium-catalyzed Suzuki-Miyaura reaction is successfully implemented at the nanoliter scale on droplet microarrays for the synthesis of an 800-compound library of biphenyls. The synthesis of these compounds requires minimal reagents and solvent volume, and the obtained compounds can be purified and cleaved from excess reactants and catalyst. This novel approach expands the capabilities of droplet microarrays for miniaturized high-throughput chemical synthesis and opens up possibilities for future synthesis and screening of chemical compounds in a single platform.
Article
Chemistry, Physical
Jonathan De Tovar, Franck Rataboul, Laurent Djakovitch
Summary: The study on a series of palladium(II) complexes with bis(NHC) ligands immobilized on TiO2 surface reveals that these complexes evolve to Pd NPs at the TiO2 surface under reaction conditions, releasing Pd species in the liquid phase. The reactivity is enhanced by the in situ generation of Mott-Schottky heterojunctions, leading to new pathways for the design of heterogenized catalysts in reverse-flow reactors.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Applied
Mingyang Gao, Jiamin Wang, Weixiang Shang, Yuchao Chai, Weili Dai, Guangjun Wu, Naijia Guan, Landong Li
Summary: Suzuki-Miyaura cross-coupling reaction is a powerful method to construct carbon-carbon bonds and is widely used in the synthesis of functional organic compounds. In this study, zeolite-encased Pd particles (Pd@MFI) were successfully prepared and investigated as promising heterogeneous catalysts for the Suzuki-Miyaura cross-coupling reaction. The Pd@MFI catalysts showed high activity, with dispersed Pd particles efficiently stabilized within the MFI zeolite matrix. The presence of basic sites adjacent to Pd sites was crucial for achieving high catalytic activity.
Article
Chemistry, Multidisciplinary
Shiguang Pan, Cong Gao, Jiatong Gui, Beibei Hu, Lifeng Gai, Changsheng Qiao, Chengwei Liu
Summary: A hierarchical titanium dioxide microspheres-supported palladium catalyst (Pd/TiO2-350) was successfully prepared and characterized. The Pd immobilization on TiO2 was confirmed with a palladium loading of 0.1 mmol g(-1) by ICP-OES analysis. Pd/TiO2-350 efficiently catalyzed the Suzuki-Miyaura reaction and could be reused multiple times without significant loss of activity, with a decreased loading of palladium species to 0.001 mol% and high turnover number and turnover frequency of 99,000 and 0.57 s(-1), respectively.
ARABIAN JOURNAL OF CHEMISTRY
(2023)
Article
Polymer Science
Haniyeh Daneshafruz, Hossein Barani, Hassan Sheibani
Summary: The study utilizes graphene oxide as a stable support for palladium nanoparticles, resulting in a heterogeneous nanocatalyst. The nanocatalyst demonstrates excellent catalytic efficiency through various characterization techniques. It is efficient, cost-effective, and environmentally friendly, maintaining its catalytic activity after multiple uses.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2022)
Article
Chemistry, Applied
Andrei Baran, Mariia Babkova, Jana Petkus, Kirill Shubin
Summary: A convenient and general method for Suzuki-Miyaura double cross-coupling of various dibromothiophenes was developed. Using a simple and cheap catalytic system, diarylthiophenes, useful in the synthesis of metal-organic frameworks (MOFs), can be obtained in moderate to excellent yields. The efficiency of the catalytic process and excess of boronic acids help to suppress side products and simplify the purification of products.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Xiao-Jing Wei, Bingxiang Xue, Jens Handelmann, Zhiyong Hu, Heidar Darmandeh, Viktoria H. Gessner, Lukas J. Goossen
Summary: In this study, a novel catalyst prYPhos was developed to promote Pd-catalyzed Suzuki-Miyaura couplings. Under mild reaction conditions, this catalyst efficiently produced various (hetero)biaryls with good tolerance towards sensitive functional groups and steric hindrance. The results demonstrated that this catalyst exhibited high selectivity in selectively coupling chlorides and leaving triflate groups intact.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Puja Singh, Aslam C. Shaikh
Summary: Sonogashira coupling, discovered in 1975, is a Nobel reaction that forms a C-C bond using palladium and copper co-catalysts. Incorporating alkyne functionalities in macro or micro molecules through this reaction has proven its viability in synthetic chemistry. Recently, visible light photoredox catalysts have emerged as an advanced tool, and this review aims to provide a comprehensive summary of modern visible light photo redox catalyzed Sonogashira reaction, discussing alternative strategies, metal-based nanomaterial photocatalysts, copper or palladium-free photocatalytic methods, and organo-photolytic and bioinspired photocatalysts, along with mechanistic aspects and substrate scope.
CHEMICAL COMMUNICATIONS
(2023)
Article
Biochemistry & Molecular Biology
Gongshu Wang, Jiwei Wang, Zhangpei Chen, Jianshe Hu
Summary: In this study, a metal-organic framework material based on chitosan microspheres was successfully prepared, and the catalytic activity and stability were further enhanced by encapsulating nanoparticles. The universal applicability of this preparation strategy was also demonstrated, and the material exhibited biodegradability and excellent recycling properties.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2022)
Article
Chemistry, Applied
Kanticha Khomthawee, Nattaporn Nilada, Antika Homchuen, Pranorm Saejueng
Summary: The CS-EDTA-Pd catalyst was prepared by dissolving chitosan and EDTA in acetic acid, forming beads, adsorbing palladium(II), and reducing it to palladium(0) with ethanol reflux. The catalyst was characterized by various techniques. It was then tested in the Suzuki-Miyaura cross-coupling reaction and showed good catalytic activity. The catalyst is inexpensive, easy to prepare, and can be reused multiple times with only a slight loss in product yields.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Karl Ridier, William Nicolazzi, Lionel Salmon, Gabor Molnar, Azzedine Bousseksou
Summary: Molecular spin-crossover (SCO) compounds are a promising class of photoactive materials that exhibit efficient photoinduced phase transitions (PIPT). Through the study of the spatiotemporal dynamics of a single crystal PIPT within the thermodynamic metastability region, it was found that the PIPT occurs through the sequential activation of two switching mechanisms on sub-microsecond and millisecond timescales. The main discovery is that thermodynamic metastability has no influence on the sub-millisecond switching dynamics.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Montserrat Miranda-Olvera, Rafael Arcos-Ramos, Mauricio Maldonado-Dominguez, Lionel Salmon, Gabor Molnar, Azzedine Bousseksou, Maria del Pilar Carreon-Castro
Summary: A series of small benzothiadiazole (BTD)-based derivatives with a D-A-D architecture were synthesized and characterized for their potential use as building blocks of organic semiconducting materials. One derivative (BuO-BTD) was identified as a strong candidate for use as an electron transport layer in organoelectronic devices.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Physical
Mario Piedrahita-Bello, Yue Zan, Alejandro Enriquez-Cabrera, Gabor Molnar, Bertrand Tondu, Lionel Salmon, Azzedine Bousseksou
Summary: Macroscopic, soft bilayer spin crossover@polymer actuators were fabricated by embedding [Fe(NH(2)trz)(3)]SO4 spin crossover particles in a P(VDF-TrFE) matrix and incorporating silver flakes for electro-thermal actuation. The speed and amplitude of the actuator bending movement, as well as its charge capacity and ability to follow a sinusoidal position, were investigated.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Engineering, Electrical & Electronic
Bertrand Tondu, Mario Piedrahita-Bello, Lionel Salmon, Gabor Molnar, Azzedine Bousseksou
Summary: This study demonstrates an electro-thermally actuated, bilayer bending actuator based on spin crossover molecules, showing that a simple closed-loop PID control can significantly reduce the response time and achieve satisfactory tracking performance.
SENSORS AND ACTUATORS A-PHYSICAL
(2022)
Article
Chemistry, Physical
Qiuxia Zhao, Naixin Kang, Marta Martinez Moro, Eduardo Guisasola Cal, Sergio Moya, Emerson Coy, Lionel Salmon, Xiang Liu, Didier Astruc
Summary: In this study, a novel nanocatalyst system was reported for hydrogen generation from water under ambient conditions. The system, named nanozymes, exhibits similar function and mechanism to hydrogenase enzymes. It was found that the Au4Rh1 system shows the best synergy in the dark and can complete the hydrogen generation reaction in a short period of time. Additionally, visible light irradiation can further enhance the catalytic activity of the Au-Rh catalyst.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Nanoscience & Nanotechnology
Oleksandr Ye. Horniichuk, Karl Ridier, Lijun Zhang, Yuteng Zhang, Gabor Molnar, Lionel Salmon, Azzedine Bousseksou
Summary: This study reports on the fabrication, characterization, and application of high-quality nanometric thin films of the molecular spin-crossover complex [Fe(HB(1,2,3-triazol-1-yl)3)2], with thicknesses in the range 20-200 nm. The films were obtained by vacuum thermal evaporation and characterized using various techniques. The films exhibit a gradual spin conversion centered at approximately 374 K and can enhance the UV-light thermoreflectance coefficient of reflective surfaces.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Physical
Naixin Kang, Xiaorong Wei, Ruofan Shen, Baojun Li, Eduardo Guisasola Cal, Sergio Moya, Lionel Salmon, Changlong Wang, Emerson Coy, Murielle Berlande, Jean-Luc Pozzo, Didier Astruc
Summary: This study reports the efficient performance of AuNi@ZIF-8 alloys as nanocatalysts for H2 evolution from ammonia borane hydrolysis under visible-light illumination. The catalytic activity of AuNi@ZIF-8 alloys under visible light was found to be 3.4 times higher than that of the monometallic Ni catalyst in the dark. This improvement is attributed to the superior support of ZIF-8 in Au0.5Ni0.5@ZIF-8 and the localized surface plasmon resonance induced between 450 and 620 nm. The results also reveal that the activation of water is always the rate-determining step.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Physical
Naixin Kang, Ruofan Shen, Baojun Li, Fangyu Fu, Bruno Espuche, Sergio Moya, Lionel Salmon, Jean-Luc Pozzo, Didier Astruc
Summary: The synthesized AuPd@ZIF-8-alloyed nanoparticles serve as an excellent nanocatalyst for the methanolysis reaction of aminoborane under visible light irradiation, producing H-2 at a high rate. The visible-light-induced acceleration is attributed to the Au plasmonic excitation provoking hot electron transfer from Au to Pd-substrate ensemble.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Nanoscience & Nanotechnology
Yue Liu, Fangyu Fu, Lionel Salmon, Bruno Espuche, Sergio Moya, Murielle Berlande, Jean-Luc Pozzo, Jean-Rene Hamon, Didier Astruc
Summary: A new type of catalyst support, involving the addition of metal ion precursors to core-shell ZIF-8@ZIF-67, was proposed and its performance exceeded that of nanocatalysts in ZIF-8 or ZIF-67. Under visible-light illumination, the optimized nanocatalysts achieved a turnover frequency of 430 h-1 for selective formic acid dehydrogenation. The superiority of ZIF-8@Pd2Ag1@ZIF-67 over other catalysts was confirmed in the benchmarking model of 4nitrophenol reduction, indicating the interest in this novel catalyst design.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Seyed Ehsan Alavi, Baptiste Martin, Yue Zan, Xinyu Yang, Mario Piedrahita-Bello, William Nicolazzi, Jean-Francois Ganghoffer, Lionel Salmon, Gabor Molnar, Azzedine Bousseksou
Summary: This study investigates the interplay between the thermomechanical and spin-crossover properties of stimuli-responsive polymer composites containing [Fe(NH2trz)3]SO4 and [Fe(Htrz)(trz)2]BF4 particles embedded in thermoplastic polyurethane and P(VDF-TrFE) matrices. The composites exhibit characteristic elastic softening and increased mechanical damping around the spin transition temperature, resulting from the significant spin state-volume strain coupling in the particles. The transformation strain and stress in the composites significantly increase and decrease, respectively, in soft matrices, as explained by micromechanical simulations. These findings offer a fundamental understanding and quantitative guidelines for the design of spin-crossover polymer composites for mechanical transducer applications.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Damian Paliwoda, Laure Vendier, Livia Getzner, Frederico Alabarse, Davide Comboni, Baptiste Martin, Seyed Ehsan Alavi, Mario Piedrahita Bello, Lionel Salmon, William Nicolazzi, Gabor Molnar, Azzedine Bousseksou
Summary: Two benchmark Fe(II)-triazole spin-crossover compounds, [Fe(Htrz)2trz]BF4 (1) and [Fe(NH2trz)3]SO4 (2), were investigated using various techniques to evaluate their transformation strain, compressibility, and anisotropy. Elastic softening and mechanical damping were observed during the spin-crossover process in both compounds, suggesting a coupling between spin state and lattice strain. The elastic potential energy, stored elastic work, and frictional work were assessed, providing important insights for understanding the behavior of this compound family and guiding their technological applications.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Lijun Zhang, Karl Ridier, Oleksandr Ye. Horniichuk, Steïphane Calvez, Lionel Salmon, Gaïbor Molnar, Azzedine Bousseksou
Summary: The formation of hybrid light-matter states, which allows control of quantum-mechanical states and manipulation of molecular materials, has been observed in switchable strong light-matter coupling involving bistable spin-crossover molecules. The thermally induced switching between low-spin and high-spin states of these molecules enables fine control of the light-matter hybridization strength, offering the possibility of reversible switching between ultrastrong- and weak-coupling regimes within a single photonic structure. This work demonstrates the potential of spin-crossover molecular compounds in the development of tunable polaritonic devices and polaritonic chemistry.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Automation & Control Systems
Yue Zan, Mario Piedrahita-Bello, Seyed E. Alavi, Gabor Molnar, Bertrand Tondu, Lionel Salmon, Azzedine Bousseksou
Summary: The paper presents a bilayer bending cantilever actuator made of thermoplastic polyurethane (TPU) with embedded [Fe(NH(2)trz)(3)](SO4) molecular spin-crossover (SCO) particles. The actuator is capable of converting electrothermal input into mechanical response, and exhibits a curvature change of 0.11 mm^-1, a free transformation strain of 1.6%, and an effective work density of 1.25 mJ cm^-3. The actuator also demonstrates a fast response time and robustness in closed-loop experiments.
ADVANCED INTELLIGENT SYSTEMS
(2023)
Article
Chemistry, Inorganic & Nuclear
Xinyu Yang, Alejandro Enriquez-Cabrera, Dorian Toha, Yannick Coppel, Lionel Salmon, Azzedine Bousseksou
Summary: A pure mixed-anion Fe(NH(2)trz)(3)(BF4)(SiF6)(0.5) spin crossover complex is obtained through a solid-liquid post synthetic modification approach from the Fe(NH(2)trz)(3)(BF4)(2) parent complex. Highly crystalline powder samples incorporating homogeneous micrometric (1 & mu;m long) rod-shaped particles can be achieved using this method. This compound exhibits an abrupt spin crossover behavior with a narrow (10 K) hysteresis loop centered just above room temperature (320 K), making it highly interesting for integration into various application devices.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Alejandro Enriquez-Cabrera, Livia Getzner, Lionel Salmon, Lucie Routaboul, Azzedine Bousseksou
Summary: The influence of solvent on the post-synthetic modification of the spin crossover complex with [Fe(NH(2)trz)(3)](NO3)(2) and p-anisaldehyde was comprehensively studied. It was found that using a suitable solvent like ethanol led to complete modification, while unsuitable solvents like toluene or 1-octanol resulted in incomplete reactions or undesired species.
NEW JOURNAL OF CHEMISTRY
(2022)
