Long-range electron and excitation energy transfer in donor–bridge–acceptor systems

Donor–bridge–acceptor (D-B-A) systems, either as supermolecules or on surfaces, have been extensively studied with respect to long-range electron (ET) and excitation energy (EET) transfer. In more recent years, the main research objective has been to develop knowledge on how to construct molecular-based devices, with predetermined electron transfer properties, intended for application in electronics and photovoltaics. At present, such construction is in general hampered for several reasons. Most importantly, the property of a D-B-A system is not a simple linear combination of properties of the individual components, but depends on the specific building blocks and how they are assembled. An important example is the ability of the bridge to support the intended transfer process. The mediation of the transfer is characterized by an attenuation factor, β, often viewed as a bridge specific constant but which also depends on the donor and the acceptor, i.e. the same bridge can either be poorly or strongly conducting depending on the donor and acceptor. This review gives an account of the experimental exploration of the attenuation factor β in a series of bis(porphyrin) systems covalently linked by bridges of the oligo(phenyleneethynylene) (OPE) type. Attenuation factors for ET as well as for both singlet and triplet EET are discussed. A report is also given on the dependence of the transfer efficiency on the energy-gap between the donor and bridge states relevant for the specific transfer process. The experimental variation of β with varying donor and acceptor components is shown for a range of conjugated bridges by representative examples from the literature. The theoretical rationalization for the observed variation is briefly discussed. Based on the Gamow tunneling model, the observed variations in β-values with varying donors and acceptors for the same bridges is simulated successfully simultaneously as the observed energy-gap dependence is modelled.     

Temperature dependence of photoinduced electron transfer in hydrogen-bonded donor–acceptor systems

We have studied the temperature dependence of photoinduced electron transfer (PET) reactions in three hydrogen-bonded donor–acceptor systems in the range 220–298 K. For the hydrogen-bonded system in the normal region, the PET rate constant was found to increase with increase in temperature. For the two systems in the inverted region, the rate constants were nearly independent of temperature. We have analyzed the results using electron transfer theories.     

DFT study of the electronic and charge transfer properties of perfluoroarene–thiophene oligomers

The ground state structures of 5,5″-diperfluorophenyl-2,2′:5′,2″:5″,2‴-quaterthiophene (1), 5,5′-bis{1-[4-(thien-2-yl)perfluorophenyl]}-2,2′-dithiophene (2), 4,4′-bis[5-(2,2′-dithiophenyl)]-perfluorobiphenyl (3), 5,5″-diperfluorophenyl-2,2′:5′,2″-tertthiophene (4), 5,5′-diperfluorophenyl-2,2′-dihiophene (5), and 5,5-diperfluorophenylthiophene (6) have been optimized at the B3LYP/6-31G(d), B3LYP/6-31G(d,p), PBE0/6-31G(d), and PBE0/6-31G(d,p) level of theories. The B3LYP/6-31+G(d) and PBE0/6-31+G(d) level of theories have been applied to investigate the absorption spectra. The PBE0 functional is good to predict the C–S bond lengths while the C–F bond lengths are good envisaged with B3LYP functional. The increment of thiophene rings between two perfluoroarene rings leads to red shift in absorption spectra. The electron affinities are energetically destabilized while energetic stabilization of the radical-cation increases by decreasing the thiophene rings from four to one. The perfluoroarene rings leads to enhance the electron injection.     

Tuning the electronic structures and optical properties of fluorene-based donor–acceptor copolymers by changing the acceptors: a theoretical study

Five fluorene-based conjugated copolymers were studied to explore the effect of acceptor on the electronic and optical properties. Their ground-state, excited-state electronic structures and the tunable optical properties were theoretically investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The acceptors including quinoxaline (Q), 2,1,3-benzothiadiazole (BT), thieno[3,4-b]pyrazine (TP), 2,1,3-benzooxadiazole (BO), and pyridopyrazine (PP) can significantly influence the copolymers’ electronic structures, molecular orbitals, geometric conformations, and optical properties. Calculations were made on systems containing one, two, three, and four oligomers in the neutral, cationic, and anionic structures, which can be extrapolated to infinite chain length polymers. The result indicated that the sequence of the band gap was on the reverse trend of emission wavelength. The strong electron-withdrawing strength of TP unit and coplanar backbone in poly[2,7-(9,9′-dihexylfluorene)-alt-2,3-dimethyl-5,7-dithien-2-yl-thieno[3,4-b] pyrazine] resulted in the enhanced degree of intramolecular charge transfer (ICT) and lowest band gap. The contribution of acceptors to IP was also found to follow the sequence of TP < Q < PP < BT < BO. The absorption and emission spectra exhibited red-shift with increasing the conjugation lengths. The present study suggested that the electronic and optical properties of donor–acceptor conjugated copolymers were affected by the acceptor structure.     

Synthesis and photophysical properties of donor–acceptor system based bipyridylporphyrins for dye-sensitized solar cells

Bipyridylporphyrin derivatives possessing a porphyrin moiety as the electron donor and bipyridyl moiety as the electron–acceptor were designed and synthesized for dye-sensitized solar cells(DSSCs). The photophysical and electrochemical properties were investigated by absorption spectrometry and cyclic voltammetry. Density functional theory(DFT) was employed to study electron distribution. From the photovoltaic performance measurements, a maximum conversion efficiency(η) of 0.38% was achieved based on the bipyridylporphyrin ruthenium dye A7(J_(SC)= 1.33 mA/cm~2, V_(OC)= 0.45 V, FF = 0.64) under 1.5 irradiation(100 mW/cm~2).     

Synthesis and properties of π-conjugated donor–acceptor macrocycles derived from phenanthrylene building blocks

Phenanthrylene-ethynylidene macrocycles combining electron donor and electron acceptor subunits in their shape-persistent fully conjugated core were synthesized. The donor subunits consisted of two 9,10-dialkoxyphenanthrenes linked either with 1,2-ethynylidene or 2,5-thienylene bridge. The acceptors were 9,10-phenanthroquinone and dibenzoquinoxaline and dibenzophenazines derived from it. Solvatochromic photoluminescence from intramolecular-charge-transfer (ICT) excited state was observed mainly in non-polar solvents. In more polar solvents, the excited states favor non-radiative relaxation. DFT calculated HOMO/LUMO energies of the macrocycles correlate well with spectroscopic and electrochemical data. In the series of substituted dibenzophenazine acceptors a good correlation with Hammett substituent constants σ_p^– was found.     

New opportunities in multiplexed optical bioanalyses using quantum dots and donor–acceptor interactions

In this study, we investigated the feasibility of using a novel volatile organic compound (VOC)-based metabolic profiling approach with a newly devised chemometrics methodology which combined rapid multivariate analysis on total ion currents with in-depth peak deconvolution on selected regions to characterise the spoilage progress of pork. We also tested if such approach possessed enough discriminatory information to differentiate natural spoiled pork from pork contaminated with Salmonella typhimurium, a food poisoning pathogen commonly recovered from pork products. Spoilage was monitored in this study over a 72-h period at 0-, 24-, 48- and 72-h time points after the artificial contamination with the salmonellae. At each time point, the VOCs from six individual pork chops were collected for spoiled vs. contaminated meat. Analysis of the VOCs was performed by gas chromatography/mass spectrometry (GC/MS). The data generated by GC/MS analysis were initially subjected to multivariate analysis using principal component analysis (PCA) and multi-block PCA. The loading plots were then used to identify regions in the chromatograms which appeared important to the separation shown in the PCA/multi-block PCA scores plot. Peak deconvolution was then performed only on those regions using a modified hierarchical multivariate curve resolution procedure for curve resolution to generate a concentration profiles matrix C and the corresponding pure spectra matrix S. Following this, the pure mass spectra (S) of the peaks in those region were exported to NIST 02 mass library for chemical identification. A clear separation between the two types of samples was observed from the PCA models, and after deconvolution and univariate analysis using N-way ANOVA, a total of 16 significant metabolites were identified which showed difference between natural spoiled pork and those contaminated with S. typhimurium.     

Spectral and intramolecular charge transfer properties in terminal donor/acceptor-substituted all-trans-α,ω-diphenylpolyenes and α,ω-diphenylpolyynes

The absorption spectra and intramolecular charge transfer (CT) properties of terminal donor/acceptor-substituted all-trans-α,ω-diphenylpolyenes (DPE) and α,ω-diphenylpolyynes (DPY) molecules with different conjugated bridge length and substitution modes were investigated by using quantum chemical calculations. We calculated the ground state structures and energy of two series of terminal donor/acceptor DPE and DPY by DFT method. The dependence of conjugation length and substitution modes of the electronic absorption spectra was obtained by TDDFT calculation. The hybrid-GGA XC-functional PBE0 employed in this work was selected from several functionals by comparing the calculated electronic spectral data with experimental value. The CIS-based generalized Mulliken-Hush (GMH) approach was further used to calculate coupling values H(AD) of the CT process. The calculation shows that both the HOMO-LUMO energy gaps and average bond length alternations between unsaturated multiple (C≡C and C=C) and saturated single bonds (C-C) decrease regularly with the extension of conjugation. The effective conjugated length (ECL) of DPE and DPY with the same order MM > MP/PM > PP is found together with the regular red shift of the electronic absorption spectra with the extension of conjugation, resulting from the different π-electron delocalization and conjugation efficiency. The GMH analysis further suggests that the CT process in both DPE and DPY is predominated by the through-bond mechanism. The remarkable difference of the conjugated length dependence of squared CT coupling between substituted DPE and DPY is the result of the energetic matching degree of the frontier molecular orbitals between donor/acceptor and the conjugated bridge.     

Reorganization energy of supramolecular donor–acceptor dyad of octaethylporphyrin isomers and axial-coordinated acceptor: Experimental and computational study

The internal reorganization energy (λ_V) of photoinduced electron transfer (ET) in the supramolecular donor–acceptor dyads of 2,3,7,8,12,13,17,18-octaethylporphinatozinc(II) (ZnOEP) and electron acceptor ligands was compared with those of structural isomers, 2,3,7,8,11,12,17,18-octaethylhemiporphycenatozinc(II) (ZnHPc) and 2,3,6,7,12,13,16,17-octaethylporphycenatozinc(II) (ZnPcn). First, ET process of the supramolecular donor–acceptor dyads of ZnOEP was investigated by means of the transient absorption spectroscopy mainly. The formation of supramolecular dyads was confirmed by absorption spectral change, from which the association constant was estimated. The ET process was confirmed by the observation of radical cation of ZnOEP during the laser flash photolysis. The ET rates of these dyads are in the order of ZnOEP > ZnHPc > ZnPcn, when the driving forces for ET are similar to each other. From the free energy dependence of ET rates, the λ_V values of OEP and its isomers were estimated. The estimated λ_V value was in the order of ZnOEP < ZnHPc < ZnPcn. This tendency was reproduced by calculation at B3LYP/6-31G(d) and BHandHLYP/6-31G(d) levels. The origin of this tendency was discussed on the basis of the structural change during the ET process.     

The synthesis and spectral properties of a stimuli-responsive D–π–A charge transfer dye based on indole donor and 2-cyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran acceptor moieties

A particular chromogenic and fluorophoric dye chemosensor was designed and synthesized, which was based on the stimuli-responsive D–π–A charge transfer system. Indole moiety as a donor unit and furan moiety as an acceptor unit were used. This prepared dye sensor showed the selective fluoride ion sensing effects in UV–vis absorption and fluorescence emission properties. Clear absorption changes and highly selective fluorescence quenching effects with fluoride ion were determined. Experimental data and images were collected and supported to provide a better understanding of this particular dye sensor.     

Multistep energy and electron transfer processes in novel rotaxane donor–acceptor hybrids generating microsecond-lived charge separated states

A new set of [Cu(phen)₂]⁺ based rotaxanes, featuring [60]-fullerene as an electron acceptor and a variety of electron donating moieties, namely zinc porphyrin (ZnP), zinc phthalocyanine (ZnPc) and ferrocene (Fc), has been synthesized and fully characterized with respect to electrochemical and photophysical properties. The assembly of the rotaxanes has been achieved using a slight variation of our previously reported synthetic strategy that combines the Cu(i)-catalyzed azide–alkyne cycloaddition reaction (the “click” or CuAAC reaction) with Sauvage''s metal-template protocol. To underline our results, complementary model rotaxanes and catenanes have been prepared using the same strategy and their electrochemistry and photo-induced processes have been investigated. Insights into excited state interactions have been afforded from steady state and time resolved emission spectroscopy as well as transient absorption spectroscopy. It has been found that photo-excitation of the present rotaxanes triggers a cascade of multi-step energy and electron transfer events that ultimately leads to remarkably long-lived charge separated states featuring one-electron reduced C₆₀ radical anion (C₆₀˙^–) and either one-electron oxidized porphyrin (ZnP˙⁺) or one-electron oxidized ferrocene (Fc˙⁺) with lifetimes up to 61 microseconds. In addition, shorter-lived charge separated states involving one-electron oxidized copper complexes ([Cu(phen)₂]²⁺ (τ < 100 ns)), one-electron oxidized zinc phthalocyanine (ZnPc˙⁺; τ = 380–560 ns), or ZnP˙⁺ (τ = 2.3–8.4 μs), and C₆₀˙^– have been identified as intermediates during the sequence. Detailed energy diagrams illustrate the sequence and rate constants of the photophysical events occurring with the mechanically-linked chromophores. This work pioneers the exploration of mechanically-linked systems as platforms to position three distinct chromophores, which are able to absorb light over a very wide range of the visible region, triggering a cascade of short-range energy and electron transfer processes to afford long-lived charge separated states.     

Synthesis, characterization, spectrophotometric, structural and antimicrobial studies of the newly charge transfer complex of p-phenylenediamine with π acceptor picric acid

Charge transfer complex (CTC) of donor, p-phenylenediamine (PPD) and acceptor, 2,4,6-trinitrophenol (picric acid) has been studied in methanol at room temperature. The CT complex was synthesized and characterized by elemental analysis, FTIR spectra, 1H NMR spectroscopy and electronic absorption spectra which indicate the CT interaction associated with proton migration from the acceptor to the donor followed by hydrogen bonding via N+-H?O-. The thermal stability of CT complex was studied using TGA and DTA analyses techniques. The CT complex was screened for its antifungal activity against Aspergillus niger (Laboratory isolate), Candida albicans (IQA-109) and Penicillium sp. (Laboratory isolate) and antibacterial activity against two Gram-positive bacteria Staphylococcus aureus (MSSA 22) and Bacillus subtilis (ATCC 6051) and two Gram-negative bacteria Escherichia coli (K 12) and Pseudomonas aeruginosa (MTCC 2488). It gives good antimicrobial activity. The stoichiometry of the CT complex was found to be 1:1. The physical parameters of CT complex were evaluated by the Benesi-Hildebrand equation. On the basis of the studies, the structure of CT complex is [(PPDH)+(PA)-], and a general mechanism for its formation is proposed.     

Preparation and optical–electrical properties of Al-doped ZnO films

Among the various semiconducting metal oxide materials, ZnO thin films are highly attractive in the development of materials area. In this paper, Al-doped ZnO thin films were prepared by sol–gel dipping and drawing technology and their composition, structure and optical–electrical properties were investigated. XRD results shows that the Al-doped ZnO thin film is of polycrystalline hexagonal wurtzite structure, and the (002) face of the thin film has the strongest orientation at the annealing temperature of 550 °C. The surface resistance of Al-doped ZnO thin film firstly drops and then increases with the increase in annealing temperature. Al doping concentration is also an important factor for improving the conductivity of modified ZnO thin films, and the surface resistance has the tendency to drop at first and then to increase when the Al concentration is increasing. The surface resistance of modified ZnO thin films drops to the lowest point of 139 KΩ sq^?1 when the Al concentration is 1.6 at% and the annealing temperature is 500 °C. The light transmission measurements show that the doping concentration has little influence on light transmittance. The transmittance at the visible region of films is all over 80 %, and the highest value is up to 91 %.     

Synthesis,properties and photochromism of novel charge transfer compounds with Keggin anions and protonated 2,2′-biquinoline

Several novel compounds with protonated 2,2′-biquinoline (biqui) and Keggin polyoxoanions (α-isomers), having the general formula (Hbiqui)_m[XM₁₂O₄₀]·nsolv, X=P (m=3), Si (m=4); M=Mo, W; n=0, 3; solv=H₂O, N,N-dimethylformamide (dmf), were synthesized and characterized by analytical, spectroscopic and X-ray diffraction techniques. Electronic spectroscopy (visible/UV) indicated the presence of intermolecular charge transfer between the organic and inorganic moieties in the solid state. Evidence for the existence of intermolecular electronic interaction in solution was found for compounds with the [SiW₁₂O₄₀]⁴⁻ anion, a fact quite uncommon for charge transfer compounds based on Keggin anions. A single crystal X-ray diffraction study could be performed on (Hbiqui)₄[SiW₁₂O₄₀]·3dmf crystals, but the refinements revealed the presence of highly disordered 2,2′-biquinoline molecules and α-[SiW₁₂O₄₀]⁴⁻ anions. Photosensitivity to sunlight and to W-lamp visible light was assessed for all compounds. Photochromic properties were found for solids with [XMo₁₂O₄₀]^m− Keggin anions. Reduction of these anions upon irradiation was observed by diffuse reflectance and EPR spectroscopy. After a minimum of 5 h under sunlight, the extent of anion reduction followed the order (Hbiqui)₃[PMo₁₂O₄₀]·3dmf>(Hbiqui)₄[SiMo₁₂O₄₀]·3dmf>(Hbiqui)₃[PMo₁₂O₄₀]>(Hbiqui)₄[SiMo₁₂O₄₀]·4H₂O. The Kurtz powder test was used to evaluate the second-order non-linear optical properties of the prepared compounds. (Hbiqui)₄[SiW₁₂O₄₀]·3H₂O originated a second harmonic generation signal with intensity about 15% that of urea for 1064 nm radiation.     

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.     

Unsymmetrical donor–acceptor oligothiophenes end-capped with triphenylamine and phenyldicyanovinyl units

Highly stable unsymmetrical donor–acceptor oligothiophenes equipped with terminal electron-donating triphenylamine and an electron-withdrawing phenyldicyanovinyl groups have been synthesized. An influence of the length of conjugated oligothiophene π-spacer between the donor and acceptor blocks on solubility, thermal, optical and electrochemical properties of such compounds has been revealed.     

The synthesis and spectral properties of a stimuli-responsive D-π-A charge transfer dye

A new donor-π-acceptor (D-π-A) type isophorone dye was synthesized by the condensation reaction between 2-(3,5,5-trimethylcyclohex-2-enylidene)-malononitrile and indole-3-carboxaldehyde. The chemical structure of the dye was characterized by 1H NMR, EA and MS. A novel, chromogenic, fluorescent dye based on indol as donor unit and isophorone as acceptor unit displayed marked UV-visible absorption changes and highly selective fluorescence quenching in the presence of fluoride ion. The dye also exhibited sizeable colour changes when used as a pH-induced molecular switch and as a detector for volatile organic compounds. The absorption and fluorescent intensity of the dye can be reversibly selected by protonation/deprotonation of the amine moiety via control of intramolecular charge transfer (ICT), leading to a molecular switch with "on" and "off" states.     

Gallium trichloride-mediated reactions of ‘double’ donor–acceptor cyclopropanes with alkenes and dienes

The reactions of ‘double’ donor–acceptor cyclopropanes containing a p- or m-phenylene moiety with alkenes or dienes in the presence of GaCl₃ comprise formation of gallium 1,2-zwitterionic intermediates, the structure of final products being substrate dependent. In contrast to the para-or meta-isomers, reaction of 2,2'-(1,2-phenylene)bis(cyclopropane-1,1-dicarboxylate) does not involve alkene and affords isomeric tricyclo[6.2.2.0^2,7]dodeca-2,4,6-triene-9,9,11,11-tetra-carboxylate, a product of intramolecular rearrangement.