Tuning the optical and electrochemical properties of core-substituted naphthalenediimides with styryl imide substituent

Fernando, Roshan; Etheridge, Forrest S.; Muller, Evan; Sauvé, Geneviève

doi:10.1039/c4nj01645a

Cited by 6 publications

(7 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To prevent irreversible oxidations, the CV was carried out only in the cathodic region. Thus, both hNDI and sNDI chromophores were also measured between −2 and 0 V. The amino substituted nNDI chromophore showed reduction potentials at −1.43 and −1.77 V that are in the same range as previously observed for the similar amino core‐substituted NDIs [49,50,55] . The LUMO energy estimated from the CV is −3.37 eV resulting in the HOMO energy level of −5.31 eV, which is comparable to previously reported results [50] .…”

Section: Resultssupporting

confidence: 87%

“…Thus, both hNDI and sNDI chromophores were also measured between À 2 and 0 V. The amino substituted nNDI chromophore showed reduction potentials at À 1.43 and À 1.77 V that are in the same range as previously observed for the similar amino core-substituted NDIs. [49,50,55] The LUMO energy estimated from the CV is À 3.37 eV resulting in the HOMO energy level of À 5.31 eV, which is comparable to previously reported results. [50] However, each of the two anodic and cathodic peak potential pairs differ for about 0.3 V. Electrode films of some newly formed species as an explanation for these broad peaks can be excluded, since the experiments were carried out with freshly cleaned electrodes and are reproducible over several measurements.…”

Section: Electrochemical Propertiessupporting

confidence: 89%

See 1 more Smart Citation

Synthesis and Surface Behaviour of NDI Chromophores Mounted on a Tripodal Scaffold: Towards Self‐Decoupled Chromophores for Single‐Molecule Electroluminescence

Balzer

Lukášek

Valášek

et al. 2021

Chemistry A European J

View full text Add to dashboard Cite

This paper reports the efficient synthesis, absorption and emission spectra, and the electrochemical properties of a series of 2,6‐disubstituted naphthalene‐1,4,5,8‐tetracarboxdiimide (NDI) tripodal molecules with thioacetate anchors for their surface investigations. Our studies showed that, in particular, the pyrrolidinyl group with its strong electron‐donating properties enhanced the fluorescence of such core‐substituted NDI chromophores and caused a significant bathochromic shift in the absorption spectrum with a correspondingly narrowed bandgap of 1.94 eV. Cyclic voltammetry showed the redox properties of NDIs to be influenced by core substituents. The strong electron‐donating character of pyrrolidine substituents results in rather high HOMO and LUMO levels of ‐5.31 and ‐3.37 eV when compared with the parental unsubstituted NDI. UHV‐STM measurements of a sub‐monolayer of the rigid tripodal NDI chromophores spray deposited on Au(111) show that these molecules mainly tend to adsorb flat in a pairwise fashion on the surface and form unordered films. However, the STML experiments also revealed a few molecular clusters, which might consist of upright oriented molecules protruding from the molecular island and show electroluminescence photon spectra with high electroluminescence yields of up to 6×10−3. These results demonstrate the promising potential of the NDI tripodal chromophores for the fabrication of molecular devices profiting from optical features of the molecular layer.

show abstract

Section: Resultssupporting

confidence: 87%

Section: Electrochemical Propertiessupporting

confidence: 89%

Synthesis and Surface Behaviour of NDI Chromophores Mounted on a Tripodal Scaffold: Towards Self‐Decoupled Chromophores for Single‐Molecule Electroluminescence

Balzer

Lukášek

Valášek

et al. 2021

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Thanks to the low resistance of the Ru−C bonds, 28 metal core electrons might spill into the organic capping ligands, which would render the electroreduction of the particle-bound NA moieties to take place at a more negative potential position. 29,30 This is consistent with results from the PL measurements (Figure 2), which suggests that the particlebound functional moieties behave analogously to the dimeric counterparts.…”

Section: Methodssupporting

confidence: 89%

Chemical Reactivity of Naphthalenecarboxylate-Protected Ruthenium Nanoparticles: Intraparticle Charge Delocalization Derived from Interfacial Decarboxylation

Chen

Deming

et al. 2015

J. Phys. Chem. C

View full text Add to dashboard Cite

Ruthenium nanoparticles were prepared by thermolytic reduction of RuCl 3 in 1,2-propanediol containing sodium 2-naphthalenecarboxylate. Transmission electron microscopic measurements showed that the average diameter of the resulting 2-naphthalenecarboxylate-protected ruthenium nanoparticles (RuCOONA) was 1.30 ± 0.27 nm. Interestingly, hydrothermal treatment of the nanoparticles at controlled temperatures led to decarboxylation at the metal−ligand interface, and the naphthalenyl moieties became directly bonded to the metal cores, which was confirmed by infrared and X-ray photoelectron spectroscopic measurements. In comparison with the as-produced RuCOONA nanoparticles, the decarboxylated nanoparticles (RuNA) exhibited markedly different optical and electronic properties, as manifested by an apparent red shift of the photoluminescence profiles, which was ascribed to electronic coupling between the particle-bound naphthalene groups. Electrochemical measurements exhibited consistent results where a negative shift was observed of the formal potential of the particle-bound naphthalene moieties. This was attributed to intraparticle charge delocalization that led to extended spilling of nanoparticle core electrons to the naphthalene moieties. ■ INTRODUCTIONOrganically capped metal nanoparticles have been attracting extensive interest because the material properties may be readily controlled by the chemical nature of the metal cores and the organic protecting ligands as well as their interfacial bonding interactions. 1−5 In fact, the bonding linkages at the metal−ligand interface have been observed to impact the nanoparticle dimensions, morphology, and stability; inversely, metal nanoparticles also have influence on the ligand physical and chemical property, reactivity, and configuration. 4,6,7 Of these, ruthenium nanoparticles have been intensively studied due to its stability and affinity to many organic capping ligands, such as mercapto derivatives, alkylamines, diazo, acetylene, nitrene, and carboxylate moieties. 4,7−11 For instance, for ruthenium nanoparticles functionalized by acetylene derivatives, the formation of conjugated metal−ligand π-bonds leads to intraparticle charge delocalization, and hence, the nanoparticles exhibit new optical/electronic characteristics that are analogous to those of diacetylene derivatives. 11−13 These results highlight the significance of interfacial engineering in the manipulation of nanoparticle materials properties.Conjugated metal−ligand interfacial bonds may also be produced by exploiting the unique interfacial reactivity of organic ligands on nanoparticle surfaces. For instance, we recently observed that alkene derivatives might self-assemble onto platinum nanoparticle surfaces, forming platinum−vinylidene or −acetylide bonds as a consequence of platinumcatalyzed dehydrogenation and transformation of the olefin groups. 14 In another study, 15 ruthenium nanoparticles were protected by ferrocenecarboxylates, and galvanic exchange reactions with Pd(II) led to the deposition of a s...

show abstract

“…11 Compounds 1, 2, 3, 4, b, and c were synthesized according to literature procedures with slight modications. 12,[17][18][19][20] Methods 1 H and 13 C were recorded using a Varian 400 mHz spectrometer.…”

Section: Discussionmentioning

confidence: 99%

“…RF2-2S has a l max in the near-IR at 733 nm and an optical gap of 1.59 eV, which is very low for this type of molecule. Compounds 1, 2, 3, 4, b, and c were synthesized according to literature procedures with slight modications 12,[17][18][19][20]. dianhydride (NDA) (Aldrich), 2-ethylhexylamine (Aldrich), Lawesson's reagent (Aldrich), sulphuric acid (Fisher), acetic acid (Fisher), ammonium acetate (Fisher), dibromoisocyanuric acid (DBI) (TCI America) were used as received.…”

mentioning

confidence: 99%

Tuning the optoelectronic properties of core-substituted naphthalene diimides by the selective conversion of imides to monothioimides

et al. 2015

View full text Add to dashboard Cite

Selective sulfur substitution of the distal carbonyls of a core-substituted naphthalene diimide was obtained when a combination of core and imide substituents were used. The substituents appear to inhibit thionation of the proximal carbonyl by steric hindrance. Each thionation caused a 50 nm bathochromic shift of the visible absorption band and an anodic shift of the reduction potentials. The dithionated compound has a l max in the near-IR at 733 nm and an optical gap of 1.59 eV, which is unusually low for this type of molecule. Thionation of carbonyls offers a useful avenue for tuning optoelectronic properties of NDIbased materials.

show abstract

Tuning the optical and electrochemical properties of core-substituted naphthalenediimides with styryl imide substituent

Abstract: Unusually broad thin-film visible absorption (500–800 nm) for naphthalenediimide molecules was obtained by using the combination of alkylamino core substituents and styryl imide substituents.

Cited by 6 publications

References 24 publications

Synthesis and Surface Behaviour of NDI Chromophores Mounted on a Tripodal Scaffold: Towards Self‐Decoupled Chromophores for Single‐Molecule Electroluminescence

Synthesis and Surface Behaviour of NDI Chromophores Mounted on a Tripodal Scaffold: Towards Self‐Decoupled Chromophores for Single‐Molecule Electroluminescence

Chemical Reactivity of Naphthalenecarboxylate-Protected Ruthenium Nanoparticles: Intraparticle Charge Delocalization Derived from Interfacial Decarboxylation

Tuning the optoelectronic properties of core-substituted naphthalene diimides by the selective conversion of imides to monothioimides

Contact Info

Product

Resources

About