Injecting electronic excitation energy into an artificial antenna system through an Ru2+ complex

The Ru2+ complex [Ru(bpy)2(bpy-ph4-Si(CH3)3)]2+ can be electrostatically bound to the negatively charged channel entrances of dye-loaded zeolite L crystals where it acts as a functional stopcock molecule. Impressive electronic triplet-singlet excitation energy transfer from the Ru2+ complex to the acceptor dye oxazine 1 (Ox1) located inside the channels can be observed when the donor molecule is selectively excited. Time-resolved luminescence experiments have been performed on the separate components and on the assembled donor-acceptor material. The luminescence lifetime of the Ru2+ complex attached to the zeolite is reduced by a factor of 30 when Ox1 acceptor molecules are present. The fluorescence decay of Ox1 incorporated in zeolite L is single exponential with a lifetime of 3 ns. The much longer lifetime in zeolite L than in solution is due to the fact, that the diethyl groups are sterically restricted when the dye is inside the host.     

Dye-modified nanochannel materials for photoelectronic and optical devices

Artificial photonic antenna systems have been realised by incorporating organic dyes into zeolite L. The size and aspect ratio of the cylindrically shaped zeolite crystals can be tuned over a wide range, adding to the versatility of this host material. A 600 nm sized crystal, for example, consists of about 96 000 one-dimensional channels oriented parallel to the cylinder axis. Geometrical constraints imposed by the host structure lead to supramolecular organisation of the guests, allowing high concentrations of non- or only very weakly interacting dye molecules. A special twist is added to these systems by plugging the channel openings with a second type of fluorescent dye, a so-called stopcock molecule. The two types of molecules are precisely tuned to each other; the stopcocks are able to accept excitation energy from the dyes in the channels, but cannot pass it back. The supramolecular organisation of dyes in the zeolite channels corresponds to a first stage of organisation, allowing light-harvesting within the volume of a cylindrical crystal and radiationless energy transport to either the cylinder ends or centre. The second stage of organisation represents the coupling to an external acceptor or donor stopcock fluorophore at the channel entrances, which can then trap or inject electronic excitation energy. The third stage of organisation is realised by interfacing the material to an external device through a stopcock intermediate. We observed that electronic-excitation-energy transfer in dye-zeolite L materials occurs mainly along the channel axis and we have shown that macroscopically organised materials can be prepared. The new materials offer unique possibilities as building blocks for optical, electro-optical and sensing devices.     

Electrochemiluminescence resonance energy transfer between quantum dots (QDs) as the donor and Cy5 dye molecules as the acceptor in QD-Cy5 conjugates with biomolecules as the linker

Electrochemiluminescence resonance energy transfer (ECRET) between CdSe/Zns quantum dots (QDs) as the donor and cyanine dye (Cy5) molecules as the acceptor in QD-Cy5 conjugates with DNA or protein as the linker was reported. When a negative potential was applied, the excited-state CdSe/ZnS* was produced in 0.1 mol/L phosphate buffer (pH 7.4) containing 0.1 mol/L K₂S₂O₈ and 0.1 mol/L KNO₃ (PB-K₂S₂O₈). The CdSe/ZnS* went back to the ground-state CdSe/ZnS to emit light at 590 nm or to transfer energy to proximal ground-state Cy5 molecules. The resultant excited-state Cy5 molecules relaxed to their ground state by emitting a light at 675 nm. The ECRET between QDs and Cy5 was used to evaluate interactions between DNAs and to measure conformational changes of DNAs and proteins.     

荧光法研究药物分子与人血清白蛋白的结合作用

本文应用荧光光谱和能量转移技术首次研究了心血管病药物盐酸地尔硫卓、盐酸川芎嗪和甘草酸三种药物分子与人血清白蛋白的结合作用。研究结果表明, 盐酸川芎嗪和盐酸地尔硫卓在溶液中与白蛋白形成缔合物, 荧光猝灭机理符合静态机制, 缔合物的稳定常数分别为: 盐酸川芎嗪Ks=1.12×10^4(mol/L)^-^1(25℃),Ks=6.95×10^3 (mol/L)^-^1(40℃); 盐酸地尔硫卓Ks=4.71×10^2(mol/L)^-^1(25℃), Ks=3.00×10^2(mol/L)^-^1(40℃)。甘草酸与白蛋白的作用符合动态猝灭机理, 动态猝灭常数为Kd=4.76×10^(mol/L)^-^1(25℃), Kd=6.19×10^2(mol/L)^-^1(40℃)。基于Forster 偶极-偶极无辐射能量转移机理确定了药物分子盐酸川芎嗪在人血清白蛋白中与第214位色氨酸残基之间的距离R=1.76nm(25℃), R=1.80nm(40℃)。     

CdTe量子点与罗丹明B间的荧光共振能量转移研究

以巯基乙酸为稳定剂, 在水溶液中合成了CdTe量子点. 以发射波长522 nm的量子点为给体, 罗丹明B为受体, 研究了在十六烷基三甲基溴化铵胶束介质中, 量子点与罗丹明B之间的荧光共振能量转移. 实验结果表明, 在pH＝5.00的缓冲溶液中, 当十六烷基三甲基溴化铵的浓度为1.37×10－4 mol/ L时, 量子点与罗丹明B之间的距离为2.65 nm, 1个量子点给体最多可与6个罗丹明B受体发生有效的共振能量转移, 能量转移效率为0.69.     

全合成双分子膜分子激发态能量转移的研究

研究了全合成双分子膜内的分子激发态能量转移行为,给体为囊泡双亲分子上的联苯生色基,受体是通过静电相互作用结合在囊泡表面上的荧光黄阴离子.荧光黄猝灭联苯的荧光强度符合Sern-Volmer猝灭定律.探讨了囊泡在能量转移过程中的组织作用、转移效率与机制.通过研究由静电作用结合在囊泡表面上的荧光黄给体和四苯基卟啉受体间的能量转移,改善了光的输出,扩展了光波的覆盖范围.全合成双分子膜是能量转移的有效介质和良好的膜模拟剂.     

Effect of donor-acceptor interaction strength on excitation energy migration and diffusion at high donor concentrations

The migration and diffusion modulated excitation energy transfer has been studied in a new dye pair 7-diethylamino-4-methylcoumarin (donor) to 3,3'-dimethyloxacarbocyanine iodide (acceptor) by steady-state and picosecond time-resolved spectroscopy. To reduce the artifact of self-absorption, at high donor concentrations, the time-resolved studies have been carried out in thin films of polyvinyl alcohol (solid matrix) and in methanol (liquid phase) at front-face geometry of excitation. The Forster-type (nonradiative) energy transfer [Discuss. Faraday Soc. 27, 7 (1959)] takes place directly from donor to acceptor in case of solid matrix, while Yokota-Tanimoto model [J. Phys. Soc. Jpn. 22, 779 (1967)] for diffusion has been found to be operating in the liquid phase. It has been found here that the high interaction strength between donor and acceptor molecules as compared to that among donors masks the effect of energy migration and diffusion at high donor concentrations. The rate and efficiency of energy transfer increase with increasing the acceptor concentration. This has been confirmed by the study of acceptor kinetics.     

Self-assembled pi-nanotapes as donor scaffolds for selective and thermally gated fluorescence resonance energy transfer (FRET)

Self-assembled nanotapes of a few tailor-made oligo(p-phenylenevinylene)s (OPVs) have been prepared and used as supramolecular donor scaffold to study the fluorescence resonance energy transfer (FRET) to a suitable acceptor. In nonpolar solvents, FRET occurs with nearly 63-81% efficiency, exclusively from the self-assembled OPVs to entrapped Rhodamine B, resulting in the quenching of the donor emission with concomitant formation of the acceptor emission at 625 nm. The efficiency of FRET is considerably influenced by the ability of the OPVs to form the self-assembled aggregates and hence could be controlled by structural variation of the molecules, and polarity of the solvent. Most importantly, FRET could be controlled by temperature as a result of the thermally reversible self-assembly process. The FRET efficiency was significantly enhanced (ca. 90%) in a xerogel film of the OPV1 which is dispersed with relatively less amount of the acceptor (33 mol %), when compared to that of the aggregates in dodecane gel. FRET is not efficient in polar solvents due to weak self-organization of the chromophores. These results indicate that energy transfer occurs exclusively from the self-assembled donor and not directly from the individual donor molecules. The present study illustrates that the self-assembly of chromophores facilitates temperature and solvent controlled FRET within pi-conjugated nanostructures.     

Förster resonance energy transfer in poly(methyl methacrylates) copolymers bearing donor–acceptor 1,3‐thiazole dyes

The Förster resonance energy transfer (FRET) properties in poly(methyl methacrylate) copolymers containing 2‐(pyridine‐2‐yl) thiazole dyes were studied upon systematic variation of the donor‐to‐acceptor ratio. To this end, 2‐(pyridine‐2‐yl) thiazole dyes specially designed for the usage as energy donor and acceptor molecules were incorporated within one polymer chain. Poly(methyl methacrylate) copolymers containing these donor and acceptor dyes were synthesized using the RAFT polymerization method. Copolymers with a molar mass (M_n) of nearly 10,000 g/mol were achieved with dispersity index values (?) under 1.3. The presented copolymers act as a model system for the FRET investigation. Förster resonance energy transfer properties of the copolymers are characterized by steady state as well as time resolved fluorescence spectroscopy. The results indicate that the energy transfer rates and the transfer efficiencies are tunable by variation of the donor‐acceptor‐ratio. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4765–4773     

Interlayer triplet-triplet energy transfer in nanosized molecular layers

The results of the study of interlayer triplet-triplet energy transfer from anthracene molecules to Nile Red molecules in Langmuir-Blodgett films are presented. The observed sensitized delayed fluorescence of the energy acceptor is shown to be due to annihilation of migrating triplet excitons. It has been found that the decay kinetics of delayed fluorescence of the donor and the acceptor has a complex form and is described by a combination of the power and exponential functions. The dependence of the energy transfer efficiency on the distance between the donor and acceptor layers was studied.     

Photophysical properties of novel fluorescent poly(oxyethylene phosphate) tris(β-diketonate) europium (III) complexes

In the present study, photophysical properties of fluorescent poly(oxyethylene phosphate) tris(β-diketonate) europium (III) complexes have been studied by means of stationary and time-resolved fluorescence spectroscopy (in ethanol at room temperature). The luminescent quantum yields and efficiency for the energy transfer from β-diketonate ligands to Eu(III) ion have been determined for the studied complexes by using diffusion-enhanced fluorescence resonance energy transfer. Obtained results show effect of the polymer ligands upon photophysical properties of the complexes and a relation has been established with length of the oxyethylene spacer between two phosphonate groups. The Förster radiuses of the synthesized compounds with SulfoRhodamine 101 as acceptor have been calculated. Measured distances between molecules of the donors and acceptor at identical acceptor/donor molar ratios have been illustrated the difference in structure of the ternary and polymer complexes in solution even at low concentration.     

Time-resolved measurements of intramolecular energy transfer in single donor/acceptor dyads

We have investigated electronic excitation energy transfer in a specifically designed bichromophoric donor/acceptor dyad in which the donor (perylenediimide) and acceptor (terrylenediimide) are linked by a rigid heptaphenyl-spacer. Because of the choice of the bridge, which defines the distance and orientation of the two chromophores, donor as well as acceptor emission is observed. The significantly smaller photostability of the donor allows for time-resolved measurements of the acceptor emission at the single-molecule level with and without energy transfer from the donor. By analyzing the differences of the rise/decay profiles for both pathways, we could determine time constants of energy transfer with high accuracy for single dyads. The results show that the experimental approach presented here works even for situations in which the energy transfer times are smaller than the temporal resolution of the detection system.     

Intramolecular electronic excitation energy transfer in donor/acceptor dyads studied by time and frequency resolved single molecule spectroscopy

Electronic excitation energy transfer has been studied by single molecule spectroscopy in donor/acceptor dyads composed of a perylenediimide donor and a terrylenediimide acceptor linked by oligo(phenylene) bridges of two different lengths. For the shorter bridge (three phenylene units) energy is transferred almost quantitatively from the donor to the acceptor, while for the longer bridge (seven phenylene units) energy transfer is less efficient as indicated by the occurrence of donor and acceptor emission. To determine energy transfer rates and efficiencies at the single molecule level, several methods have been employed. These comprise time-correlated single photon counting techniques at room temperature and optical linewidth measurements at low temperature (1.4 K). For both types of measurement we obtain broad distributions of the rate constants of energy transfer. These distributions are simulated in the framework of Forster theory by properly taking into account static disorder and the flexibility of the dyads, as both effects can substantially contribute to the distributions of energy transfer times. The rate constants of energy transfer obtained from the calculated distributions are smaller on average than those extracted from the experimental distributions, whereby the discrepancy is larger for the shorter bridge. Furthermore, by plotting the experimentally determined transfer rates against the individual spectral overlaps, approximately linear dependencies are found being indicative of a Forster-type contribution to the energy transfer. For a given single molecule such a linear dependence could be followed by spectral diffusion induced fluctuations of the spectral overlap. The discrepancies between measured energy transfer rates and rates calculated by Forster theory are briefly discussed in light of recent results of quantum chemical calculations, which indicate that a bridge-mediated contribution is mainly responsible for the deviations from Forster theory. The availability of the inhomogeneous distributions of donor and acceptor electronic transition frequencies allows for comparing the energy transfer process at liquid helium and room temperature for the same set of molecules via simple simulations. It is found that on average the energy transfer is by a factor of approximately 3 faster at room temperature, which is due to an increase of spectral overlap.     

Role of diffusion in excitation energy transfer and migration

Effect of diffusion on excitation energy transfer and migration in a dye pair sodium fluorescein (donor) and Rhodamine-6G (acceptor) has been studied for different viscosities by both steady state and time domain fluorescence spectroscopic measurements. The donor-donor interaction appears to be weaker as compared to donor-acceptor interaction and thus favors direct Forster-type energy transfer. Interestingly, at low viscosity (water in this case) transfer appears to be controlled by material diffusion/energy migration. Further, acceptor dynamics reveals the fact that direct Forster transfer dominates in viscous media.     

Polariton-assisted manipulation of energy relaxation pathways: donor–acceptor role reversal in a tuneable microcavity

Resonant interaction between excitonic transitions of molecules and localized electromagnetic field allows the formation of hybrid light–matter polaritonic states. This hybridization of the light and the matter states has been shown to significantly alter the intrinsic properties of molecular ensembles placed inside the optical cavity. Here, we have observed strong coupling of excitonic transition in a pair of closely located organic dye molecules demonstrating an efficient donor-to-acceptor resonance energy transfer with the mode of a tuneable open-access cavity. Analysing the dependence of the relaxation pathways between energy states in this system on the cavity detuning, we have demonstrated that predominant strong coupling of the cavity photon to the exciton transition in the donor dye molecule can lead not only to an increase in the donor–acceptor energy transfer, but also to an energy shift large enough to cause inversion between the energy states of the acceptor and the mainly donor lower polariton energy state. Furthermore, we have shown that the polariton-assisted donor–acceptor chromophores'' role reversal or “carnival effect” not only changes the relative energy levels of the donor–acceptor pair, but also makes it possible to manipulate the energy flow in the systems with resonant dipole–dipole interaction and direct energy transfer from the acceptor to the mainly donor lower polariton state. Our experimental data are the first confirmation of the theoretically predicted possibility of polariton-assisted energy transfer reversal in FRET systems, thus paving the way to new avenues in FRET-imaging, remote-controlled chemistry, and all-optical switching.

Polariton-assisted donor–acceptor role reversal in resonant energy transfer between organic dyes tagged with the terminus of the closed oligonucleotide-based molecular beacon strongly coupled to electromagnetic modes of a tuneable microcavity.     

Theoretical characterization and design of small molecule donor material containing naphthodithiophene central unit for efficient organic solar cells

To seek for high‐performance small molecule donor materials used in heterojunction solar cell, six acceptor–donor–acceptor small molecules based on naphtho[2,3‐b:6,7‐b′]dithiophene ( NDT ) units with different acceptor units were designed and characterized using density functional theory and time‐dependent density functional theory. Their geometries, electronic structures, photophysical, and charge transport properties have been scrutinized comparing with the reported donor material NDT(TDPP)₂ ( TDPP = thiophene‐capped diketopyrrolopyrrole). The open circuit voltage (V_oc), energetic driving force(ΔE_L‐L), and exciton binding energy (E_b) were also provided to give an elementary understanding on their cell performance. The results reveal that the frontier molecular orbitals of 3–7 match well with the acceptor material PC₆₁BM , and compounds 3–5 were found to exhibit the comparable performances to 1 and show promising potential in organic solar cells. In particular, comparing with 1 , system 7 with naphthobisthiadiazole acceptor unit displays broader absorption spectrum, higher V_oc, lower E_b, and similar carrier mobility. An in‐depth insight into the nature of the involved excited states based on transition density matrix and charge density difference indicates that all S₁ states are mainly intramolecular charge transfer states with the charge transfer from central NDT unit to bilateral acceptor units, and also imply that the exciton of 7 can be dissociated easily due to its large extent of the charge transfer. In a word, 7 maybe superior to 1 and may act as a promising donor candidate for organic solar cell. © 2013 Wiley Periodicals, Inc.     

Theory of excitation energy transfer regarded as nonadiabatic transition 2: Calculational evidence of nonadiabatic interaction causing intermolecular excitation energy transfer

To clarify whether the excitation energy transfer from a donor molecule or aggregate to a remote acceptor molecule or aggregate can be caused by nonadiabatic interaction as expected in our previous studies 4 ; 5 , we carried out ab initio calculations for three donor–acceptor systems. Even when the acceptor is separated from the donor by 15 Å, it was found that nonadiabatic coupling elements have moderately large values in the nuclear configuration region where the potential energy surfaces at two excited states for the donor–acceptor system are close to each other; otherwise, the conical intersection between the two excited‐state potential energy surfaces appears. In addition, it was found that the adiabatic approximation for the donor–acceptor system holds in the nuclear configuration region in which the initial and final wave packets in the process of the excitation energy transfer lie. These findings lead to the conclusion that the excitation energy transfer between two remote molecules or aggregates can be caused by the nonadiabatic interaction. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 36–43, 2003     

Synthesis, Characterization, and Theoretical Study of Sulfur-Containing Donor-Acceptor DCNQI Derivatives with Photoinduced Intramolecular Electron Transfer

The donor-acceptor compounds N,N'-dicyanobenzo[b]naphtho[2,3-e][1,4]dithiin-6,11-quinonediimine (9a) and N,N'-dicyanobenzo[b]naphtho[2,3-e][1,4]oxathiin-6,11-quinonediimine (10a) and their methyl-substituted derivatives (9b and 10b-d, respectively) have been prepared, and their structural and electronic properties have been characterized by both experimental techniques and quantum-chemical calculations. The (1)H-NMR spectra evidence the existence of a syn/anti isomerism in solution. Both experimental and theoretical data suggest that the preferred configuration of the N-CN groups corresponds to a syn isomer for 9 and to an anti isomer for 10. The X-ray analysis performed for 9b reveals that molecules are not planar and pack in vertical stacks showing an overlap between donor and acceptor moieties of adjacent molecules. In agreement with X-ray data, theoretical calculations predict that both for 9 and 10 the acceptor DCNQI moiety is folded and adopts a butterfly-type structure and the donor moiety is bent along the line passing through the heteroatoms. The energy difference between planar and butterfly structures is calculated to be < 3 kcal/mol at the ab initio 6-31G level. The UV-vis spectra present a broad absorption in the visible which corresponds to a photoinduced intramolecular electron transfer from the high-energy HOMO furnished by the donor moiety to the low-energy LUMO located on the DCNQI fragment. Cyclic voltammetry displays one oxidation peak to the cation and two one-electron reduction waves to the anion and dianion. Theoretical calculations show the planarization of the acceptor/donor moiety induced by reduction/oxidation. The formation of stable radical anions is corroborated by the intense EPR signals recorded for reduced 9. The assignment of the hyperfine coupling constants of the EPR spectra is consistent with the existence of a preferred syn configuration.     

Host-guest antenna materials

The focus of this review is on host-guest composites with photonic antenna properties. The material generally consists of cylindrical zeolite L crystals the channels of which are filled with dye molecules. The synthesis is based on the fact that molecules can diffuse into individual channels. This means that, under the appropriate conditions, they can also leave the zeolite by the same way. In some cases, however, it is desirable to block their way out by adding a closure molecule. Functionalization of the closure molecules allows tuning of, for example, wettability, refractive index, and chemical reactivity. The supramolecular organization of the dyes inside the channels is a first stage of organization. It allows light harvesting within a certain volume of a dye-loaded nanocrystalline zeolite and radiationless transport to both ends of the cylinder or from the ends to the center. The second stage of organization is the coupling to an external acceptor or donor stopcock fluorophore at the ends of the channels, which can trap or inject electronic excitation energy. The third stage of organization is the coupling to an external device through a stopcock molecule. The wide-ranging tunability of these highly organized materials offers fascinating new possibilities for exploring excitation-energy-transfer phenomena, and challenges for developing new photonic devices.