New fluorene-substituted TTF derivatives as photofunctional materials

Fujiwara, Hideki; Tsujimoto, Keijiro; Sugishima, Yasuo; Takemoto, Shinji; Matsuzaka, Hiroyuki

doi:10.1016/j.physb.2009.11.053

Cited by 8 publications

(3 citation statements)

References 14 publications

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“…We synthesized new TTF-fluorene D-A dyads with a s-bonded thiomethylene spacer (1a-d) or a p-conjugated ethylene spacer (2a-b) (Chart 1) to create photoresponsive materials such as photoinduced conductors and photoelectric conversion materials. 31 In this paper, we report synthesis, electrochemical and optical properties, photoelectric conversion functionality of dyads 1a-d, 2a-b, and crystal structure analysis and photoconductivity of a single crystalline sample of molecule 1d. Furthermore, we will also report on the crystal structure analyses, photoconductivity and magnetic properties of the cation radical salts, 2b 2 M(CN) 2 (M = Ag, Au).…”

Section: Introductionmentioning

confidence: 99%

TTF–fluorene dyads and their M(CN)₂⁻(M = Ag, Au) salts designed for photoresponsive conducting materials

et al. 2014

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To explore photoresponsive conducting materials, we developed new tetrathiafulvalene (TTF)-fluorene D-A dyads with a s-bonded thiomethylene spacer (1a-d) or a p-conjugated ethylene spacer (2a-b) and reported their synthesis, electrochemical and optical properties. Fluorescence studies suggested that the fluorescence from an excited fluorene part is quenched by an intramolecular electron transfer process from the electrondonating TTF part to the fluorene part, and the intramolecular interaction through the p-conjugated ethylene spacer is stronger and shows more suppression than the non-planar s-bonded thiomethylene spacer. We also investigated photoelectric conversion functionality by a photoelectrochemical method using the thin films of dyads 1-2 spin-coated on ITO-coated glass substrates. We observed electric current generation that depends on the absorption spectra of thin films, suggesting that absorbed photons are converted to electric currents on the thin film/ITO electrode. Crystal structure analysis and measurement of photoconductivity of a single crystalline sample of molecule 1d having 4,5-bis(methylthio)-substituents suggest generation of photocurrents along the stacking direction of the TTF parts by the photoinduced intramolecular electron transfer and the resultant charge-separated state. Furthermore, we also reported the crystal structure analyses, photoconductivity and magnetic properties of the cation radical salts, 2b 2 M(CN) 2 (M = Ag, Au), where 2b contains a 4,5-ethylenedithio-substituent. The Ag(CN) 2 salt showed a semiconducting behaviour with a room temperature conductivity of 0.088 S cm À1 due to a half-filled Mott insulating band structure of this crystal that originates from a strongly dimerized intermolecular interaction. Upon photoirradiation, this salt showed a slight enhancement of conductivities of ca. 14%.

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Section: Introductionmentioning

confidence: 99%

TTF–fluorene dyads and their M(CN)₂⁻(M = Ag, Au) salts designed for photoresponsive conducting materials

et al. 2014

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“…Particularly, photoinduced intramolecular electron transfer (PET) process between electron-donating TTF derivatives (D) and electron-accepting parts (A) such as fluorophores, C 60 and chelating ligands has yielded several photofunctional materials such as chemical sensors based on fluorescence probe functionalities, organic photovoltaic (OPV) cells and nonlinear optical devices [1][2][3][4][5][6][7]. Among them, to develop photoinduced conducting materials and photo-electric conversion materials, we have investigated the photofunctional materials using the TTF-based D-A type dyads containing strongly fluorescent parts such as 2, 5-diphenyl-1, 3, 4-oxadiazole (PPD) [8,9], 1, 3-benzothiazole (BTA) [10][11][12], fluorene [13,14] and 4, 4-difluoro-4-bora-3a, 4a-diaza-s-indacene (BOD-IPY) [15,16] as antennas for photoexcitation. On the other hand, since the first fabrication of organic light-emitting diodes (OLEDs) using tris(8-quinolinato)aluminum (Alq 3 , q = 8-quinolinato) [17], various kinds of 8-quinolinato transition metal complexes Mq x have attracted much attention because of their strongly fluorescent character, high thermal stability and excellent electron transport properties [18][19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Physical Properties of Tetrathiafulvalene-8-Quinolinato Zinc(II) and Nickel(II) Complexes

2021

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To develop donor–acceptor–donor (D–A–D) type new photo-electric conversion materials, new tetrathiafulvalene (TTF)-Mq2-TTF complexes 1 and 2 were synthesized, where two bis(n-hexylthio)tetrathiafulvalene moieties were attached to the Mq2 part (1: M = Zn, 2: M = Ni, q = 8-quinolinato) through amide bonds. UV-Vis absorption spectra of these complexes showed strong and sharp absorption maxima at 268 nm and small absorption maxima around 410 nm, corresponding to those of Znq2 and Niq2 parts. Furthermore, complexes 1 and 2 exhibited absorption tails up to a much longer wavelength region of ca. 700 nm, suggesting the appearance of charge transfer absorption from TTF to the Mq2 parts. The photoelectrochemical measurements on the thin films of these complexes casted on ITO-coated glass substrates suggest that positive photocurrents can be generated by the photoinduced intramolecular electron transfer process between the TTF and Mq2 parts.

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“…Development of photofunctional materials using donor–acceptor (D–A) type dyads based on TTF frameworks, where TTF is tetrathiafulvalene, has been intensively studied for application to organic materials such as fluorescence switches, metal ion sensors, photovoltaic cells, and nonlinear optics. − We developed several D–A dyads using the TTF framework and fluorescent molecules such as 2,5-diphenyl-1,3,4-oxadiazole (PPD) and fluorene and reported their crystal structures and electrochemical and optical properties. − Among them, a new D–A dyad, TTF–CHCH–BTA, 1 , in which a 1,3-benzothiazole (BTA) ring is connected with the TTF part through an ethylene spacer, was synthesized to realize photoswitchable conductors and photoelectric conversion materials . A single-crystalline sample of 1 showed generation of photocurrents along the segregated stackings of the TTF and BTA parts by a photoinduced intramolecular electron transfer and resultant formation of a charge-separated state.…”

Section: Introductionmentioning

confidence: 99%

Cu^IIand Cu^ICoordination Complexes Involving Two Tetrathiafulvalene-1,3-benzothiazole Hybrid Ligands and Their Radical Cation Salts

et al. 2013

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Preparations, crystal structure analyses, and magnetic property investigations on a new Cu(II)(hfac)2 complex coordinated with two TTF-CH═CH-BTA ligands, where hfac is hexafluoroacetylacetonate, TTF is tetrathiafulvalene, and BTA is 1,3-benzothiazole, are reported together with those of its dicationic AsF6(-) salt, [Cu(hfac)2(TTF-CH═CH-BTA)2](AsF6)2, in which each TTF part is in a radical cation state. In these Cu(II)(hfac)2 complexes, two ligands are bonded to the central Cu atom of the Cu(hfac)2 part through the nitrogen atom of the 1,3-benzothiazole ring and occupy the two apical positions of the Cu(hfac)2 complex with an elongated octahedral geometry. These two ligands are located parallelly in a transverse head-to-tail manner, and the Cu(hfac)2 moiety is closely sandwiched by these two ligands. In the AsF6(-) salt of the Cu(hfac)2 complex, each TTF dimer is separated by the AsF6(-) anions and has no overlap with each other within the one-dimensional arrays, resulting in an insulating behavior. Both Cu(hfac)2 complexes showed the simple Curie-like temperature dependence of paramagnetic susceptibilities (χM), indicating that no interaction exists between the paramagnetic Cu(II) d spins. Furthermore, crystal structure analysis and magnetic/conducting properties of a radical cation ReO4(-) salt of the Cu(I) complex with two TTF-CH═CH-BTA ligands, [Cu(TTF-CH═CH-BTA)2](ReO4)2, are also described. Two nitrogen atoms of the ligands are connected to the central Cu(I) in a linear dicoordination with a Cu-N bond length of 1.879(9) Å. Two TTF parts of the neighboring complexes form a dimerized structure, and such a TTF dimer forms a one-dimensional uniform array along the a direction with a short S-S contact of 3.88 Å. Magnetic property measurement suggested the existence of a strongly antiferromagnetic one-dimensional uniform chain of S = 1/2 spins that originate from the radical cation states of the TTF dimers. Due to the construction of the one-dimensional uniform array of the radical cation state of the TTF dimer along the a axis, a semiconducting behavior is observed with σ(rt) = of 6 × 10(-5) S cm(-1) and an activation energy of E(a) = 0.16 eV.

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New fluorene-substituted TTF derivatives as photofunctional materials

Cited by 8 publications

References 14 publications

TTF–fluorene dyads and their M(CN)₂⁻(M = Ag, Au) salts designed for photoresponsive conducting materials

TTF–fluorene dyads and their M(CN)₂⁻(M = Ag, Au) salts designed for photoresponsive conducting materials

Synthesis and Physical Properties of Tetrathiafulvalene-8-Quinolinato Zinc(II) and Nickel(II) Complexes

Cu^IIand Cu^ICoordination Complexes Involving Two Tetrathiafulvalene-1,3-benzothiazole Hybrid Ligands and Their Radical Cation Salts

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New fluorene-substituted TTF derivatives as photofunctional materials

Cited by 8 publications

References 14 publications

TTF–fluorene dyads and their M(CN)2−(M = Ag, Au) salts designed for photoresponsive conducting materials

TTF–fluorene dyads and their M(CN)2−(M = Ag, Au) salts designed for photoresponsive conducting materials

Synthesis and Physical Properties of Tetrathiafulvalene-8-Quinolinato Zinc(II) and Nickel(II) Complexes

CuIIand CuICoordination Complexes Involving Two Tetrathiafulvalene-1,3-benzothiazole Hybrid Ligands and Their Radical Cation Salts

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TTF–fluorene dyads and their M(CN)₂⁻(M = Ag, Au) salts designed for photoresponsive conducting materials

TTF–fluorene dyads and their M(CN)₂⁻(M = Ag, Au) salts designed for photoresponsive conducting materials

Cu^IIand Cu^ICoordination Complexes Involving Two Tetrathiafulvalene-1,3-benzothiazole Hybrid Ligands and Their Radical Cation Salts