Article
Chemistry, Multidisciplinary
Changguang Yao, Tonghuan Zhang, Theo P. Goncalves, Kuo-Wei Huang
Summary: In contrast to typical C-sp2-H activation, the (PNP)-P-3-Nickel complex chemoselectively cleaved the benzylic C-sp3-H bond of toluene in the presence of KHMDS, forming various compounds with different functional groups under similar conditions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Giulio Bresciani, Stefano Zacchini, Guido Pampaloni, Marco Bortoluzzi, Fabio Marchetti
Summary: A series of novel metal-organic compounds were synthesized by reacting with internal alkynes using a tricarbonyl precursor and catalyst, leading to the formation of unique structures.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Chao Zhang, Xusheng Guo, Xuwen Da, Zhanhua Wang, Xuesong Wang, Qianxiong Zhou
Summary: The Ru1 compound designed in this study exhibits multiple anticancer mechanisms and significantly enhanced photocytotoxicity under 600 nm light irradiation, making it a promising candidate for photodynamic therapy and photoactivated chemotherapy.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Lindsey Paul, Melissa Gu, Sydney Moise, Daniel P. Harrison, Michael R. Norris
Summary: In this study, four Ru complexes containing bidentate polypyridyl ligands were synthesized. It was found that these complexes can selectively reduce CO2 to liquid fuels, with the involvement of amines playing a crucial role in this process.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Morris E. Olumba, Hanah Na, Alan E. Friedman, Thomas S. Teets
Summary: In this study, a facile [4 + 4] coordination-driven self-assembly of cyclometalated iridium(III) using linear aryldiisocyanide bridging ligands (BLs) is demonstrated. A family of nine new [Ir(C^N)2(μ-BL)](4)(4+) coordination cages was prepared with isolated yields of 40-83%, and detailed photophysical studies revealed the nature of the luminescent triplet states in these complexes. This work illustrates that aromatic diisocyanide ligands enable coordination-driven assembly of inert iridium(III) nodes under mild conditions, producing supramolecular coordination complexes with desirable photophysical properties.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Evangelos Pilichos, Annia Tubau, Saskia Speed, Merce Font-Bardia, Albert Escuer, Arnald Grabulosa, Julia Mayans
Summary: A new family of lanthanide compounds with different structures and properties have been synthesized using dppeO(2) as a ligand. The compounds exhibit a two-dimensional or one-dimensional structure depending on the lanthanide cation. Some of the compounds have magnetic or luminescent properties, and they can be used as structural probes or for specific applications.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Multidisciplinary
Marcus W. Drover
Summary: This tutorial review focuses on recent research (2015-2021) concerning ligand construction and its relation to the design of secondary coordination spheres (SCSs). It highlights the importance of SCSs in metalloenzymes and biomimetic chemistry and showcases the advances in organic and inorganic chemistry in constructing SCSs. These studies have led to exciting findings in transformations relevant to clean fuel generation.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Inorganic & Nuclear
Rain Ng, Man-Chun Chong, Wai-Man Cheung, Herman H-Y Sung, Ian D. Williams, Wa-Hung Leung
Summary: Heterometallic mu-nitrido complexes have been synthesized from organometallic complexes containing O/S-donor ligands and a ruthenium(VI) nitride. The bonding in these complexes is described as double bond character of the Ir-N-(nitride) bonds. The reactions of these complexes with other ligands and reagents were also studied.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Maria L. Buil, Javier A. Cabeza, Miguel A. Esteruelas, Susana Izquierdo, Carlos J. Laglera-Gandara, Antonio Nicasio, Enrique Onate
Summary: The reaction of hexahydride OsH6(PiPr(3))(2) with a P,Ge,P-germylene-diphosphine leads to an osmium tetrahydride derivative with a Ge,P-chelate, serving as a bifunctional catalyst for formic acid dehydrogenation. The study reveals that hydrogen formation occurs exclusively on the coordination sphere of the metal center, while both the metal center and the sigma-donor Lewis acid cooperatively participate in CO2 release, which is the rate-determining step.
INORGANIC CHEMISTRY
(2021)
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, Physical
Ernest Ubasart, Irene Mustieles Marin, Juan Manuel Asensio, Gabriel Mencia, Angela M. Lopez-Vinasco, Cristina Garcia-Simon, Iker del Rosal, Romuald Poteau, Bruno Chaudret, Xavi Ribas
Summary: The synthesis of metallic nanoparticles with high surface area and controlled shape is crucial for improving their catalytic performance. In this study, a synthetic methodology for sub-nanometric Ru nanoparticles was developed using a tetragonal prismatic supramolecular nanocapsule. The catalytic properties of these sub-nanometric nanoparticles were tested and the encapsulation of [Ru-5] clusters inside the nanocapsule was observed. A thorough study enlightened the nature of the trapped clusters and proposed them as the first-grown seeds of subsequent formation of the subnanometric Ru nanoparticles. The double role of the nanocapsule in stabilizing nanoparticles and hosting ultra-small Ru clusters is unprecedented and may lead to the synthesis of ultra-small metallic clusters for catalytic purposes.
NANOSCALE HORIZONS
(2022)
Article
Chemistry, Inorganic & Nuclear
A. Ziolkowska, N. Szynkiewicz, J. Ryl, L. Ponikiewski
Summary: The reactivities of two selected phosphanylphosphaalkenes, Ph2C=P-PtBu2 (1a) and (p-MeO-Ph)(2)C=P-PtBu2 (1b), towards CuCl, AgCl and (tht)AuCl (tht = tetrahydrothiophene) were investigated. New phosphanylphosphaalkene dimeric and monomeric complexes (Cu and Ag dimeric, and Au monomeric) were formed as a result. All obtained products were stable in air and moisture, and were insensitive to light.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Gary J. Ryan, Thorfinnur Gunnlaugsson, Susan J. Quinn
Summary: Bi-chromophoric ruthenium polypyridyl complexes with nitro-1,8-naphthalimide groups demonstrate off-on light switching properties and effective DNA binding. The DNA affinity is influenced by the linker length and the number of naphthalimides, and the binding is attributed to naphthalimide intercalation and electrostatic interaction. The substitution position of the nitro group affects DNA binding and optical properties.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Marianna Pioli, Cecilia Loffi, Paolo Pio Mazzeo, Alessia Bacchi, Paolo Pelagatti
Summary: Two different N-substituted naphthalimide ligands have been synthesized and reacted with a cationic organometallic fragment, showing different coordination behaviors. One ligand forms a sandwich complex with six coordination sites, while the other forms two isomeric complexes with different stabilities.
INORGANICA CHIMICA ACTA
(2021)
Article
Biochemistry & Molecular Biology
Izabela Pospieszna-Markiewicz, Marta A. Fik-Jaskolka, Zbigniew Hnatejko, Violetta Patroniak, Maciej Kubicki
Summary: Homodinuclear complexes were synthesized using a newly synthesized 2-((2-(benzoxazol-2-yl)-2-methylhydrazono)methyl)phenol ligand and lanthanide(III) nitrates. Spectroscopic data and crystal structure determination confirmed the characteristics and composition of these complexes.
Article
Chemistry, Multidisciplinary
Angela Fong, Cameron L. Campbell, Silvia Huynh, Laura J. McCormick McPherson, Simon J. Teat, Magnus W. P. Bebbington, Scott J. Dalgarno
Summary: The ring-opening of furans at the equatorial methylene bridge positions of a calix[4]arene provides access to a variety of new molecules with widespread potential impact in supramolecular chemistry and other areas, yielding good results.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Inorganic & Nuclear
Lucinda R. B. Wilson, Marco Coletta, Marco Evangelisiti, Stergios Piligkos, Scott J. Dalgarno, Euan K. Brechin
Summary: The calix[4]arene scaffold is a versatile supramolecular platform that can be used to synthesize a variety of polymetallic clusters with consistent coordination preferences and assembly behaviors.
DALTON TRANSACTIONS
(2022)
Article
Crystallography
Dominic Taylor, Irene Ling, Filipe Vilela, Scott J. Dalgarno
Summary: The crystallization of 5,17-dibromo-11,27,23,25-tetraone-26,28-dipropoxycalix[4]arene resulted in the rare observation of two different conformations within the same single crystal X-ray structure. NMR spectroscopy analysis showed that only one conformation was present in solution. Unlike other reported calix[4]arenes and calix[4]quinones, both conformations in this crystal structure had a pinched shape, reducing Br-Br separation and associated cavity sizes.
Article
Chemistry, Multidisciplinary
Marjan Hosseinzadeh, Sergio Sanz, Jan van Leusen, Natalya V. Izarova, Euan K. Brechin, Scott J. Dalgarno, Paul Koegerler
Summary: Phosphate ester bonds are stable in nature and can be isolated using a combination of phosphoryl and calix[4]arene moieties. In this study, hydrolyzed phosphoryl-calix[4]arene ligands were formed through Ln(III)-mediated P-OEt bond cleavage in L-PO. The resulting Ln(III) species were trapped as dimers, and the Dy derivative exhibited slow magnetization relaxation. This strategy can be further applied to create a broader range of hydrolyzed platforms that mimic nuclease enzymes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Crystallography
Monica Bernard Tan, Alexandre N. N. Sobolev, Colin L. L. Raston, Scott J. J. Dalgarno, Irene Ling
Summary: This study examines the single crystal structures of two bulky phosphonium compounds and investigates their self-assembly behavior. It is found that the organic cations form stable stacked columns with voids occupied by anions or solvent molecules. The analysis suggests that hydrogen bonding plays a dominant role in stabilizing the self-assembly.
Article
Nanoscience & Nanotechnology
Liefeng Hu, Chuxiao Xiong, Jun-Jie Zou, Junrong Chen, Hengyu Lin, Scott J. Dalgarno, Hong-Cai Zhou, Jian Tian
Summary: This study developed a novel chemiluminescence-photodynamic therapy (PDT) nanosystem by integrating an oxygen-supplying protein (hemoglobin, Hb) and a luminescent donor (luminol, Lum) into hierarchically engineered mesoporous porphyrinic metal-organic framework (MOF) nanoparticles. The system activated luminescence through chemiluminescence resonance energy transfer and produced reactive oxygen species for cancer cell killing, resulting in an excellent anticancer activity both in vitro and in vivo. This self-illuminating, oxygen-self-supplying nanosystem integrates essential components of PDT and holds great potential for selective phototherapy of deep-seated cancer.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Euan K. Brechin, Jurgen Schnack, Marco Evangelisti, Constantinos J. Milios, Thomais G. Tziotzi, David Gracia, Scott J. Dalgarno
Summary: Reaction of Gd(OAc)3 center dot 4H2O, salicylaldehyde, and CH3ONa in MeCN/MeOH leads to the formation of [Gd12Na6(OAc)25(HCO2)5(CO3)6(H2O)12]center dot 9H2O.0.5MeCN (1 center dot 9H2O.0.5MeCN), which exhibits a quadruple-wheel structure composed of two {Na3} and two {Gd6} rings. The magnetic properties of 1 show weak antiferromagnetic interactions between GdIII ions, resulting in a record magnetocaloric effect at low magnetic fields and temperatures. The magnetic entropy change reaches -Delta Sm= 29.3 J kg-1 K-1 for full demagnetization from B = 1 T at T = 0.5 K.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiangquan Hu, Wenjuan Tian, Yuan Jiao, Steven P. Kelley, Ping Wang, Scott J. Dalgarno, David A. Atwood, Sisi Feng, Jerry L. Atwood
Summary: This study reports a method for the controlled self-assembly of vanadium-seamed metal-organic nanocapsules with specific metal oxidation state distributions. Crystallographic studies reveal the structural complexity and geometries of the new capsules, while the differences in metal oxidation state greatly affect their photoelectric conversion properties. This work represents a significant advancement in the construction of intricate metal-organic architectures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Rodavgi Karakousi, Pinelopi A. Tsami, Maria-Areti I. Spanoudaki, Scott J. Dalgarno, Vassileios C. Papadimitriou, Constantinos J. Milios
Summary: In this study, two complexes were synthesized through a solvothermal reaction in methanol, forming two-dimensional and three-dimensional coordination polymers connected by Schiff base ligands. Both complexes exhibit similar strong emission properties in solution and solid state, with complex 2 displaying a slightly longer lifetime.
CHEMISTRY-SWITZERLAND
(2023)
Article
Chemistry, Inorganic & Nuclear
Lucinda R. B. Wilson, Marco Coletta, Mukesh K. Singh, Simon J. Teat, Adam Brookfield, Muralidharan Shanmugam, Eric J. L. McInnes, Stergios Piligkos, Scott J. Dalgarno, Euan K. Brechin
Summary: The reaction of 2,2'-bis-p-Bu-t-calix[4]arene (H8L) with Cu(NO3) (2)center dot 3H(2)O and N-methyldiethanolamine (MedeaH(2)) in a basic dmf/MeOH mixture results in the formation of [Cu-II (16)(L)(2)(Me-dea)(4)(mu(4)-NO3)(2)(mu-OH)(4)(dmf)(3.5)(MeOH)(0.5)(H2O)(2)] (H6L)center dot 16dmf center dot 4H(2)O (4). The metallic skeleton of the compound consists of a tetracapped square prism, [Cu-12], with Cu-II ions housed in the calix[4]arene polyphenolic pockets. Magnetic measurements show antiferromagnetic exchange interactions and a ground state of S = 1, while EPR indicates a large zero-field splitting.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Thomais G. Tziotzi, David Gracia, Scott J. Dalgarno, Juergen Schnack, Marco Evangelisti, Euan K. Brechin, Constantinos J. Milios
Summary: The reaction of Gd(OAc)3 center dot 4H2O, salicylaldehyde, and CH3ONa in MeCN/MeOH yielded [Gd12Na6(OAc)25(HCO2)5(CO3)6(H2O)12]center dot 9H2O.0.5MeCN, which consists of a quadruple-wheel composed of two {Na3} and two {Gd6} rings. The magnetic properties of this compound exhibit weak antiferromagnetic interactions between GdIII ions, resulting in a record magnetocaloric effect at low temperatures and applied magnetic fields. The magnetic entropy change reaches -Delta Sm= 29.3 J kg-1 K-1 for full demagnetization at T = 0.5 K from B = 1 T.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiangquan Hu, Meirong Han, Leicheng Wang, Li Shao, Yadav Peeyush, Jialei Du, Steven P. Kelley, Scott J. Dalgarno, David A. Atwood, Sisi Feng, Jerry L. Atwood
Summary: Here we present a Cu2+-seamed coordination nanocapsule that acts as an efficient semiconductor photocatalyst for activating molecular oxygen. The capsule is formed through the self-assembly of cuprous bromide and C-pentyl-pyrogallol[4]arene facilitated by redox reaction. Photophysical and electrochemical studies indicate its strong visible-light absorption and photocurrent polarity switching effect. This novel molecular solid material can activate molecular oxygen into reactive oxygen species under simulated sunlight, enabling catalytic aerobic oxidation reactions. This work provides new insights into designing nonporous discrete metal-organic supramolecular assemblies for solar-driven molecular oxygen activation.
Article
Chemistry, Multidisciplinary
Dominic Taylor, Thomas Malcomson, Adilet Zhakeyev, Georgina M. Rosair, Martin J. Paterson, Jose Marques-Hueso, Scott J. Dalgarno, Filipe Vilela
Summary: Regioselective stepwise phenylation of 4,7-diarylbenzo[c][1,2,5]thiadiazole fluorophores was achieved by a facile one-pot, three-step synthetic strategy involving sequential borylation, hydroxydechlorination, and Suzuki-Miyaura cross-coupling reactions. Selectivity was achieved by using BCl3 to install a boronic acid group in the ortho-position of only one of the diaryl groups. The introduction of ortho-phenyl groups through Suzuki-Miyaura cross-coupling resulted in twisted structures with hindered intramolecular rotation, allowing for adjustment of the fluorophore absorption and emission properties.
Article
Chemistry, Multidisciplinary
Irene Ling, Cameron L. Campbell, Alexandre N. Sobolev, Scott J. Dalgarno
Summary: This study reports four ternary multi-component crystal structures containing water-soluble p-sulfonatocalix[4]arene anion as the cavitand, along with different types of positively charged guest molecules and aquated lanthanide(iii) ions (Gd(iii) or Ce(iii)). Crystallographic analysis reveals that all positively charged imidazole rings are encapsulated by p-sulfonatocalix[4]arene. A molecular capsule is formed in all structures, regardless of the type of guest species.
Article
Chemistry, Inorganic & Nuclear
Yushu Jiao, Sergio Sanz, Natalya V. Izarova, Jan van Leusen, Sidra Sarwar, Scott J. Dalgarno, Euan K. Brechin, Paul Koegerler
Summary: The complementarity between calixarene and polyoxometalate ligands leads to the formation of the first organic-inorganic hybrid compound [(ML)-L-III{Mo5O13(OMe)(4)(NO)}](2-) (M = Y, Gd and Dy), which exhibits a distorted square-antiprismatic MO8 ligand field and shows slow relaxation of magnetisation in the Dy derivative.
DALTON TRANSACTIONS
(2022)
