A Donor–Acceptor Tetrathiafulvalene Ligand Complexed to Iron(II): Synthesis, Electrochemistry, and Spectroscopy of [Fe(phen)2(TTF-dppz)](PF6)2

Dupont, Nathalie; Ran, Ying-Fen; Liu, Shixia; Grilj, Jakob; Vauthey, Eric; Decurtins, Silvio; Hauser, Andreas

doi:10.1021/ic3019277

Cited by 19 publications

(14 citation statements)

References 59 publications

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“…3a) as shown after complex formation. 32 In contrast, the free molecules do not bind to a Na + cation and show a charge distribution (Fig. 4e) as predicted for DA molecules with a positive charge located at the donor region and a negative charge at the acceptor site.…”

Section: Resultssupporting

confidence: 53%

Donor–Acceptor Properties of a Single-Molecule Altered by On-Surface Complex Formation

et al. 2017

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Electron donor-acceptor molecules are of outstanding interest in molecular electronics and organic solar cells for their intramolecular charge transfer controlled via electrical or optical excitation. The preservation of their electronic character in the ground state upon adsorption on a surface is cardinal for their implementation in such single-molecule devices. Here, we investigate by atomic force microscopy and scanning tunneling microscopy a prototypical system consisting of a π-conjugated tetrathiafulvalene-fused dipyridophenazine molecule adsorbed on thin NaCl films on Cu(111). Depending on the adsorption site, the molecule is found either in a nearly undisturbed free state or in a bound state. In the latter case, the molecule adopts a specific adsorption site, leading to the formation of a chelate complex with a single Na alkali cation pulled out from the insulating film. Although expected to be electronically decoupled, the charge distribution of the complex is drastically modified, leading to the loss of the intrinsic donor-acceptor character. The chelate complex formation is reversible with respect to lateral manipulations, enabling tunable donor-acceptor molecular switches activated by on-surface coordination.

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Section: Resultssupporting

confidence: 53%

Donor–Acceptor Properties of a Single-Molecule Altered by On-Surface Complex Formation

et al. 2017

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“…12 The photophysical properties of the related [Fe(phen) 2 (L)] 2+ complex have been reported. 13 Compound 1·(CH 2 Cl 2 ) 2 crystallises in the triclinic space group P-1 (N°2). ‡ The ORTEP drawing of 1 is shown in Figure 1 (150 K).…”

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Thermal and near-infrared light induced spin crossover in a mononuclear iron(ii) complex with a tetrathiafulvalene-fused dipyridophenazine ligand

et al. 2016

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“…Compounds 1 b ( E red 1 =−1.15 V, E red 2 =−1.52 V) and 8 ( E red 1 =−1.36 V, E red 2 =−1.76 V) also possess two reduction peaks (Figure d). These two peaks are assigned to reduction of the Pz unit . The value of E red 1 of 1 c is comparable to that of 1 b because the LUMO energy levels of 1 c and 1 b are close (Figure c).…”

Section: Resultsmentioning

confidence: 83%

Tetrathiafulvalene‐Fused Heterabuckybowl: Protonation‐Induced Electron Transfer and Self‐Sensitized Photooxidation

Liu

Bai

et al. 2020

Chemistry A European J

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The electron donor tetrathiafulvalene (D 1 )w as fused onto the electron-rich heterabuckybowl trichalcogenasumanene( D 2 )t hrougha ne lectron-deficient pyrazine unit (A) to give 1c, 1d, 2c,a nd 2d,f eaturing the D 1 -A-D 2 structure. Both D 1 and D 2 play ap ivotalr ole in intramolecular charge-transfer (ICT) transitions, consequently 1c, 2d, 2c, and 2d show ab road ICT band at 450-720 nm in steady state. They exhibit two charge-separated transient states, CS 1 and CS 2 ,t hat appear in sequence. CS 1 has as hort lifetime (542 fs), and the D 1 moiety on CS 1 is in the radical cation state with an absorption maximum (l max )a t8 89 nm. CS 1 then converts into CS 2 (l max ,1 105 nm) through an ICT betweenD 1 C + and D 2 ,a ffording D 1 (1Àd) C + and D 2 d C + .C ompounds 1c, 1d, 2c,a nd 2d show protonation-induced intramolecular electron transfer that leads to absorption at l = 700-1300 nm. Owing to the existence of an electron-rich C=Cb ond on the D 1 moiety and in situ generation of 1 O 2 by the pyrazine-fusedD 2 moiety,c ompounds 1c, 1d, 2c,a nd 2d display self-sensitized photooxidation in 50 s.[a] Dr.Scheme1.Synthesis of 1c, 1d, 2c,and 2d and relatedc ompounds:a)FeCl 3 , CH 2 Cl 2 /CH 3 NO 2 ,RT, 2h;b )1,2-diaminobenzene,A cOH,8 08C, 4h;c)P(OEt) 3 / toluene, 120 8C, 3h;d )AcOH,8 08C, 0.5-1.0 h, Ar atmosphere.Scheme4.Photooxidation reactions for 1c and 9.The structures of 10 and 11 were also determined by means of single-crystalX RD.Scheme5.Proposed reaction mechanism for the self-sensitized photooxidation of 1c'.The Gibbs free energies of 1c'(GS) and 3 O 2 are set to 0.0 kcal mol À1 as ar eference. IC = internal conversion, ISC = intersystem crossover, IM = intermediate, TS = transition state.

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A Donor–Acceptor Tetrathiafulvalene Ligand Complexed to Iron(II): Synthesis, Electrochemistry, and Spectroscopy of [Fe(phen)₂(TTF-dppz)](PF₆)₂

Cited by 19 publications

References 59 publications

Donor–Acceptor Properties of a Single-Molecule Altered by On-Surface Complex Formation

Donor–Acceptor Properties of a Single-Molecule Altered by On-Surface Complex Formation

Thermal and near-infrared light induced spin crossover in a mononuclear iron(ii) complex with a tetrathiafulvalene-fused dipyridophenazine ligand

Tetrathiafulvalene‐Fused Heterabuckybowl: Protonation‐Induced Electron Transfer and Self‐Sensitized Photooxidation

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