Adsorption of TCNQH-functionalized quinonoid zwitterions on gold and graphene: evidence for dominant intermolecular interactions

Kong, Lingmei; Routaboul, Lucie; Braunstein, Pierre; Park, Hong-Gi; Choi, Jaewu; Córdova, John P. Colón; Vega, Esther; Rosa, Luis G.; Doudin, B.; Dowben, Peter A.

doi:10.1039/c3ra40930a

Cited by 5 publications

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References 52 publications

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“…Calculations of the molecular orbitals, both occupied and unoccupied, of the polymer blend were performed for purposes of comparison with the density of states deduced from the UPS-IPES experiments. As in previous studies, 6,7,30,32,[45][46][47] the orbital energies of the single molecules (as in a gas phase experiment) were performed with the SPARTAN 10 package, based on density functional theory (DFT), using the conventional B3LYP hybrid functional and the 6-31 G(d,p) basis set, while the semiempirical calculations followed the PM3 methodology. The calculated density of states (DOS) were obtained by applying equal Gaussian envelopes of 1 eV full width halfmaximum to each molecular orbital energy to account for the solid state broadening in photoemission, followed by the summing of all envelopes to form the theoretical DOS spectra.…”

Section: Theorymentioning

confidence: 99%

Changing molecular band offsets in polymer blends of (P3HT/P(VDF–TrFE)) poly(3-hexylthiophene) and poly(vinylidene fluoride with trifluoroethylene) due to ferroelectric poling

et al. 2014

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Changing molecular band offsets in polymer blends of (P3HT/P(VDF-TrFE)) poly(3-hexylthiophene) and poly(vinylidene fluoride with trifluoroethylene) due to ferroelectric poling" (2013). Peter Dowben Publications. 249. Photoelectron emission and inverse photoemission spectroscopy studies of polymer blends of poly(vinylidene fluoride (70%)trifluoroethylene (30%)) P(VDF-TrFE 70 : 30) and regio-regular poly(3hexylthiophene) (P3HT) provide evidence of changes in the molecular band offsets as a result of changes in the ferroelectric polarization in P(VDF-TrFE). Investigation of the blends with higher concentrations of the semiconducting P3HT component revealed that the organic semiconductor component of the blend dominates the electronic structure in the vicinity of the chemical potential. Specifically, the states of P3HT at the conduction band minimum and valence band maximum fall within the HOMO-LUMO gap of the dielectric ferroelectric P(VDF-TrFE) but the P3HT does not exhibit a change in the molecular band offset with respect to the Fermi level or band bending with polarization reversal, unlike P(VDF-TrFE).

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Section: Theorymentioning

confidence: 99%

Changing molecular band offsets in polymer blends of (P3HT/P(VDF–TrFE)) poly(3-hexylthiophene) and poly(vinylidene fluoride with trifluoroethylene) due to ferroelectric poling

et al. 2014

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“…The single‐crystal X‐ray analysis of 3 confirmed the zwitterionic quinonoid/biscyanine nature of dactylocyanines, (Figure ). Indeed, the bond lengths confirmed the presence of two delocalized 6 π‐systems [anionic O

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O and cationic RHN

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NHR] . The length of the C−C bonds connecting the two π‐systems indicates a single‐bond order and therefore no conjugation between the two independent cyanines.…”

Section: Resultsmentioning

confidence: 89%

An Unprecedented Blue Chromophore Found in Nature using a “Chemistry First” and Molecular Networking Approach: Discovery of Dactylocyanines A–H

Bonneau

Chen

Lachkar

et al. 2017

Chemistry A European J

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Guided by a "chemistry first" approach using molecular networking, eight new bright-blue colored natural compounds, namely dactylocyanines A-H (3-10), were isolated from the Polynesian marine sponge Dactylospongia metachromia. Starting from ilimaquinone (1), an hemisynthetic phishing probe (2) was prepared for annotating and matching structurally related natural substances in D. metachromia crude extract network. This strategy allowed characterizing for the first time in Nature the blue zwitterionic quinonoid chromophore. The solvatochromic properties of the latter are reported.

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Reversible Switching of the Coordination Modes of a Pyridine-Functionalized Quinonoid Zwitterion; Its Di- and Tetranuclear Palladium Complexes

et al. 2014

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The coordination chemistry of a new functional quinonoid zwitterion (E)-3-oxo-4-((2-(pyridin-2-yl)ethyl)amino)-6-((2-(pyridin-2-yl)ethyl)iminio)cyclohexa-1,4-dienolate (2, H2L), in which a CH2CH2 spacer connects the N substituents of the quinonoid core with a pyridine group, was explored in Pd(II) chemistry. Different coordination modes have been observed, depending on the experimental conditions and the reagents. The reaction of H2L with [Pd(μ-Cl)(dmba)]2 (dmba = o-C6H4CH2NMe2-C,N) afforded the dinuclear complex [{PdCl(dmba)}2(H2L)] (3) in which H2L acts as a NPy,NPy bidentate ligand. Deprotonation of this complex with NaH resulted in the formation of the dinuclear complex [{Pd(dmba)}2(μ-L)] (4) in which a shift of the Pd(II) centers from the NPy sites to the N,O donor sites of the zwitterion core has occurred, resulting in a N2O2 tetradentate behavior of ligand L. Reaction of 4 with HCl regenerates 3 quantitatively. Chloride abstraction from 3 with AgOTf (OTf = trifluoromethanesulfonate) resulted in loss of one of the two dmba ligands and formation of an unusual tetranuclear Pd(II) complex, [{Pd(dmba)}(μ-L)Pd]2(OTf)2 (5), in which two dinuclear entities have dimerized, one pyridine donor group from each dimer forming a bridge with the other dinuclear entity. This results in a N2, O2, NPy, NPy hexadentate behavior for the ligand L. Complexes 3 and 4 constitute an unprecedented reversible, switchable system where deprotonation or protonation promotes the reversible migration of the [Pd(dmba)](+) moieties, from the NPy sites in 3, to the N,O donor sites of the quinonoid core in 4, respectively. This switch modifies the extent of π-delocalization involving the potentially antiaromatic quinonoid moiety and is accompanied by a significant color change, from red in 3 to green in 4. The presence of uncoordinated pyridine donor groups in 4 allowed the use of this complex for the preparation of the neutral tetranuclear complex [{Pd(dmba)}2(μ-L){PdCl(dmba)}2] (6) in which 4 acts as a NPy,NPy-bidentate metalloligand toward two PdCl(dmba) moieties. Halide abstraction from 6 afforded the monocationic, tetranuclear complex [{Pd(dmba)}2(μ-L){Pd(dmba)}2(μ-Cl)]PF6 (7) in which the two Pd(dmba) moieties are connected by ligand L and a bridging chloride. By Cl/PF6 anion metathesis, it was possible to switch quantitatively from complex 6 to 7 and vice versa. All new compounds were unambiguously characterized by IR, NMR, and mass spectroscopy. Single-crystal X-ray diffraction is also available for molecules 2-5 and 7.

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Adsorption of TCNQH-functionalized quinonoid zwitterions on gold and graphene: evidence for dominant intermolecular interactions

Cited by 5 publications

References 52 publications

Changing molecular band offsets in polymer blends of (P3HT/P(VDF–TrFE)) poly(3-hexylthiophene) and poly(vinylidene fluoride with trifluoroethylene) due to ferroelectric poling

Changing molecular band offsets in polymer blends of (P3HT/P(VDF–TrFE)) poly(3-hexylthiophene) and poly(vinylidene fluoride with trifluoroethylene) due to ferroelectric poling

An Unprecedented Blue Chromophore Found in Nature using a “Chemistry First” and Molecular Networking Approach: Discovery of Dactylocyanines A–H

Reversible Switching of the Coordination Modes of a Pyridine-Functionalized Quinonoid Zwitterion; Its Di- and Tetranuclear Palladium Complexes

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