Mono‐ and Dinuclear Co/Ni Complexes Bearing Redox‐Active Tetrathiafulvaleneacetylacetonate Ligands – Syntheses, Crystal Structures, and Properties

Xiong, Jing; Li, Gao‐Nan; Sun, Lei; Li, Yi‐Zhi; Zuo, Jing‐Lin; You, Xiao‐Zeng

doi:10.1002/ejic.201100627

Cited by 11 publications

(2 citation statements)

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“…NMR spectra were measured on a Bruker AM 500 spectrometer. 2,6(7)-Bis[(2-cyanoethyl)thio]-3,7(6)-bis(methylthio)tetrathiafulvalene ( cis -/ trans - P 1 ) and 2,3-bis(methylthio)-6,7-bis(3-sulfanyl-2,4-pentanedione)tetrathiafulvalene ( P 3 ) were synthesized in high yields according to literature methods …”

Section: Methodsmentioning

confidence: 99%

Tricarbonyl Mono- and Dinuclear Rhenium(I) Complexes with Redox-Active Bis(pyrazole)–Tetrathiafulvalene Ligands: Syntheses, Crystal Structures, and Properties

et al. 2012

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Two new bis(3,5-dimethylpyrazole)-substituted tetrathiafulvalene ligands, 2,6(7)-bis(methylthio)-3,7(6)-bis(3sulfanyl-3,5-dimethylpyrazole)tetrathiafulvalene (L 1 ) and 2,3-bis(methylthio)-6,7-bis(3-sulfanyl-3,5-dimethylpyrazole)tetrathiafulvalene (L 2 ), have been prepared and characterized. On the basis of the two ligands, three interesting rhenium(I) tricarbonyl mono-or dinuclear complexes, ClRe(CO) 3 (cis-L 1 ) (1), [ClRe(CO) 3 (trans-L 1 )] 2 (2), and [ClRe(CO) 3 (L 2 )] 2 (3), have been prepared and structurally characterized. Electrochemical studies show sequential oxidation processes of the compounds to the corresponding radical cation and dication states, suggesting that redox events are essentially dependent on the structures of the rhenium(I) complexes. The results have evidenced electronic interactions between the TTF cores in complexes 1 and 2. Geometric and electronic structures as well as the spectroscopic properties for complexes 1−3 have been investigated by using DFT and TDDFT calculations.

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Section: Methodsmentioning

confidence: 99%

Tricarbonyl Mono- and Dinuclear Rhenium(I) Complexes with Redox-Active Bis(pyrazole)–Tetrathiafulvalene Ligands: Syntheses, Crystal Structures, and Properties

et al. 2012

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“…One could say that the necessary oxidation (partial) of the TTF moiety to promote electronic transport does not preserve the chemical integrity of the complex (dissociation) except when both TTF core and coordinating moiety are not fused [27]. Despite several attempts, there is no SMM based on TTF and strongly anisotropic 3-D transition metals such as Co(II) and Ni(II) [12,13,28,29]. But TTF performed in the field of SMMs with plethora of mononuclear and polynuclear complexes which possess a magnetic memory in the absence and, in less extent, in the presence of an external constant magnetic field.…”

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Tetrathiafulvalene-Based Magnets of Lanthanides

Cador

Pointillart

2018

Topics in Organometallic Chemistry

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Introduction 30 Magnets have been discovered about four millenniums ago in ancient Greece. 31 Nowadays, in 2015, permanent magnets market is valued to 15 billion € and is 32 expected to grow according to the demands for medical and industrial devices. In 33 this market, the segment occupied by the badly named rare-earth 1-based magnets 34 continues to expand owing to superior properties (such as saturation magnetization). 35 In the 1990s, a new class of magnets emerged in the scientific community with the discovery of the single-molecule magnets (SMMs) [1]. In these magnets, the magnetic memory is stored by the magnetic moment of a single molecule constituted of 12 manganese ions. This scientific finding reduced the size of a storage unit (byte) to nanometer. At the same time, the storage capacity of hard disks based on molecules would increase drastically. The drawback is the operating temperature range, below liquid helium (À269 C). In the last three decades, the quest for better SMMs never really stopped. In 2003, Ishikawa et al. [2] discovered that a single lanthanide ion (Ln ¼ Tb III) embedded in a doubledecker complex behaved as a SMM. To date, the lanthanide series is the most productive SMMs line in Mendeleev's periodic table with a recent tremendous record of closure of the magnetic hysteresis loop at 60 K [3, 4], close to liquid nitrogen. 47 Tetrathiafulvalene (TTF) and its analogues are well known in the field of molec-48 ular materials to produce organic metals, semiconductors, and superconductors 49 [5, 6]. The functionalization of the electron donor TTF core by an acceptor moiety 50 contributed to the development of functional materials such as switches, sensors, 51 photovoltaic cells, and nonlinear optical systems [7-9]. It was then logical to adapt 52 the acceptor moiety to coordinate transition metals for (1) elaboration of 53 multifunctional materials with both paramagnetism and electrical conductivity 54 [10, 11] and (2) the synthesis of polynuclear transition metal complexes exhibiting 55 SMM properties embedded in a conducting material [12-16]. One must admit that 56 all tentative proposals were not very successful except Oshio's work [17] which 57 shows SMM behavior but without conductivity.

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