Article
Chemistry, Physical
Sunwoo Kang, Taekyung Kim, Jin Yong Lee
Summary: A series of Ir- and Pt-based blue phosphorescent materials were theoretically investigated using DFT calculations to improve their chemical stability in the excited state. Introducing intra- and inter-ligand interactions in Ir and Pt complexes significantly increased the Delta E((MC)-M-3-T-1) to prevent decomposition reactions, resulting in the highest reported values to date. The research provides insights into improving device lifetimes by enhancing the excited state chemical stability of deep blue phosphorescent materials.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Hui Hu, Zhen-Wei Zhang, Da-Shuai Zhang, Xue Zhou, Hui Ji, Yong-Zheng Zhang, Yuchen Deng, Longlong Geng, Xiuling Zhang, Chao Lv, Rongmin Wei, Jin-Hua Wang
Summary: In this study, a series of coordination polymers with similar one-dimensional chain structures were synthesized by hydrothermal reactions. These compounds showed blue-emission properties, which could be easily modulated by using different solvents. Among them, Hui-3-DMA exhibited an excellent quantum yield performance of 54.1%, indicating its potential as a blue-emission material. Moreover, fluorescence studies at different temperatures revealed a good linear or exponential decline in their emission intensity, suggesting the potential of these compounds as fluorescent thermometers.
Article
Chemistry, Inorganic & Nuclear
Si-Hai Wu, Rong Yang, Bin Sun, Jian-Hong Tang, Zhong-Liang Gong, Junjie Ma, Lianhui Wang, Jieqing Liu, Dian-Xue Ma, Jiang-Yang Shao, Yu-Wu Zhong
Summary: Three tris-heteroleptic mononuclear Ru(II) complexes with dual fluorescence and phosphorescence were designed and used as ratiometric light-response probes for DNA, where two of the complexes exhibited stronger preference for calf thymus DNA. The interactions of these complexes with different DNAs were investigated by various methods, including spectroscopy and molecular modeling, providing valuable insights for potential applications in DNA sensing.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Daehoon Kim, Mina Ahn, Kyung-Ryang Wee, Dae Won Cho
Summary: A series of iridium complexes with different ancillary ligands were synthesized to study their photophysical properties. Experimental results showed that the ancillary ligands play a significant role in influencing the emission changes, including energy transfer and emission intensity variations. Through theoretical calculations and experimental observations, it was found that the interligand energy transfer occurs exothermically and leads to changes in emission properties.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Inorganic & Nuclear
Ross Davidson, Yu-Ting Hsu, Mark A. Fox, Juan A. Aguilar, Dmitry Yufit, Andrew Beeby
Summary: This study investigates the emission behavior of Ir(ppy)2(acac) complexes with OPE3 motifs and finds that the complexes containing OPE3 structures have long emission lifetimes, which can be achieved through intramolecular reversible electronic energy transfer (REET) with even longer-lived localized OPE3 states. This finding is important for oxygen sensing and cellular imaging applications.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Mansoor Akhtar, Ali Muhammad Arif, Shifa Ullah Khan, Guo-Gang Shan, Hong-liang Xu, Zhong-Min Su
Summary: Density functional theory calculations were employed to investigate the geometric structures, electronic properties, and second-order nonlinear optical (NLO) properties of two synthesized iridium(iii) complexes with different substituted ancillary ligands. The first hyperpolarizabilities were found to be easily modulated by the introduction of different units, and the changes in properties could be qualitatively explained by means of the charge transfer pattern. The theoretical investigation of these complexes is expected to aid in designing high-performance and versatile NLO materials.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Soheila Karimi, Hashem Shahroosvand, Narges Yaghoobi Nia, Aldo Di Carlo, Mohammad Khaja Nazeeruddin
Summary: This paper presents a simple strategy for tuning the electroluminescence color of solid-state light-emitting devices (ss-LEDs) by adding an ionic additive. The researchers developed an active ionic emissive compound and used it in a light-emitting electrochemical cell (LEC) to improve the electroluminescence characteristics. The experiments showed that this method significantly increased the luminescence intensity, improved the efficiency, and allowed color tuning.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Deepak Gupta, Geraldine Chanteux, Gulshan Kumar, Koen Robeyns, Alexandru Vlad
Summary: This study reports the formation of robust supramolecular frameworks using hetero-polytopic metal complexes interacting with different ancillary ions. The choice of ancillary ions was found to have no significant impact on the formation of the frameworks. The resulting porous structure of the frameworks makes them suitable candidates for gas sorption, separation, and chemical sensing applications.
Article
Chemistry, Multidisciplinary
Deepak Gupta, Geraldine Chanteux, Gulshan Kumar, Koen Robeyns, Alexandru Vlad
Summary: This study reports the formation of robust supramolecular frameworks built from hetero-polytopic metal complexes and interacting with different ancillary ions. The functionalized phenanthroline ligands control the overall charge stoichiometry, leading to the formation of 2D porous honeycomb networks without significant alteration in the molecular packing.
Article
Chemistry, Inorganic & Nuclear
Satabdee Tanaya Sahoo, Aisa Mohanty, Raju Sharma, Prosenjit Daw
Summary: The developed bifunctional NNN-Ru complex exhibits high catalytic efficiency for the selective production of hydrogen and glycolic acid from ethylene glycol. The optimized reaction conditions allow for further dehydrogenation of the organic substrate, resulting in higher hydrogen production. Mechanistic investigations were conducted to understand the role of the bifunctional catalyst.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ivan Soriano-Diaz, Enrique Orti, Angelo Giussani
Summary: In this study, density functional theory calculations were used to investigate three cyclometallated Ir(III) complexes, [Ir(ppy)(2)(bpy)](+), [Ir(ppy)(2)(pbpy)](+), and [Ir(ppy)(2)(dpbpy)](+), in order to explain their different photophysical properties. Despite sharing the same molecular skeleton, the complexes exhibited different emission quantum yields, which was previously attributed to a different ability to non-radiatively decay through axial metal-centered triplet states. This study revealed a new non-radiative decay path mediated by equatorial metal-centered states, which better explained the observed photoemission properties.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Anant Kumar Jain, Michael R. Gau, Patrick J. Carroll, Karen I. Goldberg
Summary: The synthesis of Vaska-type complexes with all four common halides was attempted, and it was found that the complexes were ionic in the solid-state and in equilibrium in solution. The absence of the Ir-III-H species in the fluoride analog was attributed to strong hydrogen bonding interactions.
Review
Chemistry, Inorganic & Nuclear
Mikhail A. Kinzhalov, Elena V. Grachova, Konstantin V. Luzyanin
Summary: This review examines the use of metal complexes featuring acyclic diaminocarbene ligands as powerful emitters in OLEDs and other electroluminescent technologies. It discusses the photophysical properties of these complexes in relation to the carbene ligand structure and metal characteristics, highlighting the advantages that they provide to transition-metal-based phosphors.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Ke Zhang, Xianwen Meng, Lei He
Summary: This study reports a series of new phosphorescent cationic iridium complexes and their application in solution-processed OLEDs with high-efficiency electroluminescence. Particularly, complex 2 exhibits the best performance in green-blue OLEDs, with high external quantum efficiency and small efficiency roll-off.
Review
Chemistry, Multidisciplinary
Qiuran Wang, Sam H. Brooks, Tianchang Liu, Neil C. Tomson
Summary: Cluster complexes have recently been designed with ligand scaffolds specifically tailored to support multinuclear transition metal cores in order to facilitate cooperative small molecule activation. The incorporation of geometric flexibility and redox-active ligands in the ligand design allows for unique small molecule activation modes, providing significant analogies to heterogeneous and metalloenzyme catalysts.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Giulio Bresciani, Lorenzo Biancalana, Stefano Zacchini, Guido Pampaloni, Gianluca Ciancaleoni, Fabio Marchetti
Summary: The catalytic activity of a series of diiron complexes based on the {Fe2Cp2(CO)(x)} core (x = 2-3) and containing a bridging aminocarbyne ligand was screened in the transfer hydrogenation reaction of cyclohexanone from isopropanol. The best catalyst among these complexes was [Fe2Cp2(CN)(CO)(mu-CO){mu-CN(Me)(4-C6H4OMe)}], 3a, which exhibited moderate activity and showed a carbyne-centered mechanism, stabilized by the cyanide co-ligand, as supported by DFT calculations and IR analyses.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Daniel Pecorari, Emanuele Giuliani, Andrea Mazzanti, Stefano Stagni, Valentina Fiorini, Giulia Vigarani, Francesco Zinna, Gennaro Pescitelli, Michele Mancinelli
Summary: Bis-aryl carbazole borane derivatives with emissive properties and axial chirality were synthesized. The resolution of a thermally stable atropisomeric pair (compound 1b), which has a B-C chiral axis, was achieved using chiral stationary-phase high-performance liquid chromatography (CSP-HPLC). The complete photophysical properties of all compounds were measured and simulated using time-dependent density functional theory (TD-DFT) calculations, and circularly polarized luminescence spectra were obtained for the atropisomers of compound 1b, with their absolute configuration determined by a TD-DFT simulation of the electronic circular dichroism (ECD) spectra.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Lorenzo Bonaldi, Marco Bortoluzzi, Stefano Zacchini, Guido Pampaloni, Fabio Marchetti, Lorenzo Biancalana
Summary: The chemistry of 1,2,4,5-tetrazines has attracted attention in the synthesis and application field. Recent studies have shown that regioselective reactions with alkynes and alkenes are favored when the tetrazine ring is coordinated to certain metal centers. This study explores the reactivity of tetrazines with chalcogenocyanate anions and demonstrates the formation of new heterocycles. The resulting ruthenium complexes were characterized using various analytical and spectroscopic techniques.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ashley J. Mulder, Rhys D. Tilbury, Melissa V. Werrett, Phillip J. Wright, Payal Patel, Thomas Becker, Franca Jones, Stefano Stagni, Guohua Jia, Massimiliano Massi, Mark A. Buntine
Summary: This study reports on the effects of different N-donor ligands on the chemical composition and surface plasmon resonance (SPR) transition of copper nanoparticles (CuNPs) formed via laser ablation. Pyridines and alkylated tetrazoles showed minimal effects on the SPR transition, while the presence of tetrazoles resulted in a significant blue shift. This shift was attributed to the tetrazolate anions providing a reducing environment, preventing the formation of copper(II) oxides.
Article
Polymer Science
Giovanni Ricci, Giuseppe Leone, Giorgia Zanchin, Francesco Masi, Stefano Zacchini, Giulio Bresciani, Massimo Guelfi, Guido Pampaloni
Summary: Novel copper complexes were synthesized by reacting copper(II) dichloride and copper(II) dibromide with pyridyl-imine ligands with different substituents. The complexes were characterized and their molecular structure was determined. When combined with methylaluminoxane (MAO), the complexes acted as active and selective catalysts for the polymerization of 1,3-dienes, resulting in polymers with unusual structures.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Biochemistry & Molecular Biology
Giulio Bresciani, Stefano Zacchini, Guido Pampaloni, Marco Bortoluzzi, Fabio Marchetti
Summary: Diiron mu-aminocarbyne complexes can be synthesized by reacting sodium cyanate and tetrabutylammonium thiocyanate with pre-prepared diiron aminocarbyne complexes, yielding different substituted diiron cyanide complexes with yields of 67-81%, through substitution of the acetonitrile ligand. When reacted with potassium selenocyanate at reflux temperature, cyanide complexes can be obtained with yields of 45-67%. When reacted at room temperature in acetone, a small amount of potassium selenocyanate complexes can be obtained. All products were fully characterized and the chiral structure was determined by single crystal X-ray diffraction. DFT calculations shed light on the coordination mode and stability of the {NCSe-} fragment.
Article
Chemistry, Inorganic & Nuclear
Chiara Zappelli, Gianluca Ciancaleoni, Stefano Zacchini, Fabio Marchetti
Summary: In this study, the authors investigated the reactions of [Fe2Cp2(CO)(mu-CO){mu-eta 1:eta 3-C gamma(Fc)-C beta HC alpha(CN)NMe2}] complex with isocyanides (CNR). They were able to characterize and understand the structure and properties of the resulting products.
Article
Chemistry, Multidisciplinary
Matteo Verdi, Antonella Giuri, Andrea Ciavatti, Aurora Rizzo, Carola Esposito Corcione, Laura Basirico, Silvia Colella, Beatrice Fraboni
Summary: High sensitivity and efficient X-ray detectors are needed for medical diagnostics and radiotherapy. Recently, lead halide perovskites have been explored as a new material for X-ray detection. However, their low stability has been a challenge. In this study, a stable thin film perovskite X-ray detector was fabricated using starch as a polymeric template. The resulting device showed exceptional stability and achieved a top sensitivity of 5.5 +/- 0.2 mu C Gy(-1) s(-1) without any external bias.
ADVANCED MATERIALS INTERFACES
(2023)
Article
Chemistry, Inorganic & Nuclear
Giulio Bresciani, Serena Boni, Tiziana Funaioli, Stefano Zacchini, Guido Pampaloni, Natalia Busto, Tarita Biver, Fabio Marchetti
Summary: We synthesized and evaluated the anticancer potential of two series of diruthenium biscyclopentadienyl carbonyl complexes. Novel dimetallacyclopentenone compounds (2-4) were obtained from the thermal reaction of [Ru2Cp2(CO)(μ-CO)(μ-η^1:η^3-C(Ph)C(Ph)C(O)}], 1, with alkynes HCCR [R = C5H4FeCp (Fc), 3-C6H4(Asp), 2-naphthyl; Cp = η(5)-C5H5, Asp = OC(O)-2-C6H4C(O)Me]. The resulting complexes showed cytotoxic activity against cancer cells, different interactions with nucleic acids, and production of ROS.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Cristiana Cesari, Marco Bortoluzzi, Tiziana Funaioli, Cristina Femoni, Maria Carmela Iapalucci, Stefano Zacchini
Summary: This study reports the synthesis of Ru6C carbonyl clusters and their reactions with different reagents, the structures of the products were characterized by X-ray diffraction, and the redox behavior was investigated by electrochemical and spectroscopic methods.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Giulio Bresciani, Stefania Volante, Lorenzo Biancalana, Stefano Zacchini, Guido Pampaloni, Fabio Marchetti
Summary: Complexes [FeCpI(CO)(CNR)] and [FeCpI(CNR)2] were synthesized in 58-73% yields through the thermal reactions of [FeCpI(CO)2] with one/two equivalents of CNR, respectively, in the presence of [Fe2Cp2(CO)4] as catalyst. The catalytic potential of 1, 2a-f, and 3a-f in the bulk polymerization of rac-lactide was examined.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Lorenzo Marchi, Simone Fantuzzi, Andrea Cingolani, Alessandro Messori, Rita Mazzoni, Stefano Zacchini, Marina Cocchi, Luca Rigamonti
Summary: Iron(ii) bis-pyrazolilpyridyl (bpp-R) complexes [Fe(bpp-R)(2)](X)(2)·solvent undergo spin transition from high spin (S = 2, HS) to low spin (S = 0, LS) in the solid state, known as spin crossover (SCO). The distortion of the octahedral coordination environment is affected by crystal packing and modulates the SCO behavior. This study used a multivariate approach combining Principal Component Analysis and Partial Least Squares regression to analyze the structural data of HS structures and efficiently model and predict the spin transition temperature T-1/2 for complexes with different R groups, X- anions, and co-crystallized solvents.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sara Benetti, Maria Dalla Pozza, Lorenzo Biancalana, Stefano Zacchini, Gilles Gasser, Fabio Marchetti
Summary: Novel diiron vinyliminium complexes were synthesized and characterized by various spectroscopic techniques. Their solubility in D2O, Log Pow coefficients, and stability in aqueous media were determined. The antiproliferative activity of these complexes on cancer cell lines was evaluated and their mechanism of action was investigated by assessing their influence on mitochondrial respiration.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Roberta Colaiezzi, Chiara Saviozzi, Nicola di Nicola, Stefano Zacchini, Guido Pampaloni, Marcello Crucianelli, Fabio Marchetti, Andrea Di Giuseppe, Lorenzo Biancalana
Summary: The reductive N-monomethylation of nitroarenes can be conveniently realized in one-pot using methanol as the reductant, methylating agent, and solvent. New ruthenium(II) arene complexes were developed as efficient catalytic precursors for the tandem reduction/N-methylation of aromatic nitrocompounds with methanol, starting from commercially available and inexpensive dioxime ligands.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Inorganic & Nuclear
Cristiana Cesari, Beatrice Berti, Marco Bortoluzzi, Cristina Femoni, Tiziana Funaioli, Federico Maria Vivaldi, Maria Carmela Iapalucci, Stefano Zacchini
Summary: Heterometallic Chini-type clusters [Pt6-xNix(CO)(12)](2-) (x = 0-6) with different Pt/Ni compositions were obtained by reacting [Pt-6(CO)(12)](2-) with Ni-clusters. The site preference of Pt and Ni within their metal cages has been computationally investigated.
DALTON TRANSACTIONS
(2023)