Assembly of 2D ionic layers by reaction of alkali halides with the organic electrophile 7,7,8,8-tetracyano-p-quinodimethane (TCNQ)

Wäckerlin, Christian; Iacoviță, Cristian; Chylarecka, Dorota; Fesser, Petra; Jung, Thomas A.; Ballav, Nirmalya

doi:10.1039/c1cc12519b

Cited by 72 publications

(101 citation statements)

References 24 publications

(10 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…26 However, they have different ionic radii, which increase going from Li to Cs (see Figure 4c). 27 For each alkali metal M, we relax the periodically repeated gas phase MÀTCNQ 4 complex network for several intercomplex distances using periodic boundary conditions [see also Supporting Information (SI).…”

Section: Articlementioning

confidence: 99%

Fine-Tuning the Electrostatic Properties of an Alkali-Linked Organic Adlayer on a Metal Substrate

2013

View full text Add to dashboard Cite

The performance of modern organic electronic devices is often determined by the electronic level alignment at a metal–organic interface. This property can be controlled by introducing an interfacial electrostatic dipole via the insertion of a stable interlayer between the metallic and the organic phases. Here, we use density functional theory to investigate the electrostatic properties of an assembled structure formed by alkali metals coadsorbed with 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecules on a Ag(100) substrate. We find that the interfacial dipole buildup is regulated by the interplay of adsorption energetics, steric constraints and charge transfer effects, so that choosing chemical substitutions within TCNQ and different alkali metals provides a rich playground to control the systems’ electrostatics and in particular fine-tune its work-function shift

show abstract

Section: Articlementioning

confidence: 99%

Fine-Tuning the Electrostatic Properties of an Alkali-Linked Organic Adlayer on a Metal Substrate

2013

View full text Add to dashboard Cite

show abstract

“…[20][21][22] Regardingt ot hese distinct properties of the coordinationm otif, researchers have made substantial efforts to control metal-organic coordination self-assembly on metal surfaces, such as by alteringt he type and concentration of organic ligandso rm etallic atoms (e.g. transition, alkali and lanthanide metals), [23][24][25][26][27][28][29][30][31][32][33] by selecting substrates and by tuning the ratio of metal/organic reactants. [6,23,30] Nevertheless, because of the intermediate of substrates and the liability of coordination motifs, controlling coordination assembly,e specially at nanoscale, remainsa challenge.…”

Section: Introductionmentioning

confidence: 99%

Self‐Assembly and Local Manipulation of Au‐Pyridyl Coordination Networks on Metal Surfaces

et al. 2017

View full text Add to dashboard Cite

Using scanning tunnelling microscopy (STM), we demonstrate that Au-pyridyl coordination can be used to assemble two-dimensional coordination network structures on metal surfaces. The polymorphism of the coordination network structures can be manipulated at both the micro- and nanoscale. Using the same organic ligand, we assembled two distinct polymorphic network structures, which were assisted by threefold Au-pyridyl coordination on Ag(111) with predeposited Au atoms (α-network), and by twofold Au-pyridyl coordination on Au(111) (β-network), respectively. Specifically on the Au(111) surface, single-oriented β-network domains as large as ≈400 nm were selected by thermal annealing. We ascribe this global control strategy to distinct Au bonding modes tuned by molecule-substrate interactions. Using an STM tip, we succeeded in creating α-network domains (≈10 nm) locally within the homogeneous β-network domain areas on Au(111) in a controlled manner.

show abstract

“…In this context, TCNX ligands are either found to function as neutral π acceptors, as stable monoanionic radicals, or as dianions and, thus, can play an essential role as electron-transfer mediators in inorganic and organometallic chemistry 5, 6, 7, 8. In addition, the charge-transfer interactions of TCNX acceptor systems with various kinds of electron donors can lead to a wide variety of supramolecular binding motifs, including π—π stacking and the assembly of ionic layer structures 2, 9. These resulting materials frequently display very attractive functional properties, such as electrical conductivity, single-molecule magnetism, low-energy charge-transfer transitions, and non-linear optical activity 2, 5, 10, 11…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

Wöß

Monkowius

Knör

2012

Chemistry A European J

View full text Add to dashboard Cite

The heteroaromatic polynitrile compound tetracyanopyridine (TCNPy) is introduced as a new electron acceptor for the formation of deeply colored charge-transfer complexes. In MeCN, TCNPy is characterized by a quasireversible one-electron-reduction process at −0.51 V (versus SCE). The tetracyanopyridine radical anion undergoes a secondary chemical reaction, which is assigned to a protonation step. TCNPy has been demonstrated to generate 1:1 complexes with various electron donors, including tetrathiafulvalene (TTF) and dihydroxybenzene derivatives, such as p-hydroquinone and catechol. Visible- or NIR-light-induced excitation of the intense charge-transfer bands of these compounds leads to a direct optical electron-transfer process for the formation of the corresponding radical-ion pairs. The presence of available electron donors that contain protic groups in close proximity to the TCNPy acceptor site opens up a new strategy for the photocontrolled generation of pyridinium radicals in a stepwise proton-coupled electron-transfer (PCET) sequence.

show abstract

Assembly of 2D ionic layers by reaction of alkali halides with the organic electrophile 7,7,8,8-tetracyano-p-quinodimethane (TCNQ)

Cited by 72 publications

References 24 publications

Fine-Tuning the Electrostatic Properties of an Alkali-Linked Organic Adlayer on a Metal Substrate

Fine-Tuning the Electrostatic Properties of an Alkali-Linked Organic Adlayer on a Metal Substrate

Self‐Assembly and Local Manipulation of Au‐Pyridyl Coordination Networks on Metal Surfaces

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

Contact Info

Product

Resources

About