Investigation into Red Emission and Its Applications: Solvatochromic N-Doped Red Emissive Carbon Dots with Solvent Polarity Sensing and Solid-State Fluorescent Nanocomposite Thin Films.

In this work, a NIR emitting dye, p-toluenesulfonate (IR-813) was explored as a model precursor to develop red emissive carbon dots (813-CD) with solvatochromic behavior with a red-shift observed with increasing solvent polarity. The 813-CDs produced had emission peaks at 610 and 698 nm, respectively, in water with blue shifts of emission as solvent polarity decreased. Subsequently, 813-CD was synthesized with increasing nitrogen content with polyethyleneimine (PEI) to elucidate the change in band gap energy. With increased nitrogen content, the CDs produced emissions as far as 776 nm. Additionally, a CD nanocomposite polyvinylpyrrolidone (PVP) film was synthesized to assess the phenomenon of solid-state fluorescence. Furthermore, the CDs were found to have electrochemical properties to be used as an additive doping agent for PVP film coatings.

Modulating the Conduction Band Energies of Si Electrode Interfaces Functionalized with Monolayers of a Bay-Substituted Perylene Bisimide.

The confinement of π-conjugated chromophores on silicon (Si) electrode surfaces is a powerful approach to engineer electroresponsive monolayers relevant to microelectronics, electrocatalysis, and information storage and processing. While common strategies to functionalize Si interfaces exploit molecularly dissolved building blocks, only a handful number of studies have leveraged the structure-function relationships of π-aggregates to tune the electronic structures of hybrid monolayers at Si interfaces. Herein, we show that the semiconducting properties of n-type monolayers constructed on Si electrodes are intimately correlated to the initial aggregation state of π-conjugated chromophore precursors derived from bay-substituted perylene bisimide (PBI) units. Specifically, our study unravels that for n-type monolayers engineered using PBI π-aggregates, the cathodic reduction potentials required to inject negative charge carriers into the conduction bands can be stabilized by 295 mV through reversible switching of the maximum anodic potential (MAP) that is applied during the oxidative cycles (+0.5 or +1.5 V vs Ag/AgCl). This redox-assisted stabilization effect is not observed with n-type monolayers derived from molecularly dissolved PBI cores and monolayers featuring a low surface density of the redox-active probes. These findings unequivocally point to the crucial role played by PBI π-aggregates in modulating the conduction band energies of n-type monolayers where a high MAP of +1.5 V enables the formation of electronic trap states that facilitate electron injection when sweeping back to cathodic potentials. Because the structure-function relationships of PBI π-aggregates are shown to modulate the semiconducting properties of hybrid n-type monolayers constructed at Si interfaces, our results hold promising opportunities to develop redox-switchable monolayers for engineering nonvolatile electronic memory devices.

How to reprogram the excitonic properties and solid-state morphologies of π-conjugated supramolecular polymers.

The development of supramolecular tools to modulate the excitonic properties of non-covalent assemblies paves the way to engineer new classes of semicondcuting materials relevant to flexible electronics. While controlling the assembly pathways of organic chromophores enables the formation of J-like and H-like aggregates, strategies to tailor the excitonic properties of pre-assembled aggregates through post-modification are scarce. In the present contribution, we combine supramolecular chemistry with redox chemistry to modulate the excitonic properties and solid-state morphologies of aggregates built from stacks of water-soluble perylene diimide building blocks. The n-doping of initially formed aggregates in an aqueous medium is shown to produce π-anion stacks for which spectroscopic properties unveil a non-negligible degree of electron-electron interactions. Oxidation of the n-doped intermediates produces metastable aggregates where free exciton bandwidths (ExBW) increase as a function of time. Kinetic data analysis reveals that the dynamic increase of free exciton bandwidth is associated with the formation of superstructures constructed by means of a nucleation-growth mechanism. By designing different redox-assisted assembly pathways, we highlight that the sacrificial electron donor plays a non-innocent role in regulating the structure-function properties of the final superstructures. Furthermore, supramolecular architectures formed via a nucleation-growth mechanism evolve into ribbon-like and fiber-like materials in the solid-state, as characterized by SEM and HRTEM. Through a combination of ground-state electronic absorption spectroscopy, electrochemistry, spectroelectrochemistry, microscopy, and modeling, we show that redox-assisted assembly provides a means to reprogram the structure-function properties of pre-assembled aggregates.

Dynamics of charged excitons in electronically and morphologically homogeneous single-walled carbon nanotubes.

The trion, a three-body charge-exciton bound state, offers unique opportunities to simultaneously manipulate charge, spin, and excitation in one-dimensional single-walled carbon nanotubes (SWNTs) at room temperature. Effective exploitation of trion quasi-particles requires fundamental insight into their creation and decay dynamics. Such knowledge, however, remains elusive for SWNT trion states, due to the electronic and morphological heterogeneity of commonly interrogated SWNT samples, and the fact that transient spectroscopic signals uniquely associated with the trion state have not been identified. Here, we prepare length-sorted SWNTs and precisely control charge-carrier-doping densities to determine trion dynamics using femtosecond pump-probe spectroscopy. Identification of the trion transient absorptive hallmark enables us to demonstrate that trions (i) derive from a precursor excitonic state, (ii) are produced via migration of excitons to stationary hole-polaron sites, and (iii) decay in a first-order manner. Importantly, under appropriate carrier-doping densities, exciton-to-trion conversion in SWNTs can approach 100% at ambient temperature. Our findings open up possibilities for exploiting trions in SWNT optoelectronics, ranging from photovoltaics and photodetectors to spintronics.

A Molecular Strategy to Lock-in the Conformation of a Perylene Bisimide-Derived Supramolecular Polymer.

Locking-in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)-derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure-function relationships. Experiments that exploit variable-temperature ground-state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non-covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid-state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non-covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100-mV stabilization of the conduction band energy when compared to that recorded for the non-covalent assembly.

Quantitative Evaluation of Optical Free Carrier Generation in Semiconducting Single-Walled Carbon Nanotubes.

Gauging free carrier generation (FCG) in optically excited, charge-neutral single-walled carbon nanotubes (SWNTs) has important implications for SWNT-based optoelectronics that rely upon conversion of photons to electrical current. Earlier investigations have largely provided only qualitative insights into optically triggered SWNT FCG, due to the heterogeneous nature of commonly interrogated SWNT samples and the lack of direct, unambiguous spectroscopic signatures that could be used to quantify charges. Here, employing ultrafast pump-probe spectroscopy in conjunction with chirality-enriched, length-sorted, ionic-polymer-wrapped SWNTs, we develop a straightforward approach for quantitatively evaluating the extent of optically driven FCG in SWNTs. Owing to the previously identified trion transient absorptive hallmark (Tr+11 → Tr+nm) and the rapid nature of trion formation dynamics (<1 ps) relative to established free-carrier decay time scales (>ns), we correlate FCG with trion formation dynamics. Experimental determination of the trion absorptive cross section further enables evaluation of the quantum yields for optically driven FCG [Φ(E nn→h ++e -)] as a function of optical excitation energy and medium dielectric strength. We show that (i) E33 excitons give rise to dramatically enhanced Φ(E nn→h ++e -) relative to those derived from E22 and E11 excitons and (ii) Φ(E33→h ++e -) monotonically increases from ∼5% to 18% as the solvent dielectric constant increases from ∼32 to 80. This work highlights the extent to which the nature of the medium and excitation conditions control FCG quantum yields in SWNTs: such studies have the potential to provide new design insights for SWNT-based compositions for optoelectronic applications that include photodetectors and photovoltaics.

Molecular Road Map to Tuning Ground State Absorption and Excited State Dynamics of Long-Wavelength Absorbers.

Realizing chromophores that simultaneously possess substantial near-infrared (NIR) absorptivity and long-lived, high-yield triplet excited states is vital for many optoelectronic applications, such as optical power limiting and triplet-triplet annihilation photon upconversion (TTA-UC). However, the energy gap law ensures such chromophores are rare, and molecular engineering of absorbers having such properties has proven challenging. Here, we present a versatile methodology to tackle this design issue by exploiting the ethyne-bridged (polypyridyl)metal(II) (M; M = Ru, Os)-(porphinato)metal(II) (PM'; M' = Zn, Pt, Pd) molecular architecture (M-(PM')n-M), wherein high-oscillator-strength NIR absorptivity up to 850 nm, near-unity intersystem crossing (ISC) quantum yields (ΦISC), and triplet excited-state (T1) lifetimes on the microseconds time scale are simultaneously realized. By varying the extent to which the atomic coefficients of heavy metal d orbitals contribute to the one-electron excitation configurations describing the initially prepared singlet and triplet excited-state wave functions, we (i) show that the relative magnitudes of fluorescence (k0F), S1 → S0 nonradiative decay (knr), S1 → T1 ISC (kISC), and T1 → S0 relaxation (kT1→S0) rate constants can be finely tuned in M-(PM')n-M compounds and (ii) demonstrate designs in which the kISC magnitude dominates singlet manifold relaxation dynamics but does not give rise to T1 → S0 conversion dynamics that short-circuit a microseconds time scale triplet lifetime. Notably, the NIR spectral domain absorptivities of M-(PM')n-M chromophores far exceed those of classic coordination complexes and organic materials possessing similarly high yields of triplet-state formation: in contrast to these benchmark materials, this work demonstrates that these M-(PM')n-M systems realize near unit ΦISC at extraordinarily modest S1-T1 energy gaps (∼0.25 eV). This study underscores the photophysical diversity of the M-(PM')n-M platform and presents a new library of long-wavelength absorbers that efficiently populate long-lived T1 states.

Near-Infrared-to-Visible Photon Upconversion Enabled by Conjugated Porphyrinic Sensitizers under Low-Power Noncoherent Illumination.

We report four supermolecular chromophores based on (porphinato)zinc(II) (PZn) and (polypyridyl)metal units bridged via ethyne connectivity (Pyr1RuPZn2, Pyr1RuPZnRuPyr1, Pyr1RuPZn2RuPyr1, and OsPZn2Os) that fulfill critical sensitizer requirements for NIR-to-vis triplet-triplet annihilation upconversion (TTA-UC) photochemistry. These NIR sensitizers feature: (i) broad, high oscillator strength NIR absorptivity (700 nm < λ(max(NIR)) < 770 nm; 6 × 10(4) M(-1) cm(-1) < extinction coefficient (λ(max(NIR))) < 1.6 × 10(5) M(-1) cm(-1); 820 cm(-1) < fwhm < 1700 cm(-1)); (ii) substantial intersystem crossing quantum yields; (iii) long, microsecond time scale T1 state lifetimes; and (iv) triplet states that are energetically poised for exergonic energy transfer to the molecular annihilator (rubrene). Using low-power noncoherent illumination at power densities (1-10 mW cm(-2)) similar to that of terrestrial solar photon illumination conditions, we demonstrate that Pyr1RuPZn2, Pyr1RuPZn2RuPyr1, and Pyr1RuPZnRuPyr1 sensitizers can be used in combination with the rubrene acceptor/annihilator to achieve TTA-UC: these studies represent the first examples whereby a low-power noncoherent NIR light source drives NIR-to-visible upconverted fluorescence centered in a spectral window within the bandgap of amorphous silicon.

Fluence-dependent singlet exciton dynamics in length-sorted chirality-enriched single-walled carbon nanotubes.

We utilize individualized, length-sorted (6,5)-chirality enriched single-walled carbon nanotubes (SWNTs) having dimensions of 200 and 800 nm, femtosecond transient absorption spectroscopy, and variable excitation fluences that modulate the exciton density per nanotube unit length, to interrogate nanotube exciton/biexciton dynamics. For pump fluences below 30 µJ/cm(2), transient absorption (TA) spectra of (6,5) SWNTs reveal the instantaneous emergence of the exciton to biexciton transition (E11 → E11,BX) at 1100 nm; in contrast, under excitation fluences exceeding 100 µJ/cm(2), this TA signal manifests a rise time (τ rise ∼ 250 fs), indicating that E11 state repopulation is required to produce this signal. Femtosecond transient absorption spectroscopic data acquired over the 900-1400 nm spectral region of the near-infrared (NIR) region for (6,5) SWNTs, as a function of nanotube length and exciton density, reveal that over time delays that exceed 200 fs exciton-exciton interactions do not occur over spatial domains larger than 200 nm. Furthermore, the excitation fluence dependence of the E11 → E11,BX transient absorption signal demonstrates that relaxation of the E11 biexciton state (E11,BX) gives rise to a substantial E11 state population, as increasing delay times result in a concomitant increase of E11 → E11,BX transition oscillator strength. Numerical simulations based on a three-state model are consistent with a mechanism whereby biexcitons are generated at high excitation fluences via sequential SWNT ground- and E11-state excitation that occurs within the 980 nm excitation pulse duration. These studies that investigate fluence-dependent TA spectral evolution show that SWNT ground → E11 and E11 → E11,BX excitations are coresonant and provide evidence that E11,BX → E11 relaxation constitutes a significant decay channel for the SWNT biexciton state over delay times that exceed 200 fs, a finding that runs counter to assumptions made in previous analyses of SWNT biexciton dynamical data where exciton-exciton annihilation has been assumed to play a dominant role.

Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly.

Single-walled carbon nanotube (SWNT)-based nanohybrid compositions based on (6,5) chirality-enriched SWNTs ([(6,5) SWNTs]) and a chiral n-type polymer (S-PBN(b)-Ph4 PDI) that exploits a perylenediimide (PDI)-containing repeat unit are reported; S-PBN(b)-Ph4 PDI-[(6,5) SWNT] superstructures feature a PDI electron acceptor unit positioned at 3 nm intervals along the nanotube surface, thus controlling rigorously SWNT-electron acceptor stoichiometry and organization. Potentiometric studies and redox-titration experiments determine driving forces for photoinduced charge separation (CS) and thermal charge recombination (CR) reactions, as well as spectroscopic signatures of SWNT hole polaron and PDI radical anion (PDI(-.) ) states. Time-resolved pump-probe spectroscopic studies demonstrate that S-PBN(b)-Ph4 PDI-[(6,5) SWNT] electronic excitation generates PDI(-.) via a photoinduced CS reaction (τCS ≈0.4 ps, ΦCS ≈0.97). These experiments highlight the concomitant rise and decay of transient absorption spectroscopic signatures characteristic of the SWNT hole polaron and PDI(-.) states. Multiwavelength global analysis of these data provide two charge-recombination time constants (τCR ≈31.8 and 250 ps) that likely reflect CR dynamics involving both an intimately associated SWNT hole polaron and PDI(-.) charge-separated state, and a related charge-separated state involving PDI(-.) and a hole polaron site produced via hole migration along the SWNT backbone that occurs over this timescale.

Potentiometric, electronic, and transient absorptive spectroscopic properties of oxidized single-walled carbon nanotubes helically wrapped by ionic, semiconducting polymers in aqueous and organic media.

We report the first direct cyclic voltammetric determination of the valence and conduction band energy levels for noncovalently modified (6,5) chirality enriched SWNTs [(6,5) SWNTs] in which an aryleneethynylene polymer monolayer helically wraps the nanotube surface at periodic and constant morphology. Potentiometric properties as well as the steady-state and transient absorption spectroscopic signatures of oxidized (6,5) SWNTs were probed as a function of the electronic structure of the aryleneethynylene polymer that helically wraps the nanotube surface, the solvent dielectric, and nanotube hole polaron concentration. These data: (i) highlight the utility of these polymer-SWNT superstructures in experiments that establish the potentiometric valence and conduction band energy levels of semiconducting carbon nanotubes; (ii) provide a direct measure of the (6,5) SWNT hole polaron delocalization length (2.75 nm); (iii) determine steady-state and transient electronic absorptive spectroscopic signatures that are uniquely associated with the (6,5) SWNT hole polaron state; and (iv) demonstrate that modulation of semiconducting polymer frontier orbital energy levels can drive spectral shifts of SWNT hole polaron transitions as well as regulate SWNT valence and conduction band energies.

Single-handed helical wrapping of single-walled carbon nanotubes by chiral, ionic, semiconducting polymers.

We establish the requisite design for aryleneethynylene polymers that give rise to single-handed helical wrapping of single-walled carbon nanotubes (SWNTs). Highly charged semiconducting polymers that utilize either an (R)- or (S)-1,1'-bi-2-naphthol component in their respective conjugated backbones manifest HRTEM and AFM images of single-chain-wrapped SWNTs that reveal significant preferences for the anticipated helical wrapping handedness; statistical analysis of these images, however, indicates that ∼20% of the helical structures are formed with the "unexpected" handedness. CD spectroscopic data, coupled with TDDFT-based computational studies that correlate the spectral signatures of semiconducting polymer-wrapped SWNT assemblies with the structural properties of the chiral 1,1'-binaphthyl unit, suggest strongly that two distinct binaphthalene SWNT binding modes, cisoid-facial and cisoid-side, are possible for these polymers, with the latter mode responsible for inversion of helical chirality and the population of polymer-SWNT superstructures that feature the unexpected polymer helical wrapping chirality at the nanotube surface. Analogous aryleneethynylene polymers were synthesized that feature a 2,2'-(1,3-benzyloxy)-bridged (b)-1,1'-bi-2-naphthol unit: this 1,1'-bi-2-naphthol derivative is characterized by a bridging 2,2'-1,3 benzyloxy tether that restricts the torsional angle between the two naphthalene subunits along its C1-C1' chirality axis to larger, oblique angles that facilitate more extensive van der Waals contact of the naphthyl subunits with the nanotube. Similar microscopic, spectroscopic, and computational studies determine that chiral polymers based on conformationally restricted transoid binaphthyl units direct preferential facial binding of the polymer with the SWNT and thereby guarantee helically wrapped polymer-nanotube superstructures of fixed helical chirality. Molecular dynamics simulations provide an integrated picture tying together the global helical superstructure and conformational properties of the binaphthyl units: a robust, persistent helical handedness is preferred for the conformationally restricted transoid binaphthalene polymer. Further examples of similar semiconducting polymer-SWNT superstructures are reported that demonstrate that the combination of single-handed helical wrapping and electronic structural modification of the conjugated polymer motif opens up new opportunities for engineering the electro-optic functionality of nanoscale objects.

Ionic self-assembly provides dense arrays of individualized, aligned single-walled carbon nanotubes.

Wrap and stack: Polyanionic [arylene]ethynylene polymers that helically wrap single-walled carbon nanotubes (SWNTs) enable the production of functionalized SWNTs that are soluble in organic solvents. These SWNTs can assemble into structures featuring aligned nanotubes that maintain the optoelectronic properties of individual SWNTs.

Covalent post-assembly modification of π-conjugated supramolecular polymers delivers structurally robust light-harvesting nanoscale objects.

A two-component stapling strategy is used to covalently tether a new class of water-soluble supramolecular polymers built from bay-functionalized perylene bisimide (PBI) units. By leveraging a novel combined strategy where excitonic coupling and fluorescence data are exploited as spectroscopic reporters, structural design principles are established to form light-harvesting superstructures whose ground-state electronic properties are not sensitive to solvation environments. Moreover, we interrogate the structural properties of stapled superstructures by capitalizing on the drastic changes in fluorescence quantum yields against parent supramolecular assemblies. In essence, our work shows that the combination of excitonic coupling measurements and photoluminescence experiments delineates a more accurate understanding of the design principles required to limit the degree of structural defects and magnify short- and long-range electronic couplings between redox-active units in this new class of solvated nanoscale objects. These results highlight that the fragile conformation of non-covalent assemblies, which are regulated by weak secondary interactions, can be preserved by post-assembly modification of preformed supramolecular polymers. These synthetic and spectroscopic principles can in turn be codified as experimental handles to parameterize the optoelectronic properties of light-harvesting nanoscale objects.

Cancer cells inhibition by cationic carbon dots targeting the cellular nucleus.

Nucleus targeting is tremendously important in cancer therapy. Cationic carbon dots (CCDs) are potential nanoparticles which might enter cells and penetrate nuclear membranes. Although some CCDs have been investigated in nucleus targeting and applied in nuclear imaging, the CCDs derived from drugs, that are able to target the nucleus, bind with DNA and inhibit the growth of cancer cells have not been reported. In this project, 1, 2, 4, 5-benzenetetramine (Y15, a focal adhesion kinase inhibitor) derived cationic carbon dots (Y15-CDs) were prepared via a hydrothermal approach utilizing Y15, folic acid and 1,2-ethylenediamine as precursors. Based on the structural, optical, and morphologic characterizations, Y15-CDs possess rich amine groups and nitrogen in structure, an excitation-dependent photoluminescence emission, and a small particle size of 2 to 4 nm. The DNA binding experiments conducted through agarose gel electrophoresis, UV-vis absorption, fluorescence emission, and circular dichroism spectroscopies, prove that Y15-CDs might bind with DNA via electrostatic interactions and partially intercalative binding modes. In addition, the cell imaging and cytotoxicity studies in human foreskin fibroblasts (HFF), prostate cancer (PC3) and osteosarcoma cells (U2OS) indicate the nucleus targeting and anticancer abilities of Y15-CDs. Most interestingly, Y15-CDs exhibit a higher cytotoxicity to cancer cells (PC3 and U2OS) than to normal cells (HFF), inferring that Y15-CDs might be potentially applied in cancer therapy.

Self-assembly of charged Bodipy dyes to form Cassettes that display intracomplex electronic energy transfer and accrete into liquid crystals.

Red- and blue-absorbing boron dipyrromethene dyes, bearing opposite electronic charges, associate in solution to form a 1:2 complex having a stability constant of ca. 10(17) M(-2). The complex can be dismantled by addition of a large excess of tetra-N-butylammonium cations. The same complex displays liquid crystalline properties on heating from rt to above 150 °C, as characterized by various experimental techniques. Highly efficient electronic energy transfer from the red to the blue dye occurs in both the initial complex and the subsequent mesomorphic state.

Lanthanide ion extraction by trifluoromethyl-1,3-diketonate-functionalised ionic liquids adsorbed on silica.

While acetylacetone (acacH) derivatives are, upon deprotonation, ubiquitous ligands in coordination chemistry, their potential to form stable ionic liquids has not been studied so far. Here we describe a straightforward synthesis of novel trifluoroacetylacetone-functionalised imidazolium salts. These salts are built from an imidazolium ring substituted on one side with a flexible chain of fixed length carrying a terminal acacH group and on the opposite side a paraffin chain of various lengths. By changing the length of these flexible chains (n=4, 8, 12) and the nature of the counter-anions (PF(6)(-), BF(4)(-), NTf(2)(-)), room-temperature ionic liquids were produced. Their application for the extraction of lanthanide salts (Eu, Tb) from dilute aqueous solution has been investigated. The presence of a strong UV absorber (imidazolium ring, λ(abs)=290 nm) allows photosensitisation of the Eu(III) and Tb(III) luminescence by efficient energy transfer, and thus extraction of these two lanthanides can be followed by fluorescence techniques. It appears that loading of the ionic liquids onto silica particles pre-treated with a dilute aqueous solution of NaOH is the most efficient way to obtain fast and almost quantitative (>99.9%) extraction of the metal ions as their diketonato complexes. The procedure is reproducible and the loaded SiO(2) particles can be simply treated with acid to strip the metal ions and regenerate the adsorbed (protonated) extractant.

Excited-state properties of heteroleptic iridium(III) complexes bearing aromatic hydrocarbons with extended cores.

The synthesis, complete structural characterization, electrochemistry, and excited-state dynamics of a series of four bis-heteroleptic iridium(III) charge-transfer complexes composed of a single acac-functionalized and two ortho-metalated 2-phenylpyridine ligands. The formed iodophenyl complex (2) was used as a metallosynthon to introduce extended-core ethynyltolyl (3), ethynylpyrene (4), and ethynylperylene (5) residues into these structures projecting from the acac ancillary ligand. Static and dynamic photoluminescence along with ultrafast and conventional transient absorption measurements in conjunction with cyclic voltammetry were employed to elucidate the nature of the intramolecular energy-transfer processes occurring in the excited states of polychromophores 4 and 5 and are directly compared with those of model complexes 2 and 3. Upon charge-transfer excitation of these molecules, the long-lived triplet-state metal-to-ligand charge-transfer ((3)MLCT)-based photoluminescence readily observed in 2 and 3 (τ = 1 µs) is nearly quantitatively quenched, resulting from production of the associated triplet intraligand ((3)IL) excited states in 4 and 5 through intramolecular triplet-triplet energy transfer. The respective formation of the extended-core (3)*pyrenyl and (3)*perylenyl-localized excited states in 4 and 5 is confirmed by their ultrafast excited-state evolution, which ultimately generates features associated with these (3)IL excited states and their greatly extended excited-state lifetimes with respect to the parent complexes 2 and 3.

Leveraging the Assembly of a Rylene Dye to Tune the Semiconducting Properties of Functionalized n-Type, Hybrid Si Interfaces.

The functionalization of silicon electrodes with π-conjugated chromophores opens new avenues to engineer hybrid semiconducting interfaces relevant to information storage and processing. Notably, molecularly dissolved π-conjugated units, such as ferrocene derivatives, are traditionally exploited as building blocks to construct well-defined interfaces that establish electrochemically addressable platforms with which to investigate electron transfer properties and charge storage capabilities. In contrast, planar π-conjugated building blocks such as naphthalene diimide (NDI) cores enable the formation of solvated aggregates equipped with emergent electronic structures not manifested by the parent, molecularly dissolved building blocks. To interrogate the extent to which the aggregated states of π-conjugated chromophores can be leveraged to regulate the n-type semiconducting properties of functionalized electrodes, we have devised an amphiphilic rylene core (NDI) that demonstrates a non-negligible degree of aggregation in an aqueous medium. Characterization of the electronic structures of the NDI-derived aggregates using a combination of electrochemistry, reductive titration experiments, and spectroelectrochemistry unveils the existence of π-anion stacks, the formation of which is contingent on the initial concentration of NDI building blocks. We show that grafting n-doped NDI aggregates on silicon electrode precursors equipped with a high density of anchoring groups by means of "click" reaction enables the formation of the hybrid Si-NDI electrode (Si-NDI-15@1) that facilitates electron injection by more than 400 mV when compared to Si interfaces constructed from molecularly dissolved NDI units. Furthermore, the engineering of a Si precursor surface characterized by a low density of anchoring groups provides additional proof to highlight that the potentiometric properties recorded for Si-NDI-15@1 originate from NDI units, evidencing a non-negligible degree of aggregation. The present work delivers tools to manipulate the potentiometric properties of functionalized electrodes by leveraging on the electronic structures of aggregated, π-conjugated precursors.

Luminescent ionic liquid crystals from self-assembled BODIPY disulfonate and imidazolium frameworks.

A series of modular mesogenic salts based on the combination of anionic 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (F-BODIPY) 2,6-disulfonate dyes and trialkoxybenzyl-functionalised imidazolium cations has been designed and synthesised. Each salt contains a rigid dianionic BODIPY core associated with two imidazolium cations functionalised by 1,2,3-trialkoxybenzyl (alkyl=n-C(8), n-C(12) or n-C(16)) units or, in one case, with imidazolium cations functionalised by a trialkylgallate (3,4,5-trialkoxybenzoate) unit in which the 3,5-dialkyl groups are terminated with a polymerisable acrylate entity. All these compounds were highly fluorescent in solution with quantum yields ranging from 54 to 62%. In the solid state, the width of the emission band observed at around 650 nm is a clear signature of aggregation. With the trialkoxybenzylimidazolium cations, polarised optical microscopy (POM) and X-ray scattering experiments showed that columnar mesophases were formed. Differential scanning calorimetry (DSC) studies confirmed the mesomorphic behaviour from room temperature to about 130 degrees C for salts with alkyl chains containing 8, 12 and 16 carbon atoms. The strong luminescence of the BODIPY unit was maintained in the mesophase and fluorescence measurements confirmed the presence of J aggregates in all cases. The salt containing the gallate-functionalised imidazolium cations showed no mesomorphism but the acrylate terminal units could be used to engender photoinitiated polymerisation thereby allowing the material to be immobilised on glass plates. The polymerisation process was followed by FTIR spectroscopy and the fixed and patterned films were highly fluorescent with a solid-state emission close to that of the complex in the solid state.