“Magic” Surface Clustering of Borazines Driven by Repulsive Intermolecular Forces

Kervyn, Simon; Kalashnyk, Nataliya; Riello, Massimo; Moreton, Ben; Tasseroul, Jonathan; Wouters, Jan; Jones, T. S.; Vita, Alessandro De; Costantini, Giovanni; Bonifazi, Davide

doi:10.1002/ange.201300948

Cited by 16 publications

(12 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Whereas compound 1 features three phenyl (Ph) and three mesityl (Mes) groups bonded to the nitrogen and boron atoms, respectively, molecule 2 replaces the phenyl groups with peripherally protruding phenyl-4-ethynylphenyl moieties. Following the experimental protocols developed by us for borazine 1 , 56 , 57 molecule 2 was obtained after reaction of 4-ethynylphenylaniline with BCl 3 upon subsequent addition of three equivalents of MesLi following the route displayed in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Self‐Assembly of Decoupled Borazines on Metal Surfaces: The Role of the Peripheral Groups

Kalashnyk

Nagaswaran

Kervyn

et al. 2014

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Two borazine derivatives have been synthesised to investigate their self-assembly behaviour on Au(111) and Cu(111) surfaces by scanning tunnelling microscopy (STM) and theoretical simulations. Both borazines form extended 2D networks upon adsorption on both substrates at room temperature. Whereas the more compact triphenyl borazine 1 arranges into close-packed ordered molecular islands with an extremely low density of defects on both substrates, the tris(phenyl-4-phenylethynyl) derivative 2 assembles into porous molecular networks due to its longer lateral substituents. For both species, the steric hindrance between the phenyl and mesityl substituents results in an effective decoupling of the central borazine core from the surface. For borazine 1, this is enough to weaken the molecule–substrate interaction, so that the assemblies are only driven by attractive van der Waals intermolecular forces. For the longer and more flexible borazine 2, a stronger molecule–substrate interaction becomes possible through its peripheral substituents on the more reactive copper surface.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Ruled by a delicate interplay of short-range van der Waals (vdW) attractions and long-range Coulomb repulsions between molecules, we have shown that a hydroxyl-pentaaryl borazine assembles in small clusters, which is in striking contrast with the large-island assembly obtained for molecule 1 (Scheme 1 ). 57 …”

Section: Introductionmentioning

confidence: 99%

Self‐Assembly of Decoupled Borazines on Metal Surfaces: The Role of the Peripheral Groups

Kalashnyk

Nagaswaran

Kervyn

et al. 2014

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…Amongt he different functionalisation approaches, the replacement (i.e.,d oping) of one or more carbon atoms with electron-deficient or -rich heteroatoms is emerging as av ersatile strategyt ot une optoelectronic properties. [9] The insertion of third-group elements, such as borono ra luminium, introduces electronicv acancies (or holes), [10][11][12][13][14][15] whereas the insertion of fifth-and sixth-group elementse lectronicallye nriches carbonbased substrates to generate non-bonding states. [16][17][18][19] Phosphorescence is aforbidden radiativerelaxationo fanexcited state with spin symmetry different from that of the ground state.F or organic species, it mostly involves the decay from at riplet to as inglet state.…”

Section: Introductionmentioning

confidence: 99%

Walking Down the Chalcogenic Group of the Periodic Table: From Singlet to Triplet Organic Emitters

Kremer

Aurisicchio

Leo

et al. 2015

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The synthesis, X-ray crystal structures, ground- and excited-state UV/Vis absorption spectra, and luminescence properties of chalcogen-doped organic emitters equipped on both extremities with benzoxa-, benzothia-, benzoselena- and benzotellurazole (1X and 2X ) moieties have been reported for the first time. The insertion of the four different chalcogen atoms within the same molecular skeleton enables the investigation of only the chalcogenic effect on the organisation and photophysical properties of the material. Detailed crystal-structure analyses provide evidence of similar packing for 2O -2Se , in which the benzoazoles are engaged in π-π stacking and, for the heavier atoms, in secondary X⋅⋅⋅X and X⋅⋅⋅N bonding interactions. Detailed computational analysis shows that the arrangement is essentially governed by the interplay of van der Waals and secondary bonding interactions. Progressive quenching of the fluorescence and concomitant onset of phosphorescence features with gradually shorter lifetimes are detected as the atomic weight of the chalcogen heteroatom increases, with the tellurium-doped derivatives exhibiting only emission from the lowest triplet excited state. Notably, the phosphorescence spectra of the selenium and tellurium derivatives can be recorded even at room temperature; this is a very rare finding for fully organic emitters.

show abstract

“…Clusters containing 10 molecules (decamers) are found to be much more stable compared to clusters containing 11 molecules (undecamers), see figure 22. For borazines on Cu(1 1 1), regular heptamers appear to be most stable [178]. In addition, clusters composed of 13 molecules appear in richer abundance compared to other clusters.…”

Section: Stability Of Few-molecule Islandsmentioning

confidence: 98%

Imaging prototypical aromatic molecules on insulating surfaces: a review

Hoffmann‐Vogel

2017

Rep. Prog. Phys.

View full text Add to dashboard Cite

Insulating substrates allow for in-plane contacted molecular electronics devices where the molecule is in contact with the insulator. For the development of such devices it is important to understand the interaction of molecules with insulating surfaces. As substrates, ionic crystals such as KBr, KCl, NaCl and CaF are discussed. The surface energies of these substrates are small and as a consequence intrinsic properties of the molecules, such as molecule-molecule interaction, become more important relative to interactions with the substrates. As prototypical molecules, three variants of graphene-related molecules are used, pentacene, [Formula: see text] and PTCDA. Pentacene is a good candidate for molecular electronics applications due to its high charge carrier mobility. It shows mainly an upright standing growth mode and the morphology of the islands is strongly influenced by dewetting. A new second flat-lying phase of the molecule has been observed. Studying the local work function using the Kelvin method reveals details such as line defects in the center of islands. The local work function differences between the upright-standing and flat-lying phase can only be explained by charge transfer that is unusual on ionic crystalline surfaces. [Formula: see text] nucleation and growth is explained by loosely bound molecules at kink sites as nucleation sites. The stability of [Formula: see text] islands as a function of magic numbers is investigated. Peculiar island shapes are obtained from unusual dewetting processes already at work during growth, where molecules 'climb' to the second molecular layer. PTCDA is a prototypical semiconducting molecule with strong quadrupole moment. It grows in the form of elongated islands where the top and the facets can be molecularly resolved. In this way the precise molecular arrangement in the islands is revealed.

show abstract

“Magic” Surface Clustering of Borazines Driven by Repulsive Intermolecular Forces

Cited by 16 publications

References 47 publications

Self‐Assembly of Decoupled Borazines on Metal Surfaces: The Role of the Peripheral Groups

Self‐Assembly of Decoupled Borazines on Metal Surfaces: The Role of the Peripheral Groups

Walking Down the Chalcogenic Group of the Periodic Table: From Singlet to Triplet Organic Emitters

Imaging prototypical aromatic molecules on insulating surfaces: a review

Contact Info

Product

Resources

About