Long‐Lived Charge Separation in Novel Axial Donor–Porphyrin–Acceptor Triads Based on Tetrathiafulvalene, Aluminum(III) Porphyrin and Naphthalenediimide

Poddutoori, Prashanth K.; Zarrabi, Niloofar; Moiseev, Andrey G.; Gumbau‐Brisa, Roger; Vassiliev, S.; Est, Art van der

doi:10.1002/chem.201202995

Cited by 53 publications

(68 citation statements)

References 94 publications

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“…], in which e is the elementary charge, ϵ 0 is the electric constant and ϵ r is the relative static permittivity . These values result in a Δ ET G ° value of (−61.5±6.8) kJ mol −1 (−0.64 eV) in dichloromethane, which is in the upper range for similar supramolecular D‐A systems . Therefore, the charge separation between the excited D*‐A complex and D + ‐A − is thermodynamically highly favoured.

true Δ_{ET} G^{\circ} = E_{normalg}^{el} - \frac{e}{4 π ϵ_{0} ϵ_{r} r_{DA}} - E_{normalg}^{opt}

…”

Section: Resultsmentioning

confidence: 99%

“…[63] These values result in a D ET G8 value of (À61.5 AE 6.8) kJ mol À1 www.chemeurj.org (À0.64 eV) in dichloromethane, which is in the upper range for similar supramolecular D-A systems. [64][65][66][67] Therefore, the charge separation between the excited D*-A complex and D + -A À is thermodynamically highly favoured.…”

Section: Optoelectronic Properties Of [2]rotaxanementioning

confidence: 99%

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A Divalent Pentastable Redox‐Switchable Donor–Acceptor Rotaxane

Schröder

Hupatz

Achazi

et al. 2017

Chemistry A European J

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Donor-acceptor materials with small HOMO-LUMO gaps are important in molecular electronics, but are often difficult to synthesise. A simple and efficient way to position tetrathiafulvalene (TTF) as the donor and naphthalene diamide (NDI) as the acceptor in close proximity to each other in a divalent crown/ammonium pseudo[2]rotaxane is presented. The divalent design provides high chelate cooperativity and much stronger binding compared with a monovalent analogue. The pseudo[2]rotaxane was then doubly interlocked by stoppering it in a catalyst-free 1,3-dipolar cycloaddition. UV/Vis and cyclic voltammetry experiments with the resulting [2]rotaxane revealed the optoelectronic properties of an intramolecular charge transfer with a small HOMO-LUMO energy gap. Redox-switching experiments showed the rotaxane to be pentastable. DFT calculations provided insights into the electronic structures of the five redox states.

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true Δ_{ET} G^{\circ} = E_{normalg}^{el} - \frac{e}{4 π ϵ_{0} ϵ_{r} r_{DA}} - E_{normalg}^{opt}

…”

Section: Resultsmentioning

confidence: 99%

Section: Optoelectronic Properties Of [2]rotaxanementioning

confidence: 99%

A Divalent Pentastable Redox‐Switchable Donor–Acceptor Rotaxane

Schröder

Hupatz

Achazi

et al. 2017

Chemistry A European J

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“…These chemical shifts (δ) agree well with those of the axial bonding type porphyrin systems. 42,44,45,70 Hence, the Δδ values (i.e., δ monomer − δ dyad ) are a function of their proximity to the porphyrin ring. Figure 2 shows the 1 H NMR spectrum of the triad (TTFpy→AlPor-Ph-H 2 Por (bottom), that is, a 1:1 mixture of AlPorPh-H 2 Por and TTF-py) along with the individual spectra of AlPor-Ph-H 2 Por (middle) and TTF-py (top).…”

Section: ■ Introductionmentioning

confidence: 99%

Modulation of Energy Transfer into Sequential Electron Transfer upon Axial Coordination of Tetrathiafulvalene in an Aluminum(III) Porphyrin–Free-Base Porphyrin Dyad

et al. 2015

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Axially assembled aluminum(III) porphyrin based dyads and triads have been constructed to investigate the factors that govern the energy and electron transfer processes in a perpendicular direction to the porphyrin plane. In the aluminum(III) porphyrin-free-base porphyrin (AlPor-Ph-H2Por) dyad, the AlPor occupies the basal plane, while the free-base porphyrin (H2Por) with electron withdrawing groups resides in the axial position through a benzoate spacer. The NMR, UV-visible absorption, and steady-state fluorescence studies confirm that the coordination of pyridine appended tetrathiafulvalene (TTF) derivative (TTF-py or TTF-Ph-py) to the dyad in noncoordinating solvents afford vertically arranged supramolecular self-assembled triads (TTF-py→AlPor-Ph-H2Por and TTF-Ph-py→AlPor-Ph-H2Por). Time-resolved studies revealed that the AlPor in dyad and triads undergoes photoinduced energy and/or electron transfer processes. Interestingly, the energy and electron donating/accepting nature of AlPor can be modulated by changing the solvent polarity or by stimulating a new competing process using a TTF molecule. In modest polar solvents (dichloromethane and o-dichlorobenzene), excitation of AlPor leads singlet-singlet energy transfer from the excited singlet state of AlPor ((1)AlPor*) to H2Por with a moderate rate constant (k(EnT)) of 1.78 × 10(8) s(-1). In contrast, excitation of AlPor in the triad results in ultrafast electron transfer from TTF to (1)AlPor* with a rate constant (k(ET)) of 8.33 × 10(9)-1.25 × 10(10) s(-1), which outcompetes the energy transfer from (1)AlPor* to H2Por and yields the primary radical pair TTF(+•)-AlPor(-•)-H2Por. A subsequent electron shift to H2Por generates a spatially well-separated TTF(+•)-AlPor-H2Por(-•) radical pair.

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“…assembled such supramolecular donor-acceptor systems consisting of Al(III)Por with axially bounded naphthalenediimide (NDI) and tetrathiafulvalene (TTF) as acceptor and donor, respectively (Fig. 41)[127].The AlPor allowed two different groups to attach at the opposite faces of AlPor. In the triad, the NDI and TTF groups were attached on the opposite faces of the AlPor via covalent bonding and a metal-ligand coordination bond, respectively.…”

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confidence: 98%