Organic Semiconductors and Conductors with tert-Butyl Substituents

Higashino, Toshiki; Akiyama, Yuto; Kojima, Hirotaka; Kawamoto, Tadashi; Mori, Takehiko

doi:10.3390/cryst2031222

Cited by 19 publications

(15 citation statements)

References 42 publications

(54 reference statements)

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“…As the starting material TTFMe 2 was obtained by a base‐induced homocoupling reaction of 4‐methyl‐1,3‐dithiolium iodide,30 a mixture of trans and cis isomers with respect to the methyl groups was inevitable. These two isomers cannot be separated either by crystallization or by chromatography, in contrast to the similar disubstituted molecules cis ‐ and trans ‐TTF( t Bu) 2 , which can be separated by repeated recrystallization from ethanol 31. This difficulty in isomer separation persists in the iodine‐substituted compounds TTFMe 2 I 2 .…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Properties of a Mixed‐Valence Compound with Single‐Step Tunneling and Multiple‐Step Hopping Behavior

et al. 2014

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The organic precursor bis(trimethylsilylethynyl)TTFMe2 (3, TTF = tetrathiafulvalene) was prepared as a 1:1 mixture of the cis and trans isomers. Pure samples of 3‐cis and 3‐trans were obtained by crystallization and identified by XRD analysis. The treatment of pure 3‐trans and a 1:1 mixture of 3‐cis/trans with (i) potassium carbonate, (ii) the iron complex Cp*(dppe)FeCl [5, Cp* = η5‐C5Me5, dppe = 1,2‐bis(diphenylphosphanyl)ethane] in the presence of KPF6, and (iii) tBuOK provided Cp*(dppe)Fe–C≡C–TTFMe2–C≡C–Fe(dppe)Cp* as the pure geometric isomer 6‐trans (85 %) and as the 60:40 mixture 6‐cis/trans (63 %), respectively. The oxidation of 6‐trans with [(C5H5)2Fe]PF6 gave [6‐trans][PF6]n (n = 1–3). Visible, IR, near‐IR (NIR), and electron paramagnetic resonance (EPR) spectroscopy together with DFT data show that [6‐trans][PF6] is a class II mixed‐valence complex (Hab = 85 cm–1) in which the spin distribution depends on the conformation of the molecule. Intramolecular electron transfer occurs through single‐step tunneling and a multistep hoping mechanism. The triplet state is thermally accessible for [6‐trans][PF6]2.

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Section: Resultsmentioning

confidence: 99%

“…DMF was dried with activated 4 Å molecular sieves. Compounds Cp*(dppe)FeCl ( 5 )32 and TTFMe 2 31 were prepared according to published procedures. Other chemicals were purchased from commercial sources and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Properties of a Mixed‐Valence Compound with Single‐Step Tunneling and Multiple‐Step Hopping Behavior

et al. 2014

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“…For the single crystal analysis, Bruker Kappa APEX-II diffractometer was used where the data correction and data reduction were made by APEX-II and SAINT, respectively [39]. For the structure solution, SHELXS97 software [40,41] and for refinement, SHELXL2014/6 was used to minimize the structural errors [42]. For the graphical representation of the asymmetric unit, ORTEP was used while for the hydrogen bonding, PLATON was used [43].…”

Section: Generalmentioning

confidence: 99%

Green Synthesis, SC-XRD, Non-Covalent Interactive Potential and Electronic Communication via DFT Exploration of Pyridine-Based Hydrazone

et al. 2020

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Ultrasound-based synthesis at room temperature produces valuable compounds greener and safer than most other methods. This study presents the sonochemical fabrication and characterization of a pyridine-based halogenated hydrazone, (E)-2-((6-chloropyridin-2-yl)oxy)-N′-(2-hydroxybenzylidene) acetohydrazide (HBPAH). The NMR spectroscopic technique was used to determine the structure, while SC-XRD confirmed its crystalline nature. Our structural studies revealed that strong, inter-molecular attractive forces stabilize this crystalline organic compound. Moreover, the compound was optimized at the B3LYP/6-311G(d,p) level using the Crystallographic Information File (CIF). Natural bonding orbital (NBO) and natural population analysis (NPA) were performed at the same level using optimized geometry. Time-dependent density functional theory (DFT) was performed at the B3LYP/6-311G (d,p) method to calculate the frontier molecular orbitals (FMOs) and molecular electrostatic potential (MEP). The global reactivity descriptors were determined using HOMO and LUMO energy gaps. Theoretical calculations based on the Quantum Theory of Atoms in Molecules (QT-AIM) and Hirshfeld analyses identified the non-covalent and covalent interactions of the HBPAH compound. Consequently, QT-AIM and Hirshfeld analyses agree with experimental results.

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“…There are many papers related to charge transfer cocrystals published in several special issues of the journal Crystals covering different aspects, including donor-acceptor packing type of co-crystals [43,44], hydrogen-bonded co-crystals [45,46], conducting and superconducting co-crystals [47,48], etc. However, it is still worth discussing the role of stoichiometry between donor and acceptor in co-crystals.…”

Section: Of 18mentioning

confidence: 99%

The Stoichiometry of TCNQ-Based Organic Charge-Transfer Cocrystals

Gao

Zhai

et al. 2020

Crystals

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Organic charge-transfer cocrystals (CTCs) have attracted significant research attention due to their wide range of potential applications in organic optoelectronic devices, organic magnetic devices, organic energy devices, pharmaceutical industry, etc. The physical properties of organic charge transfer cocrystals can be tuned not only by changing the donor and acceptor molecules, but also by varying the stoichiometry between the donor and the acceptor. However, the importance of the stoichiometry on tuning the properties of CTCs has still been underestimated. In this review, single-crystal growth methods of organic CTCs with different stoichiometries are first introduced, and their physical properties, including the degree of charge transfer, electrical conductivity, and field-effect mobility, are then discussed. Finally, a perspective of this research direction is provided to give the readers a general understanding of the concept.

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Organic Semiconductors and Conductors with tert-Butyl Substituents

Cited by 19 publications

References 42 publications

Synthesis and Properties of a Mixed‐Valence Compound with Single‐Step Tunneling and Multiple‐Step Hopping Behavior

Synthesis and Properties of a Mixed‐Valence Compound with Single‐Step Tunneling and Multiple‐Step Hopping Behavior

Green Synthesis, SC-XRD, Non-Covalent Interactive Potential and Electronic Communication via DFT Exploration of Pyridine-Based Hydrazone

The Stoichiometry of TCNQ-Based Organic Charge-Transfer Cocrystals

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