Interactions of iodoperfluorobenzene compounds with gold nanoparticles

Understanding the interactions of small molecules with gold nanoparticles is important for controlling their surface chemistry and, hence, how they can be used in specific applications. The interaction of iodoperfluorobenzene compounds with gold nanoparticles was investigated by UV-Vis difference spectroscopy, surface enhanced Raman spectroscopy (SERS) and Synchrotron X-ray photoelectron spectroscopy (XPS). Results from UV-Vis difference spectroscopy demonstrated that iodoperfluorobenzene compounds undergo charge transfer complexation with gold nanoparticles. SERS of the small molecule–gold nanoparticle adducts provided further evidence for formation of charge transfer complexes, while Synchrotron X-ray photoelectron spectroscopy provided evidence of the binding mechanism. Demonstration of interactions of iodoperfluorobenzene compounds with gold nanoparticles further expands the molecular toolbox that is available for functionalising gold nanoparticles and has significant potential for expanding the scope for generation of hybrid halogen bonded materials.

Electrochemical current rectification – a novel signal amplification strategy for highly sensitive and selective aptamer-based biosensor

Electrochemical aptamer-based (E-AB) sensors represent an emerging class of recently developed sensors. However, numerous of these sensors are limited by a low surface density of electrode-bound redox-oligonucleotides which are used as probe. Here we propose to use the concept of electrochemical current rectification (ECR) for the enhancement of the redox signal of E-AB sensors. Commonly, the probe-DNA performs a change in conformation during target binding and enables a nonrecurring charge transfer between redox-tag and electrode. In our system, the redox-tag of the probe-DNA is continuously replenished by solution-phase redox molecules. A unidirectional electron transfer from electrode via surface-linked redox-tag to the solution-phase redox molecules arises that efficiently amplifies the current response. Using this robust and straight-forward strategy, the developed sensor showed a substantial signal amplification and consequently improved sensitivity with a calculated detection limit of 114 nM for ATP, which was improved by one order of magnitude compared with the amplification-free detection and superior to other previous detection results using enzymes or nanomaterials-based signal amplification. To the best of our knowledge, this is the first demonstration of an aptamer-based electrochemical biosensor involving electrochemical rectification, which can be presumably transferred to other biomedical sensor systems.

Pt(II) bipyridyl complexes bearing substituted fluorenyl motif on the bipyridyl and acetylide ligands : synthesis, photophysics, and reverse saturable absorption

A series of Pt(II) diimine complexes bearing benzothiazolylfluorenyl (BTZ-F8), diphenylaminofluorenyl (NPh2- F8), or naphthalimidylfluorenyl (NI-F8) motifs on the bipyridyl or acetylide ligands (Pt-4−Pt-8), (i.e., {4,4′-bis[7-R1-F8-(≡)n-]bpy}Pt(7- R2-F8- ≡ -)2, where F8 = 9,9′-di(2-ethylhexyl)fluorene, bpy = 2,2′- bipyridine, Pt-4: R1 = R2 = BTZ, n = 0; Pt-5: R1 = BTZ, R2 = NI, n = 0; Pt-6: R1 = R2 = BTZ, n = 1; Pt-7: R1 = BTZ, R2 = NPh2, n = 1; Pt- 8: R1 = NPh2, R2 = BTZ, n = 1) were synthesized. Their ground-state and excited-state properties and reverse saturable absorption performances were systematically investigated. The influence of these motifs on the photophysics of the complexes was investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). The intense absorption bands below 410 nm for these complexes is assigned to predominantly 1π,π* transitions localized on either the bipyridine or the acetylide ligands; while the broad low-energy absorption bands between 420 and 575 nm are attributed to essentially 1MLCT (metal-to-ligand charge transfer)/ 1LLCT (ligand-to-ligand charge transfer) transitions, likely mixed with some 1ILCT (intraligand charge transfer) transition for Pt-4−Pt-7, and predominantly 1ILCT transition admixing with minor 1MLCT/1LLCT characters for Pt-8. The different substituents on the acetylide and bipyridyl ligands, and the degrees of π-conjugation in the bipyridyl ligand influence both the 1π,π* and charge transfer transitions pronouncedly. All complexes are emissive at room temperature. Upon excitation at their respective absorption band maxima, Pt-4, Pt-6, and Pt-8 exhibit acetylide ligand localized 1π,π* fluorescence and 3MLCT/3LLCT phosphorescence in CH2Cl2, while Pt-5 manifests 1ILCT fluorescence and 3ILCT phosphorescence. However, only 1LLCT fluorescence was observed for Pt-7 at room temperature. The nanosecond transient absorption study was carried out for Pt-4−Pt-8 in CH3CN. Except for Pt-7 that contains NPh2 at the acetylide ligands, Pt-4−Pt-6 and Pt-8 all exhibit weak to moderate excited-state absorption in the visible spectral region. Reverse saturable absorption (RSA) of these complexes was demonstrated at 532 nm using 4.1 ns laser pulses in a 2 mm cuvette. The strength of RSA follows this trend: Pt-4 > Pt-5 > Pt-7 > Pt-6 > Pt-8. Incorporation of electron-donating substituent NPh2 on the bipyridyl ligand significantly decreases the RSA, while shorter π-conjugation in the bipyridyl ligand increases the RSA. Therefore, the substituent at either the acetylide ligands or the bipyridyl ligand could affect the singlet and triplet excited-state characteristics significantly, which strongly influences the RSA efficiency.

An efficient hole transport material composite based on poly(3-hexylthiophene) and bamboo-structured carbon nanotubes for high performance perovskite solar cells

In this work, we have developed a new efficient hole transport material (HTM) composite based on poly(3- hexylthiophene) (P3HT) and bamboo-structured carbon nanotubes (BCNs) for CH3NH3PbI3 (MAPbI3) based perovskite solar cells. Compared to pristine P3HT, it is found that the crystallinity of P3HT was significantly improved by addition of BCNs, which led to over one order of magnitude higher conductivity for the composite containing 1–2 wt% BCNs in P3HT. In the meantime, the interfacial charge transfer between the MAPbI3 light absorbing layer and the HTM composite layer based on P3HT/BCNs was two-fold faster than pristine P3HT. More importantly, the HTM film with a superior morphological structure consisting of closely compact large grains was achieved with the composite containing 1 wt% BCNs in P3HT. The study by electrochemical impedance spectroscopy has confirmed that the electron recombination in the solar cells was reduced nearly ten-fold with the addition of 1 wt% carbon nanotubes in the HTM composite. Owing to the superior HTM film morphology and the significantly reduced charge recombination, the energy conversion efficiency of the perovskite solar cells increased from 3.6% for pristine P3HT to 8.3% for P3HT/(1 wt% BCNs) with a significantly enhanced open circuit voltage (Voc) and fill factor (FF). The findings of this work are important for development of new HTM for high performance perovskite solar cells.

Optimized multilayer indium-free electrodes for organic photovoltaics

Flexible multilayer electrodes that combine high transparency, high conductivity, and efficient charge extraction have been deposited, characterised and used as the anode in organic solar cells. The anode consists of an AZO/Ag/AZO stack plus a very thin oxide interlayer whose ionization potential is fine-tuned by manipulating its gap state density to optimise charge transfer with the bulk heterojunction active layer consisting of poly(n-3- hexylthiophene-2,5-diyl) and phenyl-C61-butyric acid methyl ester (P3HT:BC61BM). The deposition method for the stack was compatible with the low temperatures required for polymer substrates. Optimisation of the electrode stack was achieved by modelling the optical and electrical properties of the device and a power conversion efficiency of 2.9% under AM1.5 illumination compared to 3.0% with an ITO-only anode and 3.5% for an ITO:PEDOT electrode. Dark I-V reverse bias characteristics indicate very low densities of occupied buffer states close to the HOMO level of the hole conductor, despite observed ionization potential being high enough. Their elimination should raise efficiency to that with ITO:PEDOT.

Conversion of n-type CuTCNQ into p-type nitrogen-doped CuO and the implication for room temperature gas sensing

Sensors to detect toxic and harmful gases are usually based on metal oxides that are operated at elevated temperature. However, enabling gas detection at room temperature (RT) is a significant ongoing challenge. Here, we address this issue by demonstrating that microrods of semiconducting CuTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) with nanostructured features can be employed as conductometric gas sensors operating at 50°C for detection of oxidizing and reducing gases such as NO2 and NH3. The sensor is evaluated at RT and up to 200°C. It was found that CuTCNQ is transformed into a N-doped CuO material with p-type conductivity when annealed at the maximum temperature. This is the first time that such a transformation, from a semiconducting charge transfer material into a N-doped metal oxide is detected. It is shown here that both the surface chemistry and the type of majority charge carrier within the sensing layer is critically important for the type of response towards oxidizing and reducing gases. A detailed physical description of NO2 and NH3 sensing mechanism at CuTCNQ and N-doped CuO is provided to explain the difference in the response. For the N-doped CuO sensor, a detection limit of 1 ppm for NO2 and 10 ppm for NH3 are achieved.

Nanosheets Co3O4 interleaved with graphene for highly efficient oxygen reduction

Efficient yet inexpensive electrocatalysts for oxygen reduction reaction (ORR) are an essential component of renewable energy devices, such as fuel cells and metal-air batteries. We herein interleaved novel Co3O4 nanosheets with graphene to develop a first ever sheet-on-sheet heterostructured electrocatalyst for ORR, whose electrocatalytic activity outperformed the state-of-the-art commercial Pt/C with exceptional durability in alkaline solution. The composite demonstrates the highest activity of all the nonprecious metal electrocatalysts, such as those derived from Co3O4 nanoparticle/nitrogen-doped graphene hybrids and carbon nanotube/nanoparticle composites. Density functional theory (DFT) calculations indicated that the outstanding performance originated from the significant charge transfer from graphene to Co3O4 nanosheets promoting the electron transport through the whole structure. Theoretical calculations revealed that the enhanced stability can be ascribed to the strong interaction generated between both types of sheets.

A rapid and label-free dual detection of Hg (II) and cysteine with the use of fluorescence switching of graphene quantum dots

A simple and rapid method of analysis for mercury ions (Hg2+) and cysteine (Cys) was developed with the use of graphene quantum dots (GQDs) as a fluorescent probe. In the presence of GQDs, Hg2+ cations are absorbed on their negatively charged surface by means of electrostatic interactions. Thus, the fluorescence (FL) of the GQDs would be significantly quenched as a result of the FL charge transfer, e.g. 92% quenching at 450 nm occurs for a 5 μmol L−1 Hg2+ solution. However, when Cys was added, a significant FL enhancement was observed (510% at 450 nm for a 8.0 μmol L−1 Cys solution), and Hg2+ combined with Cys rather than with the GQDs in an aqueous solution. This occurred because a strong metalsingle bondthiol bond formed, displacing the weak electrostatic interactions, and this resulted in an FL enhancement of the GQDs. The limits of detection (LOD) for Hg2+ and Cys were 0.439 nmol L−1 and 4.5 nmol L−1, respectively. Also, this method was used successfully to analyze Hg2+ and Cys in spiked water samples.

Synthesis and luminescent properties of star-burst D-Pi-A compounds based on 1,3,5-triazine core and carbazole end-capped phenylene ethynylene arms

Two new star-burst compounds based on 1,3,5-triazine core and carbazole end-capped phenylene ethynylene arms (1a and 1b) were synthesized and characterized. Their photophysical properties were investigated systematically via spectroscopic and theoretical methods. Both compounds exhibit strong 1π–π⁎ transitions in the UV region and intense 1π–π⁎/intramolecular charge transfer (1ICT) absorption bands in the UV–vis region. Introducing the carbazole end-capped phenylene ethynylene arm on the 1,3,5-triazine core causes a slight bathochromic shift and enhanced molar extinction coefficient of the 1π–π⁎/1ICT transition band. Both compounds are emissive in solution at room temperature and 77 K, which exhibit pronounced positive solvatochromic effect. The emitting state could be ascribed to 1ICT state in more polar solvent, and 1π–π⁎ state in low-polarity solvent. The high emission quantum yields (Φem=0.90~1.0) of 1a and 1b (in hexane and toluene) make them potential candidates as efficient light-emitting materials. The spectroscopic studies and theoretical calculations indicate that the photophysical properties of these compounds can be tuned by the carbazole end-capped phenylene ethynylene arm, which would also be useful for rational design of photofunctional materials.

Experimental and theoretical characterization of 5,10- diminoporphodimethenes: Dearomatized porphyrinoids from palladium-catalyzed hydrazinations of 5,10-diarylporphyrins

A new dearomatized porphyrinoid, 5,10-diiminoporphodimethene (5,10-DIPD), has been prepared by palladium-catalyzed hydrazination of 5,10-dibromo-15,20-bis(3,5-di-tert-butylphenyl)porphyrin and its nickel(II) complex, by using ethyl and 4-methoxybenzyl carbazates. The oxidative dearomatization of the porphyrin ring occurs in high yield. Further oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone forms the corresponding 5,10-bis(azocarboxylates), thereby restoring the porphyrin aromaticity. The UV/visible spectra of the NiII DIPDs exhibit remarkable redshifts of the lowest-energy bands to 780 nm, and differential pulse voltammetry reveals a contracted electrochemical HOMO–LUMO gap of 1.44 V. Density functional theory (DFT) was used to calculate the optimized geometries and frontier molecular orbitals of model 5,10-DIPD Ni7c and 5,10-bis(azocarboxylate) Ni8c. The conformations of the carbamate groups and the configurations of the CNZ unit were considered in conjunction with the NOESY spectra, to generate the global minimum geometry and two other structures with slightly higher energies. In the absence of solution data regarding conformations, ten possible local minimum conformations were considered for Ni8c. Partition of the porphyrin macrocycle into tri- and monopyrrole fragments in Ni7c and the inclusion of terminal conjugating functional groups generate unique frontier molecular orbital distributions and a HOMO–LUMO transition with a strong element of charge transfer from the monopyrrole ring. Time-dependent DFT calculations were performed for the three lowest-energy structures of Ni7c and Ni8c, and weighting according to their energies allowed the prediction of the electronic spectra. The calculations reproduce the lower-energy regions of the spectra and the overall forms of the spectra with high accuracy, but agreement is not as good in the Soret region below 450 nm.

Graphene-covered perovskites: An effective strategy to enhance light absorption and resist moisture degradation

The long-term stability of methylammonium lead triiodide (MAPbI3) perovskite in moist environments is a paramount challenge to realise the commercialization of perovskite solar cells. In an attempt to address this concern, we have carried out systematic first-principles studies on the MAPbI3 perovskite with a hydrophobic graphene layer interfaced as a water barrier. We find there is a charge transfer at the graphene/MAPbI3 interface and electrons can be excited from graphene into the perovskite surface, leading to well separated electron–hole pairs, i.e. reduced recombination. By studying the optical properties, we find the hybrid graphene/MAPbI3 nanocomposite displays enhanced light absorption compared with the pristine MAPbI3. Furthermore, from an ab initio molecular dynamics simulation, the graphene/MAPbI3 nanocomposite is confirmed to be able to resist the reaction with water molecules, highlighting a great advantage of this nanocomposite in promoting long-term photovoltaic performance.

Highly efficient spin-conversion effect leading to energy up-converted electroluminescence in singlet fission photovoltaics

Free charge generation in donor-acceptor (D-A) based organic photovoltaic diodes (OPV) progresses through formation of charge-transfer (CT) and charge-separated (CS) states and excitation decay to the triplet level is considered as a terminal loss. On the other hand a direct excitation decay to the triplet state is beneficial for multiexciton harvesting in singlet fission photovoltaics (SF-PV) and the formation of CT-state is considered as a limiting factor for multiple triplet harvesting. These two extremes when present in a D-A system are expected to provide important insights into the mechanism of free charge generation and spin-character of bimolecular recombination in OPVs. Herein, we present the complete cycle of events linked to spin conversion in the model OPV system of rubrene/C60. By tracking the spectral evolution of photocurrent generation at short-circuit and close to open-circuit conditions we are able to capture spectral changes to photocurrent that reveal the triplet character of CT-state. Furthermore, we unveil an energy up-conversion effect that sets in as a consequence of triplet population build-up where triplet-triplet annihilation (TTA) process effectively regenerates the singlet excitation. This detailed balance is shown to enable a rare event of photon emission just above the open-circuit voltage (VOC) in OPVs.

Graphene-like two-dimensional ionic boron with double dirac cones at ambient condition

Recently, partially ionic boron (γ-B28) has been predicted and observed in pure boron, in bulk phase and controlled by pressure [Nature, 457 (2009) 863]. By using ab initio evolutionary structure search, we report the prediction of ionic boron at a reduced dimension and ambient pressure, namely, the two-dimensional (2D) ionic boron. This 2D boron structure consists of graphene-like plane and B2 atom pairs, with the P6/mmm space group and 6 atoms in the unit cell, and has lower energy than the previously reported α-sheet structure and its analogues. Its dynamical and thermal stability are confirmed by the phonon-spectrum and ab initio molecular dynamics simulation. In addition, this phase exhibits double Dirac cones with massless Dirac fermions due to the significant charge transfer between the graphene-like plane and B2 pair that enhances the energetic stability of the P6/mmm boron. A Fermi velocity (vf) as high as 2.3 x 106 m/s, which is even higher than that of graphene (0.82 x 106 m/s), is predicted for the P6/mmm boron. The present work is the first report of the 2D ionic boron at atmospheric pressure. The unique electronic structure renders the 2D ionic boron a promising 2D material for applications in nanoelectronics.