Lucie Routaboul

Altering the Static Dipole on Surfaces through Chemistry: Molecular Films of Zwitterionic Quinonoids

The adsorption of molecular films made of small molecules with a large intrinsic electrical dipole has been explored. The data indicate that such dipolar molecules may be used for altering the interface dipole screening at the metal electrode interface in organic electronics. More specifically, we have investigated the surface electronic spectroscopic properties of zwitterionic molecules containing 12π electrons of the p-benzoquinonemonoimine type, C(6)H(2)(···NHR)(2)(···O)(2)(R = H (1), n-C(4)H(9) (2), C(3)H(6)-S-CH(3) (3), C(3)H(6)-O-CH(3) (4), CH(2)-C(6)H(5) (5)), adsorbed on Au. These molecules are stable zwitterions by virtue of the meta positions occupied by the nitrogen and oxygen substituents on the central ring, respectively. The structures of 2-4 have been determined by single crystal X-ray diffraction and indicate that in these molecules, two chemically connected but electronically not conjugated 6π electron subunits are present, which explains their strong dipolar character. We systematically observed that homogeneous molecular films with thickness as small as 1 nm were formed on Au, which fully cover the surface, even for a variety of R substituents. Preferential adsorption toward the patterned gold areas on SiO(2) substrates was found with 4. Optimum self-assembling of 2 and 5 results in ordered close packed films, which exhibit n-type character, based on the position of the Fermi level close to the conduction band minimum, suggesting high conductivity properties. This new type of self-assembled molecular films offers interesting possibilities for engineering metal-organic interfaces, of critical importance for organic electronics.

Self-assembly of strongly dipolar molecules on metal surfaces

The role of dipole-dipole interactions in the self-assembly of dipolar organic molecules on surfaces is investigated. As a model system, strongly dipolar model molecules, p-benzoquinonemonoimine zwitterions (ZI) of type C6H2(⋯ NHR)2(⋯ O)2 on crystalline coinage metal surfaces were investigated with scanning tunneling microscopy and first principles calculations. Depending on the substrate, the molecules assemble into small clusters, nano gratings, and stripes, as well as in two-dimensional islands. The alignment of the molecular dipoles in those assemblies only rarely assumes the lowest electrostatic energy configuration. Based on calculations of the electrostatic energy for various experimentally observed molecular arrangements and under consideration of computed dipole moments of adsorbed molecules, the electrostatic energy minimization is ruled out as the driving force in the self-assembly. The structures observed are mainly the result of a competition between chemical interactions and substrate effects. The substrates role in the self-assembly is to (i) reduce and realign the molecular dipole through charge donation and back donation involving both the molecular HOMO and LUMO, (ii) dictate the epitaxial orientation of the adsorbates, specifically so on Cu(111), and (iii) inhibit attractive forces between neighboring chains in the system ZI/Cu(111), which results in regularly spaced molecular gratings.

Dipole driven bonding schemes of quinonoid zwitterions on surfaces

The permanent dipole of quinonoid zwitterions changes significantly when the molecules adsorb on Ag(111) and Cu(111) surfaces. STM reveals that sub-monolayers of adsorbed molecules can exhibit parallel dipole alignment on Ag(111), in strong contrast with the antiparallel ordering prevailing in the crystalline state and retrieved on Cu(111) surfaces, which minimizes the dipoles electrostatic interaction energy. DFT shows that the rearrangement of electron density upon adsorption is a result of donation from the molecular HOMO to the surface, and back donation to the LUMO with a concomitant charge transfer that effectively reduces the overall charge dipole.

Highly efficient reduction of ferrocenyl derivatives by borane

Abstract Borane, as a DMS or a THF complex, can efficiently reduce a large range of ferrocenyl derivatives (aldehydes, ketones, ethers, acetals, carboxylic acids, esters,…) if they bear at least one oxygen at a carbon at the α position. On the contrary, similar molecules, which contain nitrogen instead of oxygen, do not react with borane.

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

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.

Approaching an organic semimetal: Electron pockets at the Fermi level for a p-benzoquinonemonoimine zwitterion.

There is compelling evidence of electron pockets, at the Fermi level, in the band structure for an organic zwitterion molecule of the p-benzoquinonemonoimine type. The electronic structure of the zwitterion molecular film has a definite, although small, density of states evident at the Fermi level as well as a nonzero inner potential and thus is very different from a true insulator. In spite of a small Brillouin zone, significant band width is observed in the intermolecular band dispersion. The results demonstrate that Blochs theorem applies to the wave vector dependence of the electronic band structure formed from the molecular orbitals of adjacent molecules in a molecular thin film of a p-benzoquinonemonoimine type zwitterion.

Synthesis of Chiral Molecules Containing Pyridine and 1,3-Pyrimidine Units: Potential Building Blocks for Helicating and Caging Ligands

Abstract A simple and efficient method for the synthesis of new chiral polyaza heterocylic structures containing pyridines and 1,3-pyrimidine units has been developed. It is based on the reaction of the appropriate enaminones with optically pure carboxamidine derived from the commercially available (R)-(−)-myrtenal.

Influence of steric hindrance on the molecular packing and the anchoring of quinonoid zwitterions on gold surfaces

Driven by the huge potential of engineering the molecular band offset with highly dipolar molecules for improving charge injection into organic electrics, the anchoring of various N-alkyl substituted quinonoid zwitterions of formula (R = iPr, Cy, CH2CH(Et)CH2CH2CH2CH3,…) on gold surfaces is studied. The N–Au interactions result in an orthogonal arrangement of the zwitterions cores with respect to the surface, and stabilize adsorbed compact rows of molecules. IR spectroscopy is used as a straightforward diagnostic tool to validate the presence of ultra-thin molecular films. When combined with computational studies, IR measurements indicate that the presence of a CH2 group in α position to the nitrogen atom is important for a successful anchoring through N–Au interactions. The presence of such a flexible CH2 spacer, or of aryl groups, enables π-interactions with the surface, making possible the anchoring of enantiopure or sterically-hindered zwitterions. X-ray diffraction analyses indicate that the intermolecular spacing within a row of molecules can be modulated by the nature of the alkyl substituent R. This modulation is directly relevant to the electronic properties of the corresponding molecular films since these zwitterions are expected to form rows on gold surfaces similar to those observed in the bulk crystalline state.

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

We experimentally investigate the electronic structure of the strongly dipolar, quinonoid-type molecule obtained by TCNQH-functionalization (TCNQH = (NC)2CC6H4CH(CN)2) of (6Z)-4-(butylamino)-6-(butyliminio)-3-oxocyclohexa-1,4-dien-1-olate C6H2(NHR)2(O)2 (where R = n-C4H9) to be very similar after deposition from solution on either graphene or gold substrates. These zwitterion adsorbate thin films form structures that are distinct from those formed by related quinonoid molecules previously studied. We argue that adsorbate–adsorbate interactions dominate and lead to a Stranski–Krastanov ‘island growth’ mechanism.

Changes in molecular film metallicity with minor modifications of the constitutive quinonoid zwitterions

Molecular films of quinonoid zwitterions, of the general formula C6H2(O)2(NHR)2, have been shown to display electronic properties highly dependent on the nature of the N-substituent R when deposited on gold substrates. The different spacing and organization of the molecules can lead to molecular films with semi-metal or dielectric behavior. With the long term goal to establish how packing effects in the solid state correlate with properties as thin films, we first attempted to identify by X-ray diffraction analysis candidate molecules showing suitable packing arrangements in the crystalline state. To this end, we have prepared a series of new functionalized, enantiopure or sterically-hindered quinonoid zwitterions and established the crystal structure of those with R = CH2–CH2–Ph (6), CH2–CH2–CH2–Ph (7), CH2–CH2–CH2–CH2–Ph (8), CH2–CH2–CH(Ph)–Ph (9), CH(CH3)–Ph (12), CH(CH2–CH3)–Ph (13), CH2–((4–CH3)–C6H4) (15), CH2–((4–NH2)–C6H4) (19) and CH2–CH2–((3,4–(OCH3)2)–C6H3) (24). An analysis of the crystal packing of three molecules, 5, 13 and 15, selected as illustrative examples for comparisons, was carried out and it was unexpectedly found that these chemically very similar molecules gave rise to different packing in the bulk, with resulting thin films showing different electronic properties. Various methods have been used for the characterization of the films, such as synchrotron radiation-based FTIR spatial spectra-microscopy, which provided an anchoring map of zwitterion 15 on a patterned substrate (Au/SiO2) showing its selective anchoring on gold. This is one of the best examples of preferential anchoring of a zwitterion and the sole example of spatial localization for a quinonoid zwitterion thin film. We have also used combined photoemission and inverse photoemission spectra and the data were compared to occupied and unoccupied DFT density state calculations.