High efficiency photocurrent generation by two-dimensional mixed J-aggregates of cyanine dyes

Two-dimensional mixed J-aggregates of structurally and spectrally analogous anionic cyanine dyes, coadsorbed on a self-assembled monolayer of aminoalkanethiolate on Au(111), generated a high-efficiency (20-30% quantum efficiency) cathodic photocurrent and a significant photovoltaic effect in reversible Fe2+/Fe3+ redox solution.     

Electronic structure of C60 on Au(887)

We present an analysis of the electronic structure of C60 adsorbed on a vicinal Au(111) surface at different fullerene coverages using photoemission, x-ray absorption, and scanning tunneling microscopy/spectroscopy (STS). STS provides a straightforward determination of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) levels with respect to the Fermi energy. At C60 coverages of 0.5 and 1 ML a 2.7 eV wide HOMO-LUMO gap is found. The near-edge x-ray absorption fine structure (NEXAFS) spectrum for the 0.5 ML C60 nanomesh structure displays a significant intensity at the low energy side of the LUMO exciton peak, which is explained as due to absorption into HOMO-LUMO gap states localized at individual C60 cluster edges. From 0.5 to 1 ML we observe a rigid shift of the HOMO-LUMO peaks in the STS spectra and an almost complete quenching of the gap states feature in NEXAFS.     

Tuning J-aggregates of tetra(p-hydroxyphenyl)porphyrin by the headgroups of ionic surfactants in acidic nonionic micellar solution

J-aggregates of the diacid form of tetra(p-hydroxyphenyl)porphyrin (THPP) were found to be stable in nonionic micellar solution in the presence of trace ionic surfactant with an oxyacid headgroup. The excitation energy of exciton coupling depends systematically on the headgroups of the ionic surfactant, by which strong and weak coupling can be accomplished in the J-aggregates. The J-aggregates have two strong exciton bands corresponding to the B- and Q-bands of the protonated monomers. The total fluorescence of THPP is quenched through aggregate formation. A strong and sharply peaked resonance light-scattering signal that suggests a delocalized excitonic state was observed just slightly to the red of the absorption maximum of the J-aggregates. The overall resonance Raman intensities appeared to be stronger in the aggregates than in the monomers. In the kinetics of aggregation induced by sodium dodecyl sulfate (SDS), no characteristics of autocatalyzed reactions were observed, and there was only a logarithmic phase that lasted only several seconds.     

Heterogeneous exciton dynamics revealed by two-dimensional optical spectroscopy

We show that optical two-dimensional (2D) spectroscopy can recover ultrafast heterogeneous dynamics of closely spaced delocalized exciton states from a molecular exciton manifold characterized by a single absorption band. The complete experimental third-order nonlinear optical response from room-temperature J-aggregates in liquid phase is reproduced for the first time with self-consistent Frenkel exciton theory combined with modified Redfield theory. We show that exciton relaxation between the exciton states and nuclear-motion-induced exchange-narrowed energy fluctuations of individual delocalized exciton states can be distinguished because these two processes lead to a distinctively different evolution of the absolute 2D spectrum. Our technique also allows recovery of the variation of the exciton relaxation rates as well as the degree of exciton delocalization across the absorption band.     

Substituent-control exciton in J-aggregates of protonated water-insoluble porphyrins

A series of protonated porphyrin J-aggregates of various water-insoluble tetraphenylporphyrin derivatives was prepared by aggregation at the liquid-liquid or gas-liquid interface. Using atomic force microscopy, we observed microcrystalline porphyrin J-aggregates. The J-aggregates have two strong exciton bands corresponding to the B (Soret)- and Q-bands of the protonated porphyrin. Interestingly, the excitation energy of the lower exciton (denoted by S1) markedly depends on the meso-substituents, whereas that of the higher exciton (denoted by S2) does not depend on them. These results indicate that the nature of the exciton coupling of the S1 transition dipole moment can be systematically changed by the substituents.     

Electrochemical metal deposition on top of an organic monolayer

Electrochemical deposition of metals (platinum or gold) only on top of an organothiolate, 1,4-benzenedimethanethiol (BDMT) or hexanedithiol (HDT), self-assembled monolayer (SAM) on a Au(111) substrate was achieved by electrochemical reduction of PtCl(4)(2-) or AuCl(4)(-) ion, which was preadsorbed on one free thiol end group of the dithiol SAM formed on a Au surface, in a metal-ion-free sulfuric acid solution at potentials more negative than the reduction potential of the metal ion. Angle-resolved X-ray photoelectron spectroscopy (AR-XPS) measurement after the reduction of preadsorbed PtCl(4)(2-) ion on BDMT/Au(111) electrode showed the presence of Pt not underneath but on top of the BDMT SAM. After a negative potential scan of the Pt/BDMT/Au(111) electrode to -1.30 V in 0.1 M KOH solution, a typical cyclic voltammogram of a clean Au(111) electrode was obtained, showing that the BDMT SAM with a Pt layer was reductively desorbed. These results proved that a Pt-BDMT SAM-Au substrate sandwich structure without a short circuit between the two metals was successfully constructed by this technique. Furthermore, a decanethiol (DT) monolayer was constructed on a Au layer, which was formed by the reduction of preadsorbed AuCl(4)(-) ion on HDT/Au(111) electrode. The formation of DT/Au/HDT/Au(111) structure was confirmed as two cathodic peaks corresponding to reductive desorption of DT from Au on top of the HDT/Au(111) at -0.97 V and that of Au/ HDT from Au(111) at -1.12 V were observed when potential was scanned negatively to -1.35 V.     

Electron-Withdrawing Substituents Allow Boosted NIR-II Fluorescence in J-Type Aggregates for Bioimaging and Information Encryption

Developing molecular fluorophores with enhanced fluorescence in aggregate state for the second near-infrared (NIR-II) imaging is highly desirable but remains a tremendous challenge due to the lack of reliable design guidelines. Herein, we report an aromatic substituent strategy to construct highly bright NIR-II J-aggregates. Introduction of electron-withdrawing substituents at 3,5-aryl and meso positions of classic boron dipyrromethene (BODIPY) skeleton can promote slip-stacked J-type arrangement and further boost NIR-II fluorescence of J-aggregates via increased electrostatic repulsion and intermolecular hydrogen bond interaction. Notably, NOBDP-NO₂ with three nitro groups (−NO₂) shows intense NIR-II fluorescence at 1065 nm and high absolute quantum yield of 3.21 % in solid state, which can be successfully applied in bioimaging, high-level encoding encryption, and information storage. Moreover, guided by this electron-withdrawing substituent strategy, other skeletons (thieno-fused BODIPY, aza-BODIPY, and heptamethine cyanine) modified with −NO₂ are converted into J-type aggregates with enhanced NIR-II fluorescence, showing great potential to convert aggregation caused emission quenching (ACQ) dyes into brilliant J-aggregates. This study provides a universal method for construction of strong NIR-II emissive J-aggregates by rationally manipulating molecular packing and establishing relationships among molecular structures, intermolecular interactions, and fluorescence properties.     

Electric field-controlled dissociation and association of porphyrin J-aggregates in aqueous solution

The electrooptic effects of porphyrin J-aggregates of tetraphenyl porphyrin tetrasulfonic acid (TPPS) in aqueous solution were studied using electroabsorption (EA) spectroscopy. When the J-aggregates were three-dimensionally distributed, the EA spectra exhibited broadening in the exciton band. When a DC or AC electric field was applied for a long time, the J-aggregates with KCl were dissociated into monomers via N-mers (N = 2-4) as intermediate states, while those without KCl had an increase in aggregation. The EA spectra showed a red shift in the exciton band for N-mers, which indicates that N-mers are isolated microaggregates with a coherent aggregation number N, and isolated microaggregates have not been microscopically or spectrally observed until now. The estimated third-order nonlinear optical susceptibility χ((3)) for EA spectra in aqueous solution was 10(4) times larger than that in a polymer film. The molecular rearrangement model was applied to a variety of orientational distributions and the results were explained fairly well. The contribution of the electric double layer is the most probable reason for the large enhancement of χ((3)) for the solution sample. The dynamic equilibrium between two types of monomers, J-aggregates of various aggregation numbers and cations such as K(+) and H(+) was investigated to reveal that K(+) is more loosely bound to the constituent monomers in J-aggregates than H(+). Equilibrium equations also show that well-grown aggregates with N > 15 tend to dominate in a solution of J-aggregates, which explains why only well-developed aggregates can be observed spectroscopically.     

First-principles Study of Electron Transport Through Oligoacenes

The electronic transport properties of oligoacenes sandwiched between two Au（111） surfaces with serial and parrallel configurations were investigeted by using a fully self-consistent nonequilibrium Green＇s function method combined with density functional calculations. This theoretical results show that the conductivity of oligoacenes with both sandwiched configurations at low bias voltage is mainly determined by the tail of the transmission peak from the perturbed highest occupied molecular orbital. When the molecular length increases, the zero-bias voltage conductance G（0） of oligoacenes with serial configuration neither follows Magoga＇s exponential law nor displays the even-odd oscillation effect, while the G（O） of the oligoacenes sandwiched with parallel configuration monotonically increases. The reduction of energy gaps, the alignment of the Fermi level, and the spatial distribution of the perturbed molecular orbitals are used to self-consistently explore the transport mechanism through oligoacenes.     

二氢吲哚类染料用于染料敏化太阳能电池光敏剂的比较

采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对四种二氢吲哚染料进行研究, 从中筛选出相对优秀的染料敏化太阳能电池光敏剂. 对前线分子轨道的计算表明, 二氢吲哚染料的前线分子轨道结构非常有利于染料激发态向TiO2电极的电子注入. 对真空中的紫外和可见光吸收光谱的计算表明, 二氢吲哚染料的吸收光谱与太阳辐射光谱匹配较好. 对染料分子的能级计算表明, 二氢吲哚染料的能级结构比较适合于I-/I-3作电解液的TiO2纳米晶太阳能电池的光敏剂. 二氢吲哚染料最低未占据分子轨道(LUMO) 能级均比TiO2晶体导带边能级高, 能够保证激发态染料分子高效地向TiO2电极转移电子. 二氢吲哚染料最高占据分子轨道(HOMO)的能级比I-/I-3能级低, 保证了失去电子的染料分子能够顺利地从电解液中得到电子. 与实验数据比较, 得出在提高染料敏化太阳能电池转换效率方面, 对染料的关键要求是LUMO能级的位置. 染料分子的稳定性是染料敏化太阳能电池使用寿命的关键因素. 通过对化学键键长的比较表明, 二氢吲哚染料的分子稳定性基本相同. 对计算结果的分析表明, 二氢吲哚染料1(ID1)的LUMO能级最高, 分子稳定性最好, 在酒精溶液中的吸收光谱与太阳辐射光谱匹配很好, 在同类染料中是较好的染料敏化太阳能电池光敏剂.     

Effects of NaCl on the J-aggregation of two thiacarbocyanine dyes in aqueous solutions

The effects of NaCl on the aggregation of two typical thiacarbocyanine dyes (3,3'-di(3-sulfopropyl)-4,5,4',5'-dibenzo-9-phenyl-thiacarbocyanine triethyl ammonium salt (Dye 1) and 3,3'-di(3-sulfopropyl)-4,5,4',5'-dibenzo-9-methyl-thiacarbocyanine triethyl ammonium salt (Dye 2)) in aqueous solution have been studied by using absorption spectroscopy, fluorescence spectroscopy, and 1H- and 23Na-NMR measurements. It is found that the J-aggregation of two dyes can be promoted by the addition of NaCl and that the effective coherence length of the J-aggregate is shorter than that obtained without NaCl. Fluorescence spectra demonstrate that the fluorescence intensities of the J-aggregates of two dyes are quenched by addition of NaCl. This is consistent with the decrease of the effective coherence length of J-aggregates of the two dyes in the presence of NaCl. 1H-NMR spectra of two dyes show that the Na(+) ions penetrate into the J-aggregates and replace the counterion (triethylammonium ions) in two dyes. The measurements of the chemical shifts of 23Na nuclei provide further information about the interaction between the Na(+) ions and dye anions in the J-aggregates of the two dyes. Due to this interaction, the electrostatic repulsion between the dye anions in the J-aggregates can be reduced and thus accelerate the aggregation of the two dyes in the presence of NaCl. The apparent association constants between Na(+) ions and dye molecules in J-aggregates of Dye 1 and Dye 2 estimated from the measured chemical shifts of 23Na nuclei are about 2.38 M(-1) and 1.35 M(-1), respectively.     

Wavelength Dependence of the Fluorescence Quenching Efficiency of Nearby Dyes by Gold Nanoclusters and Nanoparticles: The Roles of Spectral Overlap and Particle Size

The efficiency of the glutathione monolayer-protected gold nanocluster (NC) Au(25) (1.2 nm metal core diameter (d)) in quenching the emission of dyes intercalated into DNA is compared to that of 2 and 4 nm gold nanoparticles (NPs). In all cases, the DNA/dye moieties and the gold particles are not covalently attached but rather form non-covalent ground state complexes. Under these conditions, steady-state measurements reveal that the quenching efficiency of Au(25) is a factor of 10 lower than that of plasmonic 4 nm gold NPs but comparable to that of 2 nm particles which do not show a distinct plasmon band. Nonetheless, significant emission quenching is observed even at very low (nM) concentrations of Au(25). The quenching efficiency of the 4 nm NPs is significantly higher for dyes emitting near the wavelength of the plasmon peak whereas that of the 2 nm gold NPs is well described by the nano-surface energy transfer (NSET) model proposed by the Strouse group (J. Am. Chem. Soc. 127, 3115 2005). Interestingly, for Au(25) the maximum quenching efficiency occurs for dyes emitting in the same wavelength range as that of the 2 and 4 nm NPs (490-560 nm), where it shows no discrete absorption features, rather than for wavelengths coincident with its HOMO-LUMO, intra-band or inter-band transitions. The fluorescence quenching properties of Au(25) NCs are therefore found to be distinct from those of larger NCs and NPs but do not appear to conform to theoretical predictions advanced thus far.     

A comparative study of the nonlinear optical properties of molecular J- and H-aggregates in thin films

A comparative study of the dispersion of nonlinear absorption in thin films of molecular J- and H-aggregates of polymethine dyes was performed with the use of the Z-scan (Z-scan technique) over the range 625–825 nm under conditions close to resonance absorption at nanosecond duration of excitation. The measurements were made on film samples of J- and H-aggregates prepared by spin-coating and having identical absorption spectra. The H- and J-aggregates were formed by the synthetic thioflavylium DT-3 and benzothiazole BTC18H dyes, respectively. It was found that the samples of different types of aggregates exhibit nonlinear susceptibility of the same order of magnitude with allowance for the width of exciton absorption peaks.     

In situ STM evidence for the adsorption geometry of three N-heteroaromatic thiols on Au(111)

The electrochemical behavior of three heteroaromatic thiols (MBs) (2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole (MBT), and 2-mercaptobenzoxazole (MBO)) on a Au(111) surface has been investigated by electrochemical scanning tunneling microscopy (ECSTM) and cyclic voltammetry (CV) in 0.1 M HClO(4) solution. All three thiols form oriented molecular cluster lines along the reconstruction line direction at 0.55 V. With the electrode potential shifting negatively, the molecules undergo a disordered-ordered structural transition. Molecularly resolved STM images show that all three molecules form striped adlayers in the desorption region on the Au(111) surface. The different heteroatoms in the heteroaromatic rings result in different electrochemical behavior of the MB self-assembled monolayers (SAMs). MBI, MBT, and MBO are proposed to interact with the substrate via the S-Au bonds from thiol group and the coordination interaction of N, S, and O with the substrate from the heteroaromatic ring, respectively. These results provide direct evidence of the electrochemical behavior and the adlayer structures of MB SAMs on the Au electrode.     

Excitation energy transfer between closely spaced multichromophoric systems: effects of band mixing and intraband relaxation

We theoretically analyze the excitation energy transfer between two closely spaced linear molecular J-aggregates, whose excited states are Frenkel excitons. The aggregate with the higher (lower) exciton band edge energy is considered as the donor (acceptor). The celebrated theory of F?rster resonance energy transfer (FRET), which relates the transfer rate to the overlap integral of optical spectra, fails in this situation. We point out that, in addition to the well-known fact that the point-dipole approximation breaks down (enabling energy transfer between optically forbidden states), also the perturbative treatment of the electronic interactions between donor and acceptor system, which underlies the F?rster approach, in general loses its validity due to overlap of the exciton bands. We therefore propose a nonperturbative method, in which donor and acceptor bands are mixed and the energy transfer is described in terms of a phonon-assisted energy relaxation process between the two new (renormalized) bands. The validity of the conventional perturbative approach is investigated by comparing to the nonperturbative one; in general, this validity improves for lower temperature and larger distances (weaker interactions) between the aggregates. We also demonstrate that the interference between intraband relaxation and energy transfer renders the proper definition of the transfer rate and its evaluation from experiment a complicated issue that involves the initial excitation condition. Our results suggest that the best way of determining this transfer rate between two J-aggregates is to measure the fluorescence kinetics of the acceptor J-band after resonant excitation of the donor J-band.     

On-Surface Assembly of Au-Dicyanoanthracene Coordination Structures on Au(111)

On-surface metal-organic coordination provides a promising way for synthesizing different two-dimensional lattice structures that have been predicted to possess exotic electronic properties. Using scanning tunneling microscopy (STM) and spectroscopy (STS), we studied the supramolecular self-assembly of 9,10-dicyanoanthracene (DCA) molecules on the Au(111) surface. Close-packed islands of DCA molecules and Au-DCA metal-organic coordination structures coexist on the Au(111) surface. Ordered DCA₃Au₂ metal-organic networks have a structure combining a honeycomb lattice of Au atoms with a kagome lattice of DCA molecules. Low-temperature STS experiments demonstrate the presence of a delocalized electronic state containing contributions from both the gold atom states and the lowest unoccupied molecular orbital of the DCA molecules. These findings are important for the future search of topological phases in metal-organic networks combining honeycomb and kagome lattices with strong spin-orbit coupling in heavy metal atoms.     

4-Mercaptopyridine on Au(111): a scanning tunneling microscopy and spectroscopy study

The adsorption of 4-mercaptopyridine (4MPy) molecules on reconstructed Au(111) is investigated by Scanning Tunneling Microscopy (STM) and Spectroscopy (STS) at low temperature and under ultra-high vacuum (UHV) conditions. As made visible by STM, at low coverage (<10%) 4MPy adsorbs preferentially at elbow sites of the Herringbone reconstruction and at step edges of the Au(111). Increasing coverage (but still <30%) results in formation of molecular chains followed, at even higher coverage, by a 3-dimensional growth. Detailed analysis of z-V spectroscopy (ramping the tunneling bias V while keeping the tunneling current constant) provides information on the bias dependent apparent height of a single 4MPy/Au(111) as well as on the local density of states (LDOS) of single and chain 4MPy molecules in comparison to the bare Au(111) surface revealing a significant shift of the lowest unoccupied molecular orbital (LUMO) towards lower energy for molecules within chains. Additionally, the data provide no evidence that for these samples prepared in UHV the adsorption of 4MPy on Au(111) requires mediating Au adatoms. Also, clear indications are given that the adsorption does not induce a strong reduction of the Au DOS close to its Fermi energy. Finally, in context of the apparent STM height of 4MPy molecules, the behavior of the differential barrier height Φ(diff)(V) = (?(z)?(V)I/?(V)I)(2) on bare Au(111) and 4MPy/Au(111) is analyzed and the corresponding experimental values are applied to recover the LDOS of the molecule for unoccupied states according to a previously published numerical recipe [B. Koslowski, H. Pfeifer and P. Ziemann, Phys. Rev. B, 2009, 80, 165419 and M. Ziegler, N. Néel, A. Sperl, J. Kr?ger, and R. Berndt, Phys. Rev. B, 2009, 80, 125402]. In this way, one obtains a spectrum comprising a constant DOS of the Shockley-like surface state of Au(111) and a Lorentzian line attributed to the LUMO of 4MPy.     

Amplified quenching of a conjugated polyelectrolyte by cyanine dyes

The conjugated polyelectrolyte PPESO3 features a poly(phenylene ethynylene) backbone substituted with anionic 3-sulfonatopropyloxy groups. PPESO3 is quenched very efficiently (KSV > 10(6) M(-1)) by cationic energy transfer quenchers in an amplified quenching process. In the present investigation, steady-state and picosecond time-resolved fluorescence spectroscopy are used to examine amplified quenching of PPESO3 by a series of cyanine dyes via singlet-singlet energy transfer. The goal of this work is to understand the mechanism of amplified quenching and to characterize important parameters that govern the amplification process. Steady-state fluorescence quenching of PPESO3 by three cationic oxacarbocyanine dyes in methanol solution shows that the quenching efficiency does not correlate with the Forster radius computed from spectral overlap of the PPESO3 fluorescence with the cyanines' absorption. The quenching efficiency is controlled by the stability of the polymer-dye association complex. When quenching studies are carried out in water where PPESO3 is aggregated, changes observed in the absorption and fluorescence spectra of 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide (HMIDC) indicate that the polymer templates the formation of a J-aggregate of the dye. The fluorescence dynamics in the PPESO3/HMIDC system were probed by time-resolved upconversion and the results show that PPESO3 to HMIDC energy transfer occurs on two distinctive time scales. At low HMIDC concentration, the dynamics are dominated by an energy transfer pathway with a time scale faster than 4 ps. With increasing HMIDC concentration, an energy pathway with a time scale of 0.1-1 ns is active. The prompt pathway (tau < 4 ps) is attributed to quenching of delocalized PPESO3 excitons created near the HMIDC association site, whereas the slow phase is attributed to intra- and interchain exciton diffusion to the HMIDC.     

Electron tunneling through molecular media: a density functional study of Au/Dithiol/Au systems.

We report a density functional theory study of the electronic properties of n-alkanedithiols (CnS2, with n=4, 8 and 12) sandwiched between two Au(111) infinite slab electrodes. We investigate the influence of the distance between the two electrodes and of the molecular chain length, tilt angle, and coverage on the local density of states (LDOS) at the Fermi energy (E(f)). We find that the (small) value of the LDOS at Ef near the center of the molecular wires--a quantity that is related to the tunneling current--is mainly determined by the length n of the alkane chains: it originates from the tails of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) which are broadened by the interaction with the electrodes, and decays exponentially with the length of the molecular wire. This opens a nonresonance tunneling channel for charge transport at small bias voltages. While the length of the hydrocarbon chain appears to be the determining factor, the tilt angle of the molecular wires with respect to the electrode surfaces, and therefore the distance between these, has a small influence on the LDOS at the center of the molecule, while the effect of coverage can be ignored. The picture which emerges from these calculations is totally consistent with a through-bond tunneling mechanism.