Synthesis and characterization of long perylenediimide polymer fibers: from bulk to the single-molecule level

The synthesis and characterization of perylenediimide polyisocyanides is reported. In addition to short oligomers, our synthetic approach results in the formation of extremely long, well-defined, and rigid perylenediimide polymers. Ordering and close-packing of the chromophores in these long polymers is guaranteed by attachment to a polyisocyanide backbone with amino acid side chains. Hydrogen bonding interactions between those groups stabilize and rigidify the helical polymer structure. The rodlike nature of the synthesized long perylenediimide pendant polyisocyanides as well as the helical arrangement of the chromophores is demonstrated by means of atomic force microscopy. Remarkably, polymer fibers up to 1 mum in length have been visualized, containing several thousands of perylenediimide molecules. Circular dichroism spectroscopy reveals the chiral organization of the chromophore units in the polymer, whereas absorption and emission measurements prove the occurrence of excited-state interactions between those moieties due to the close packing of the chromophore groups. However, an intricate optical behavior is encountered in bulk as a result of the coexistence of short oligomers and long polymers of perylenediimide, a situation subsequently uncovered by means of single-molecule experiments. Individual long helical perylenediimide polyisocyanides exhibit a typical red-shifted fluorescence spectrum, which, together with depolarized emission continuously decreasing in time, demonstrate that fluorescence arises from multiple excimer-like species in the polymer. Upon continuous irradiation of these long polymers, a fast decay in fluorescence lifetime is observed, a situation explained by photoinduced creation of quenching sites. Radical/ion formation by intramolecular electron transfer between close-by perylenediimide moieties is the most probable mechanism for this process. Appropriate control of the electron-transfer process might open the possibility of applying these polymers as perylenediimide-based supramolecular nanowires.     

Synthesis of a π-extended TTF-perylenediimide donor-acceptor dyad

A donor-acceptor dyad containing perylenediimide as the electron acceptor and π-extended tetrathiafulvalene as electron donor has been successfully synthesized by means of a Wittig reaction. Cyclic voltammetry and absorption spectroscopy show that both electroactive units preserve their nature, whereas preliminar photophysical investigations show a strong fluorescence quenching.     

Sub-100 fs charge transfer in a novel donor-acceptor-donor triad organized in a smectic film

Ultrafast transient absorption spectroscopy is performed on a novel donor-acceptor-donor triad made of two identical bisthiophene derivatives as electron donors and a central perylenediimide moiety as electron acceptor. The triad is extended at both ends by covalently bound siloxane chains that confer self-organisation into thin smectic films at ambient temperature. When diluted in chloroform, selective excitation of the donor moiety leads to resonance energy transfer within 130 fs to the acceptor moiety, followed by the formation of a charge transfer (CT) state in ~3 ps. The CT state recombines entirely on a 55 ps time scale. In the liquid crystal films, excitonic intermolecular coupling leads to significant changes in the dynamics. Most remarkably, ultrafast intra- and intermolecular CT state formation occurs in about 60 fs, i.e. on a time scale comparable to electronic coherence times. While the intra-molecular CT states recombine on the same time scale as in solution or even faster, inter-molecular CT states live for about 1 ns. Last, triplet states of the perylenediimide moiety dominate the differential absorption after ~1 ns. We anticipate that the fast recombination of intra-molecular CT states and the triplet state formation may severely limit the photo-current in these materials.     

Directly Linked Zinc Phthalocyanine–Perylenediimide Dyads and a Triad for Ultrafast Charge Separation

Directly linked to promote strong intramolecular interactions, donor–acceptor dyads and a donor–acceptor–donor triad featuring zinc phthalocyanine (ZnPc) as electron donor and perylenediimide (PDI) as electron acceptor have been synthesized and characterized. Owing to complementary absorption features of the entities, improved light absorption was witnessed in these conjugates. The optimized geometry and electronic structures showed the majority of the highest occupied molecular orbital (HOMO) on the ZnPc entity, whereas the lowest unoccupied molecular orbital (LUMO) was on the PDI entity, suggesting that the charge-separated states would be ZnPc ⁺ –PDI ^{. −}. The electrochemical and free-energy calculations suggested exothermic energy and/or electron transfer processes via the singlet states of PDI or ZnPc entities depending on the excitation wavelength of the laser used. The measured rates using femtosecond pump-probe spectroscopy coupled with global analysis of transient data revealed ultrafast energy transfer from ¹PDI* to ZnPc followed by charge separation. However, when ZnPc was selectively excited, only electron transfer was witnessed wherein the time constants for forward and reverse electron transfer processes followed Marcus predictions. The absorption in a wide section of the solar spectrum and the ultrafast charge separation suggest the usefulness of these systems as good photosynthetic models.     

Hydrogen bonding interfaces in fullerene*TTF ensembles

Novel thermodynamically stable supramolecular donor-acceptor dyads have been synthesized. In particular, we assembled successfully C(60), as an electron acceptor, with the strong electron donor TTF through a complementary guanidinium-carboxylate ion pair. Two strong and well-oriented hydrogen bonds, in combination with ionic interactions, ensure the formation of stable donor-acceptor dyads. The molecular architecture has been fine-tuned by using chemical spacers of different lengths (i.e., phenyl versus biphenyl) and functional groups (i.e., ester versus amide), thus providing meaningful incentives to differentiate between through-bond and through-space electron-transfer scenarios. In electrochemical studies, both the donor and acceptor character of the TTF and C(60) units, respectively, have been clearly identified. Steady-state and time-resolved emission studies, however, show a solvent-dependent fluorescence quenching in C(60)*TTF dyads as well as the formation of the C(60)(*)(-)*TTF(*)(+) radical ion pairs, for which we determined lifetimes that are in the range of hundred of nanoseconds to microseconds. The complex network that connects C(60) with TTF in the dyads and the flexible nature of the spacer result in through-space electron-transfer processes. This first example of electron transfer in C(60)-based dyads, connected by strong hydrogen bonds, demonstrates that this approach can add outstanding benefits to the construction of artificial photosynthetic systems that bear a closer resemblance to the natural one.     

Charge transfer events in semiconducting single-wall carbon nanotubes

Electron-donating ferrocene units have been attached to SWNTs, with different degrees of functionalization. By means of a complementary series of novel spectroscopic techniques (i.e., steady-state and time-resolved), we have documented that mutual interactions between semiconducting SWNT and the covalently attached electron donor (i.e., ferrocene) lead, in the event of photoexcitation, to the formation of radical ion pairs. In the accordingly formed radical ion pairs, oxidation of ferrocene and reduction of SWNT were confirmed by spectroelectrochemistry. It is, however, shown that only a few semiconducting SWNTs [i.e., (9,4), (8,6), (8,7), and (9,7)] are susceptible to photoinduced electron transfer processes. These results are of relevant importance for the development of SWNT-based photovoltaics.     

Donor–acceptor perylenediimide–ferrocene conjugates: synthesis,photophysical, and electrochemical properties

Donor–acceptor, perylenediimide–ferrocene conjugates have been synthesized by Suzuki, and Sonogashira coupling reactions. The photophysical and electrochemical properties of these conjugates are discussed. It has been shown that fluorescence as well as the electron affinity of the perylenediimide can be tuned by attaching the appropriate ferrocenyl derivatives.     

Signal transduction in a coupled hormone system: selective explicit internal signal stochastic resonance and its control

Cooperative interactions of signal transduction and environmental noise are investigated with a coupled hormone system, in which selective explicit internal signal stochastic resonance (EISSR) is observed. More specifically, the large peak of a period-2 oscillation (i.e., a strong signal) is greatly amplified by the environmental noise while the small peak (i.e., a weak signal) does not exhibit cooperative interactions with noise. The EISSR phenomenon could be controlled by adjusting the frequency or amplitude of an external signal and a critical amplitude for external signal is found. Significantly, the maximal signal-to-noise ratio increases almost linearly with the increment of control parameter, despite that the magnitude of the large peak is decreased. In addition, the noise does not alter the fundamental frequencies of the strong signal and the weak signal, which implicates that the system can keep its intrinsic oscillatory state and resist the effect of environmental fluctuations.     

Ensemble density functional theory for inhomogeneous fractional quantum hall systems

The fractional quantum Hall effect (FQHE) occurs at a certain magnetic field strengths B^*(n) in a two-dimensional electron gas of density n at strong magnetic fields perpendicular to the plane of the electron gas. At these magnetic fields strengths, the system is incompressible, i.e., there is a finite cost in energy for creating charge density fluctuations in the bulk, while the boundary of the electron gas has gapless modes of density waves. The bulk energy gap arises because of the strong electron-electron interactions. While there are very good models for infinite homogeneous systems and for the gapless excitations of the boundary of the electron gas, computational methods to accurately model finite, inhomogeneous systems with more than about 10 electrons have not been available until very recently. We will here review an ensemble density functional approach to studying the ground state of large inhomogeneous spin-polarized FQHE systems. © 1996 John Wiley & Sons, Inc.     

Copoly(peryleneimide)s containing 1,3,4‐oxadiazole rings: Synthesis and properties

New copolyimides containing perylenediimide, oxadiazole and hexafluoroisopropylidene moieties were prepared by one‐step polycondensation reaction in solution at high temperature of aromatic diamines containing preformed oxadiazole ring with a mixture of a dianhydride having a perylene ring and another dianhydride with hexafluoroisopropylidene unit. The thermal stability and glass transition temperatures of these copolyimides were measured and compared with those of related polyimides. The solid polymers were also studied by polarized light microscopy and X‐ray diffraction which revealed a semicrystalline state consisting of face‐to‐face arranged columns of perylenediimide units. The film‐forming ability and properties of the resulting thin films were investigated by using atom force microscopy and scanning electron microscopy which showed that the films were organized into self‐assembled rod‐like structures. The UV‐Vis and photoluminescence properties in solution and in solid state were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4230–4242, 2010     

Self-assembled fluorescent hexaazatriphenylenes that act as a light-harvesting antenna

In this paper we report the self-assembling nature of fluorescent hexaazatriphenylenes (HATs) 6a-d with six alkyl/alkoxy-chain-containing biphenyl groups and their application to light-harvesting antennae. In a nonpolar solvent and the film state, the HAT derivatives form one-dimensional aggregates with an H-type parallel stacking mode, which were analyzed by 1H NMR, UV-vis, and steady-state and time-resolved fluorescence spectroscopy. When HAT derivative 7 with six perylenediimide moieties is incorporated into the one-dimensional aggregates, an efficient energy transfer takes place from the self-assembled HAT moiety as a light-harvesting antenna to the perylenediimide moiety as an energy acceptor. Further, when HAT derivative 8 with six triphenylamino moieties is newly added to the light-harvesting system, an intermolecular electron transfer occurs subsequently between the electron-accepting perylenediimide molecule and the electron-donating triphenylamino molecule.     

苝二酰亚胺衍生物/三联吡啶铂配合物超分子在G-四链体检测中的应用

合成了3种三联吡啶铂(Ⅱ)配合物(Pt1、Pt2、Pt3)和两种苝二酰亚胺衍生物(PDI1、PDI2),构建了三联吡啶铂配合物/苝二酰亚胺衍生物超分子体系。所得超分子体系可作为"turn-on"型荧光传感器用于检测c-myc G-四链体。三联吡啶铂配合物可通过电子转移作用猝灭苝二酰亚胺的荧光,利用最小二乘法求得三联吡啶铂配合物与PDIs的结合常数为5.57×104~5.28×106 L/mol。加入G-四链体后,三联吡啶铂配合物/苝二酰亚胺超分子发生解离,苝二酰亚胺衍生物的荧光得到恢复。在Pt2/PDI2体系中加入1.5μmol/L c-myc G-四链体可使其荧光增强63倍。在c-myc的浓度为25nmol/L~1.0μmol/L范围内,Pt2/PDI2超分子体系荧光增强(F/F0)与c-myc的浓度呈良好的线性关系(R2=0.995),检测限为1.37nmol/L,表明Pt2/PDI2超分子体系可用于检测c-myc序列DNA。     

Anion-pi interactions

This tutorial review provides an overview of the theoretical and experimental investigations that resulted in the recognition of anion-pi interactions, i.e., non-covalent forces between electron deficient aromatic systems and anions. Several pioneering theoretical studies revealed that these interactions are energetically favorable (approximately 20-50 kJ mol(-1)). Anion-pi interactions are gaining significant recognition, and their pivotal role in many key chemical and biological processes is being increasingly appreciated. The design of highly selective anion receptors and channels represent important advances in this nascent field of supramolecular chemistry.     

Photoinduced electron transfer in a supramolecular species building of mono-6-p-nitrobenzoyl-beta-cyclodextrin with naphthalene derivatives

Photoinduced electron transfer was observed in the supramolecular complexes of p-nitrobenzoyl-beta-cyclodextrin (NBCD) with a number of naphthalene derivatives, which were stabilized clearly via hydrophobic interactions in aqueous solution. Both steady-state and time-resolved fluorescence measurements were conducted, which revealed that there were two routes of electron transfer, i.e., electron transfer between the free donor and free acceptor in solution and electron transfer between the donor and acceptor bound in a supramolecular assembly. The evidence collected demonstrates that the latter route was very efficient. As a result, the rate and quantum yield of the fluorescence quenching in the present supramolecular system were appreciably large.     

p-Phenyleneethynylene molecular wires: influence of structure on photoinduced electron-transfer properties

A series of donor-acceptor arrays (exTTF-oPPE-C60) containing pi-conjugated oligo(phenyleneethynylene) wires (oPPE) of different length between pi-extended tetrathiafulvalene (exTTF) as electron donor and fullerene (C60) as electron acceptor has been prepared by following a convergent synthesis. The key reaction in these approaches is the bromo-iodo selectivity of the Hagihara-Sonogashira reaction and the deprotecting of acetylenes with different silyl groups to afford the corresponding donor-acceptor conjugates in moderate yields. The electronic interactions between the three electroactive species were determined by using UV-visible spectroscopy and cyclic voltammetry. Our studies clearly confirm that, although the C60 units are connected to the exTTF donor through pi-conjugated oPPE frameworks, no significant electronic interactions are observed in the ground state. Theoretical calculations predict how a simple exchange from C=C double bonds (i.e., oligo(p-phenylenevinylene) to C triple chemical bond C triple bonds (i.e., oPPE) in the electron donor-acceptor conjugates considerably alters long-range electron transfer. Photoexcitation of exTTF-oPPE-C60 leads to the following features: a transient photoproduct with maxima at 660 and 1000 nm, which are unambiguously attributed to the photolytically generated radical-ion-pair state, [exTTF*+-oPPE-C60*]. Both charge-separation and charge-recombination processes give rise to a molecular-wire behaviour of the oPPE moiety with an attenuation factor (beta) of (0.2+/-0.05) A(-1).     

Polyampholyte-tuned lyotrop lamellar liquid crystalline systems

The influence of a polyampholyte, i.e., poly(N,N′-diallyl-N,N′-dimethyl-altmaleamic carboxylate) (PalH), on the lamellar liquid crystalline (LC) system sodium dodecyl sulfate (SDS)/decanol/water was investigated by means of microdifferential scanning calorimetry, small-angle X-ray diffraction (SAXS), and cryo-scanning electron microscopy. After incorporating PalH into the lamellar liquid crystalline system, SAXS measurements show that three different LC phases exist: i.e., a swelling, slightly swelling, and non-swelling one. At pH 4, the positively charged polymer with an extended conformation can directly adsorb at the anionic head groups of the surfactant and more compact vesicles are formed at room temperature. At pH 9, the electrostatic interactions between the polyampholyte (in a more coiled conformation) and the sulfate head groups of the SDS are leveled off and incompact vesicles are formed at room temperature. That means in presence of the polyampholyte the morphology of the LC phase, i.e., the supramolecular vesicle structure, can be tuned by varying the pH and/or the temperature.

Sharing orbitals: ultrafast excited state deactivations with different outcomes in bucky ferrocenes and ruthenocenes

We report on the singlet ground and singlet/triplet excited-state features of a series of bucky ferrocenes, bucky ruthenocenes, and respective reference compounds. In the bucky ferrocene conjugates, intimate contacts between the fullerenes and ferrocenes result in appreciable ground-state interactions-suggesting a substantial shift of charge density from the electron donor (i.e., ferrocene) to the electron acceptor (i.e., fullerene). In contrast, no prominent charge-transfer features were observed for the bucky ruthenocene conjugates. An arsenal of experimental techniques, ranging from fluorescence (i.e., steady state and time-resolved) and pump probe experiments (i.e., femtosecond and nanoseconds) to pulse radiolysis, were employed to examine excited-state interactions. In the excited states, bucky ferrocene conjugates are dominated by rapid charge separation reactions (0.8 +/- 0.1 ps) to yield metastable radical ion pairs. The radical ion pair lifetimes vary between 27 and 39 ps. No charge separation was, however, found in the corresponding bucky ruthenocence. Instead, an intrinsically faster excited-state deactivation (approximately 200 ps) evolves from the heavier ruthenium center-relative to iron. This effect is further augmented by the unfavorably shifted oxidation potential in ruthenocene of about 0.61 V, which in ruthenocene (-deltaG(ET) = -0.26 eV), in contrast to ferrocene (-deltaG(ET) = 0.35 eV), renders charge separation thermodynamically unfeasible.     

Metastable Chiral Azobenzenes Stabilized in a Double Racemate

The self‐assembly of chiral organic chromophores is gaining huge significance due to the abundance of supramolecular chirality found in natural systems. We report an interdigitated molecular assembly involving axially chiral octabrominated perylenediimide (OBPDI) which transfers chiral information to achiral aromatic moieties. The crystalline two‐component assemblies of OBPDI and electron‐rich aromatic units were facilitated through π‐hole???π donor–acceptor interactions, and the charge‐transfer characteristics in the ground and excited states of the OBPDI cocrystals were established through spectroscopic and theoretical techniques. The OBPDI cocrystals entail a remarkable homochiral segregation of P and M enantiomers of both molecular entities in the same crystal system, leading to twisted double‐racemic arrangements. Synergistically engendered cavities with the stored chiral information of the twisted OBPDI stabilize higher‐energy P/M enantiomers of trans‐azobenzene through non‐covalent interactions.     

Kinetics of gold nanoparticle aggregation: experiments and modeling

We investigate the aggregation kinetics of gold nanoparticles using both experimental techniques (i.e., quasi-elastic light scattering, UV-visible spectroscopy, and transmission electron microscopy) and mathematical modeling (i.e., constant-number Monte Carlo). Aggregation of gold nanoparticles is induced by replacing the surface citrate groups with benzyl mercaptan. We show that the experimental results can be well described by the model in which interparticle interactions are described by the classical DLVO theory. We find that final gold nanoparticle aggregates have a fractal structure with a mass fractal dimension of 2.1-2.2. Aggregation of approximately 11 initial gold nanoparticles appears to be responsible for the initial color change of suspension. This kinetic study can be used to predict the time required for the initial color change of a gold nanoparticle suspension and should provide insights into the design and optimization of colorimetric sensors that utilize aggregation of gold nanoparticles.     

Complementary Hydrogen Bonding Modulates Electronic Properties and Controls Self‐Assembly of Donor/Acceptor Semiconductors

A comprehensive investigation of the complementary H‐bonding‐mediated self‐assembly between dipyrrolo[2,3‐b:3′,2′‐e]pyridine (P2P) electron donors and naphthalenediimide/perylenediimide (NDI/PDI) acceptors is reported. The synthesis of parent P2P and several aryl‐substituted derivatives is described, along with their optical, redox, and single‐crystal packing characteristics. The dual functionality of heteroatoms in the P2P/NDI(PDI) assembly, which act as proton donors/acceptors and also contribute to π‐conjugation, leads to H‐bonding‐induced perturbation of electronic levels. Concentration‐dependent NMR and UV/Vis spectroscopic studies revealed a cooperative effect of H‐bonding and π–π stacking interactions. This H‐bonding‐mediated co‐assembly of donor (D) and acceptor (A) components leads to a new charge‐transfer (CT) absorption that can be controlled throughout the visible range. The electronic interactions between D and A were further investigated by time‐dependent DFT, which provided insights into the nature of the CT transition. Electropolymerization of difuryl‐P2P afforded the first conjugated polymer incorporating H‐bonding recognition units in its main chain.