Transition Metal Complexes and Radical Anion Salts of  1,10-Phenanthroline Derivatives Annulated with a  1,2,5-Tiadiazole and 1,2,5-Tiadiazole 1,1-Dioxide Moiety: Multidimensional Crystal Structures and Various  Magnetic Properties

Shuku, Yoshiaki; Awaga, Kunio

doi:10.3390/molecules19010609

Cited by 8 publications

(10 citation statements)

References 79 publications

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“…The reduction of td to a radical anion leads to a strong shortening of the C–C (“CC”) bond of the dioxothiadiazole ring by ca. 0.06 Å (based on the observations of Awaga et al 53 − 55 ). Most importantly, this particular structural change occurs regardless of the coordination mode of the ligand.…”

Section: Results and Discussionmentioning

confidence: 99%

“…However, quantum chemical methods often fail to provide correct estimates of weak magnetic interactions, especially when the coupling constant values are close to zero. 53 , 55 The total energies and ⟨S 2 ⟩ expectation values of the triplet and the BS states are presented in Table S8 in the Supporting Information . The spin density illustration of a high-spin-state system calculated with the M06 functional is showed in Figure S3 in the Supporting Information .…”

Section: Results and Discussionmentioning

confidence: 99%

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Influence of the Increasing Number of Organic Radicals on the Structural, Magnetic, and Electrochemical Properties of the Copper(II)–Dioxothiadiazole Family of Complexes

Arczyński

Pinkowicz

2020

Inorg. Chem.

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The preparation, structures, and electrochemical and magnetic properties supported by density functional theory (DFT) calculations of three new copper(II) compounds with [1,2,5]thiadiazolo[3,4- f ][1,10]phenanthroline 1,1-dioxide (td) and its radical anion (td ·– ) are reported: {[Cu II Cl(td)](μ-Cl) 2 [Cu II Cl(td)]} ( 1 ), which incorporates only neutral td ligands; [Cu II Cl(td ·– )(td)]·2MeCN ( 2 ), which comprises one neutral td and one radical td ·– ; and PPN[Cu II Cl(td ·– ) 2 ]·2DMA ( 3 ), where Cu II ions are coordinated by two radical anions td ·– (DMA, dimethylacetamide; PPN + , the bis(triphenylphosphine)iminium cation). All three compounds show interesting paramagnetic behavior with low-temperature features indicating significant antiferromagnetic coupling. The magnetic properties of 1 are dominated by Cu II ···Cu II interactions ( J CuCu ) mediated through the Cl – bridges, while the magnetic properties of 2 and 3 are governed mainly by the td ·– ···td ·– ( J tdtd ) and Cu II –td ·– ( J Cutd ) exchange interactions. The structure of 2 features only two major magnetic coupling pathways enabling the fitting of experimental data with J tdtd = −36.0(5) cm –1 and J Cutd = −12.6(2) cm –1 only. Compound 3 exhibits a complex network of magnetic contacts. Attempt to approximate its magnetic behavior using only a local magnetic contacts model resulted in J tdtd = −5.6(1) cm –1 and two J Cutd constants, −12.4(2) and −22.6(4) cm –1 . The experimental fitting is critically compared with the results of broken symmetry density functional theory (BS DFT) calculations for inter- and intramolecular contacts. More consistent results were obtained with the M06 functional as opposed to popular B3LYP, which encountered problems reproducing some of the experimental intermolecular exchange interactions. Electrochemical measurements of 2 and 3 in MeCN showed three reversible nearly overlapping redox peaks appearing in a narrow potential range of −600 to −100 mV vs Fc/Fc ...

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Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Influence of the Increasing Number of Organic Radicals on the Structural, Magnetic, and Electrochemical Properties of the Copper(II)–Dioxothiadiazole Family of Complexes

Arczyński

Pinkowicz

2020

Inorg. Chem.

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“…The first systematic investigation of the properties of dioxothiadiazoles and perhaps the first rational approach to this heterocycle as a promising candidate for the design of molecular materials was carried out by Awaga et al His group focused on dioxothiadiazoles fused to extended aromatic systems such as 1,10-phenanthroline (1,10-tdapO 2 ) or pincene and performed a general physicochemical evaluation of these systems [ 14 , 44 , 51 , 52 ]. [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (1,10-tdapO 2 ) structurally embodies all functionalities necessary to use this building block in the construction of mixed organic–inorganic coordination systems [ 53 ].…”

Section: Structure and Geometrymentioning

confidence: 99%

1,2,5-Thiadiazole 1,1-dioxides and Their Radical Anions: Structure, Properties, Reactivity, and Potential Use in the Construction of Functional Molecular Materials

Pakulski

Pinkowicz

2021

Molecules

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This work provides a summary of the preparation, structure, reactivity, physicochemical properties, and main uses of 1,2,5-thiadiazole 1,1-dioxides in chemistry and material sciences. An overview of all currently known structures containing the 1,2,5-thiadiazole 1,1-dioxide motif (including the anions radical species) is provided according to the Cambridge Structural Database search. The analysis of the bond lengths typical for neutral and anion radical species is performed, providing a useful tool for unambiguous assessment of the valence state of the dioxothiadiazole-based compounds based solely on the structural data. Theoretical methodologies used in the literature to describe the dioxothiadiazoles are also shortly discussed, together with the typical ‘fingerprint’ of the dioxothiadiazole ring reported by means of various spectroscopic techniques (NMR, IR, UV-Vis). The second part describes the synthetic strategies leading to 1,2,5-thiadiazole 1,1-dioxides followed by the discussion of their electrochemistry and reactivity including mainly the chemical methods for the successful reduction of dioxothiadiazoles to their anion radical forms and the ability to form coordination compounds. Finally, the magnetic properties of dioxothiadiazole radical anions and the metal complexes involving dioxothiadiazoles as ligands are discussed, including simple alkali metal salts and d-block coordination compounds. The last section is a prospect of other uses of dioxothiadiazole-containing molecules reported in the literature followed by the perspectives and possible future research directions involving these compounds.

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“…In 2011, Awaga et al studied [1,2,5]thiadiazole [3,4-f][1,10]phenanthroline 1,1-dioxide (L) in context of its electrochemical properties and synthesis of radical salts [35]. Later on, the same group reported a number of radical salts of L, which revealed efficient π-orbitals overlap [36,37] transmitting efficient magnetic exchange interactions varying in strength from ferro-to very strong antiferromagnetic. PPN(4,7-L).…”

Section: Introductionmentioning

confidence: 99%

Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties

2019

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Phenanthroline dioxothiadiazoles are redox active molecules that form stable radical anions suitable for the construction of supramolecular magnetic materials. Herein, the preparation, structures and magnetic properties of bis(triphenylphosphine)iminium (PPN) salts of [1,2,5]thiadiazole[3,4-f][1,10]phenanthroline 1,1-dioxide (L), [1,2,5]thiadiazole[3,4-f][4,7]phenanthroline 1,1-dioxide (4,7-L), 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL), and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL) are reported. The preparation of new bromo derivatives of the L: 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL) and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL)—suitable starting materials for further derivatization—are described starting from a commercially available and cheap 1,10-phenanthroline. All PPN salts show antiferromagnetic interactions between the pairs of radical anions, which in the case of PPN(diBrL) are very strong (−116 cm−1; using Ĥ = −2JSS type of exchange coupling Hamiltonian) due to a different crystal packing of the anion radicals as compared to PPN(L), PPN(4,7-L), and PPN(BrL).

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Transition Metal Complexes and Radical Anion Salts of 1,10-Phenanthroline Derivatives Annulated with a 1,2,5-Tiadiazole and 1,2,5-Tiadiazole 1,1-Dioxide Moiety: Multidimensional Crystal Structures and Various Magnetic Properties

Cited by 8 publications

References 79 publications

Influence of the Increasing Number of Organic Radicals on the Structural, Magnetic, and Electrochemical Properties of the Copper(II)–Dioxothiadiazole Family of Complexes

Influence of the Increasing Number of Organic Radicals on the Structural, Magnetic, and Electrochemical Properties of the Copper(II)–Dioxothiadiazole Family of Complexes

1,2,5-Thiadiazole 1,1-dioxides and Their Radical Anions: Structure, Properties, Reactivity, and Potential Use in the Construction of Functional Molecular Materials

Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties

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