Review
Chemistry, Inorganic & Nuclear
Macarena Poyatos, Eduardo Peris
Summary: Janus di-N-heterocyclic carbene (NHC) ligands are a subclass of poly-NHCs that feature coordination to two transition metals in a facially opposed manner, making them useful in areas such as homogeneous catalysis, materials chemistry, and supramolecular chemistry. This review aims to cover the most relevant advances in the use of Janus-di-NHCs over the last 15 years, classified by their specific structural features.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Jean Michel Merkes, Tobias Ostlender, Fufang Wang, Fabian Kiessling, Haitao Sun, Srinivas Banala
Summary: The increase in the number of nitrogen atoms results in a blueshift in absorption and an increase in fluorescence quantum yield. This is attributed to a decrease in HOMO energy levels without affecting LUMO levels.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Ivan Basalov, Alexander A. Kissel, Elena N. Nikolaevskaya, Nikolai O. Druzhkov, Anton Cherkasov, Jerome Long, Joulia Larionova, Georgy K. Fukin, Alexander A. Trifonov
Summary: The reactions of 2-imino-2,3-dihydrobenzoxazole with compounds containing Yb, Ca, and Y result in the formation of various coordination complexes, involving the opening of the dihydrobenzoxazole ring, elimination of nitrogen sources, and activation of C-H bonds.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Yi-Fan Zhang, Ya-Wen Zhang, Xin Li, Li-Ying Sun, Ying-Feng Han
Summary: Triarylborane-based discrete metal-carbene supramolecular cages [M-3(1)(2)](PF6)(3) (M = Ag, Au) were synthesized and characterized. The new hexacarbene assemblies show a significant solvatochromic effect in solvents of different polarity. Furthermore, the reversible fluoride binding property of [Au-3(1)(2)](PF6)(3) was investigated by UV-vis absorption and fluorescence titrations. This work holds promise for future developments in the area of highly emissive and stimulus-responsive NHC-metal assemblies.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Wiebke Drescher, Christian Kleeberg
Summary: The N-H deprotonation of diborane(4) results in a compound with Lewis basic nitrogen atoms and Lewis acidic boron atoms, which governs its reactivity and structural chemistry. While the first deprotonation is readily achieved with various bases, the second deprotonation requires a strong base like Li(tmp).
DALTON TRANSACTIONS
(2021)
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
Chemistry, Multidisciplinary
Douglas Turnbull, Marc-Andre Legare
Summary: A one-pot procedure for synthesizing aryldifluoroboranes from bench-stable arylsilanes is presented. These aryldifluoroboranes react conveniently with aryllithium reagents to form unsymmetrical boranes, which have been characterized crystallographically to study their geometric and crystal packing trends.
Article
Chemistry, Multidisciplinary
Stephen J. Geier, Justin F. Binder, Christopher M. Vogels, Lara K. Watanabe, Charles L. B. Macdonald, Stephen A. Westcott
Summary: The uncatalyzed addition of catecholborane to alpha-diimines has been studied, showing that the reactions proceed smoothly at room temperature without a catalyst or additive. This results in the formation of bis-hydroboration products with 3-coordinate boron centres or mono-hydroboration products with 4-coordinate boron centres, depending on the nature of the diimine reagent.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Ning Xu, Toshikazu Ono, Yoshitsugu Morita, Teruyuki Komatsu, Yoshio Hisaeda
Summary: The first boron complexes of porphycenes, structural isomers of porphyrin, have been successfully synthesized using a microwave-assisted method, resulting in two different coordination structures. Monoboron porphycene favors coordination on the dipyrroethene site, while the regioisomer of diboron porphycene with cisoid stereochemistry is more stable. Protonation results in red shift in both absorption and emission spectra for monoboron porphycene, with a reversible trigger using acids and bases.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Joseph A. Zurakowski, Brady J. H. Austen, Maeve C. Dufour, Moulika Bhattacharyya, Denis M. Spasyuk, Marcus W. Drover
Summary: This study reported the preparation of a novel cobalt (III) hydride and the influence of ligand design on reactivity, combining synchrotron-radiation crystallography and electrochemical studies for detailed investigation.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Svetlana E. Korolenko, Elena A. Malinina, Varvara V. Avdeeva, Andrey V. Churakov, Sergey E. Nefedov, Aleksey S. Kubasov, Anatoliy S. Burlov, Lyudmila N. Divaeva, Konstantin Yu. Zhizhin, Nikolay T. Kuznetsov
Summary: In this study, the complexation of zinc(II) and cadmium(II) with benzimidazole derivatives in the presence of a competitive inorganic ligand was investigated. The study revealed the selective isolation of mixed-ligand cadmium(II) complexes with different metal atom positions around the boron cage, as well as the influence of the steric factor of organic ligands on the structure of reaction products.
Article
Materials Science, Multidisciplinary
Xin Wang, Hua Li, Xiaofu Wu, Haiyang Shu, Hongkun Tian, Hui Tong, Lixiang Wang
Summary: By designing and synthesizing D-A-type emitters based on boron ketoiminate acceptors and DMAC donors, along with factors such as closely aligned energy levels and intramolecular hydrogen bonding, the transformation from a conventional fluorescent molecule to a highly efficient TADF molecule has been achieved successfully.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
Article
Chemistry, Inorganic & Nuclear
Kriti Pathak, Shivankan Mishra, Chandan Nandi, Suvam Saha, Sundargopal Ghosh
Summary: Several dihydridoborate group 7 metal complexes with different chelation modes have been synthesized and their structures and bonding nature have been described. Photolysis of [M-2(CO)(10)] with these borate species resulted in the formation of dihydridoborate complexes. The electronic structures of these complexes have been investigated using density functional theory calculations.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Drifa Belkhir-Talbi, Naima Ghemmit-Doulache, Souhila Terrachet-Bouaziz, Malika Makhloufi-Chebli, Amal Rabahi, Lhassane Ismaili, Artur M. S. Silva
Summary: The coordination compounds of N,N'-di(4-bromophenyl)-4-hydroxycoumarin-3-carboximidamide (L1) were synthesized and characterized. It was found that L1 acted as a monodentate ligand and coordinated through -OH and -NH groups. The synthesized compounds exhibited significant antimicrobial and antioxidant activities.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Jun Fan, An-Ping Koh, Jingsong Zhou, Zheng-Feng Zhang, Chi-Shiun Wu, Richard D. Webster, Ming-Der Su, Cheuk-Wai So
Summary: The coordination of 1,3,4,5-tetramethylimidazol-2-ylidene (IMe) with diatomic B-2 species results in the formation of a tetrakis-(N-heterocyclic carbene)-diboron(0) compound. It possesses an unprecedented electronic structure and exhibits double single-electron-transfer reactivity in small-molecule activation. This compound also undergoes a transition-metal-free SET reduction of CO2 without the need for UV/vis light conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Riccardo Bondi, Tarita Biver, Lisa Dalla Via, Federica Guarra, Mariafrancesca Hyeraci, Claudia Sissi, Luca Labella, Fabio Marchetti, Simona Samaritani
JOURNAL OF INORGANIC BIOCHEMISTRY
(2020)
Article
Chemistry, Inorganic & Nuclear
Luca Bellucci, Gregorio Bottaro, Luca Labella, Valerio Causin, Fabio Marchetti, Simona Samaritani, Daniela Belli Dell'Amico, Lidia Armelao
INORGANIC CHEMISTRY
(2020)
Article
Chemistry, Medicinal
Mariafrancesca Hyeraci, Valeria Scalcon, Alessandra Folda, Luca Labella, Fabio Marchetti, Simona Samaritani, Maria Pia Rigobello, Lisa Dalla Via
Summary: The new platinum complexes show significant antiproliferative effects on resistant ovarian carcinoma cells, demonstrating notable intracellular accumulation and the ability to interact with different intracellular targets. The mechanism of action involves interaction with DNA, collapse of mitochondrial transmembrane potential, and impairment of intracellular redox state, as well as selectivity towards selenocysteine of thioredoxin reductase.
Article
Chemistry, Inorganic & Nuclear
Laura Agnarelli, David Fioco, Daniela Belli Dell'Amico, Luca Labella, Fabio Marchetti, Simona Samaritani
Summary: Despite the generally accepted inertness of platinum(IV) complexes towards nucleophilic substitution, the title compound promptly reacts with nucleophiles to afford the corresponding acetonitrile substitution products. The reaction was followed spectroscopically, and the new platinum(II) and platinum(IV) complexes were fully characterized, with some structures studied by single crystal X-ray diffraction. Even when using protic toluidines, chemoselectivity towards substitution was observed, with addition products formed in less than 10% extent.
INORGANICA CHIMICA ACTA
(2021)
Article
Chemistry, Inorganic & Nuclear
Luca Bellucci, Luca Labella, Fabio Marchetti, Francesco Pineider, Giordano Poneti, Simona Samaritani
Summary: The two compounds exhibit different magnetic hybrid relaxation processes, with one showing slow dynamics in zero magnetic field.
INORGANICA CHIMICA ACTA
(2021)
Article
Biochemistry & Molecular Biology
Riccardo Bondi, Lisa Dalla Via, Mariafrancesca Hyeraci, Gioele Pagot, Luca Labella, Fabio Marchetti, Simona Samaritani
Summary: The newly synthesized platinum(II) iminopyridine complexes exhibit good solubility and stability, with good interactions with DNA and significant antiproliferative activity on ovarian carcinoma cells. Complex 13 shows the ability to overcome cisplatin resistance and forms a dual geometry molecular complex with DNA, with hindered interstrand cross-links compared to cisplatin. The interactions with DNA are discussed in relation to the observed cell effects.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Lorenzo Fioravanti, Luca Bellucci, Lidia Armelao, Gregorio Bottaro, Fabio Marchetti, Francesco Pineider, Giordano Poneti, Simona Samaritani, Luca Labella
Summary: The study focuses on the synthesis and characterization of multinuclear and dinuclear rare-earth metal complexes, revealing the significant impact of different metal-to-ligand ratios and ligands on the structure and properties of the complexes. Some compounds exhibit specific magnetic and luminescent properties, with slow relaxing magnetization and bright red emission typical of Eu3+.
INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Mariafrancesca Hyeraci, Laura Agnarelli, Luca Labella, Fabio Marchetti, Maria Luisa Di Paolo, Simona Samaritani, Lisa Dalla Via
Summary: Resistance to cisplatin limits its usefulness as an anticancer drug. This study describes the synthesis and characterization of two new platinum complexes and demonstrates their potential in overcoming cisplatin resistance in cancer cells. The complexes exhibited poor ability to platinate DNA but showed significant intracellular accumulation. Mechanistic studies revealed their ability to inhibit DNA relaxation and activate the apoptotic pathway. Comparison with related complexes provides insights into the resistance phenotype.
Article
Chemistry, Multidisciplinary
Luca Bellucci, Lorenzo Fioravanti, Lidia Armelao, Gregorio Bottaro, Fabio Marchetti, Francesco Pineider, Giordano Poneti, Simona Samaritani, Luca Labella
Summary: This study demonstrates the site selectivity of hetero-lanthanide tetranuclear complexes using the simple ligand pyterpyNO. The selectivity is directly dependent on the difference in ionic radii of the ions and is not exclusively governed by electrostatic interactions related to size dimensions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Multidisciplinary Sciences
Luca Bellucci, Silvia Carlotto, Gregorio Bottaro, Luca Babetto, Luca Labella, Elisa Gallo, Fabio Marchetti, Simona Samaritani, Lidia Armelao
Summary: The interest in heterometallic lanthanide-d or -p metal (Ln-M) complexes is growing due to the potential cooperative or synergistic effect of two different metals in the same molecular architecture, leading to tunable physical properties. To exploit the potential of Ln-M complexes, suitable synthesis approaches and understanding the effect of each building block on their properties are essential.
Article
Chemistry, Inorganic & Nuclear
Anna Farasat, Francesca Nerli, Luca Labella, Marco Taddei, Simona Samaritani
Summary: A series of dibromo-N-acyclic (NAC) carbene complexes of platinum(II) were synthesized using a previously optimized protocol for analogous chlorinated compounds, starting from trans-[Pt(mu-Br)Br(PPh3)](2). The synthesis involved ring opening of the dinuclear precursor using suitable isonitrile ligands, followed by addition of N,N-diethylamine to the resulting products. Separate investigations were conducted for the two reactions with a focus on the differences between brominated and chlorinated systems.
Article
Chemistry, Inorganic & Nuclear
Luca Bellucci, Luca Giordano, Silvia Carlotto, Giordano Poneti, Marzio Rancan, Simona Samaritani, Lidia Armelao, Luca Labella
Summary: Heterometallic [Ln(hfac)3Cu(acac)2] complexes (Ln = Eu 1, Dy 2, Er 3) with a dinuclear structure were synthesized. Compounds 2 and 3 can only be obtained in anhydrous conditions. Magnetic studies revealed antiferromagnetic interaction and field-induced slow relaxing magnetic moment in compound 2, while compound 3 showed no magnetization dynamics. Quantum mechanical calculations provided insights into the bond strengths and the direct interaction between Ln and Cu.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Anna Farasat, Luca Labella, Maria Luisa Di Paolo, Lisa Dalla Via, Simona Samaritani
Summary: This study synthesized a series of new N-acyclic carbene and isonitrile complexes of platinum(II). Among them, NAC derivatives showed a moderate cytotoxic effect on MSTO-211H cells.
Article
Chemistry, Physical
Luca Bellucci, Gregorio Bottaro, Luca Labella, Fabio Marchetti, Simona Samaritani, Daniela Belli Dell'Amico, Lidia Armelao
Summary: Two homometallic Coordination Polymers (CPs) were used to develop a family of ratiometric luminescent thermometers with Eu3+ and Tb3+ emitting as red and green colors respectively. The thermometric properties were studied in different mixtures of CPs, showing broad applicative temperature ranges and high relative thermal sensitivity values in the physiological temperature range. These samples exhibited continuous color variation from green to red that can be utilized as a colorimetric temperature indicator.
Article
Chemistry, Inorganic & Nuclear
Jacopo De Bellis, Luca Bellucci, Gregorio Bottaro, Luca Labella, Fabio Marchetti, Simona Samaritani, Daniela Belli Dell'Amico, Lidia Armelao
DALTON TRANSACTIONS
(2020)
