Spectral, electrochemical, and photophysical studies of a magnesium porphyrin-fullerene dyad

A covalently linked magnesium porphyrin-fullerene (MgPo-C60) dyad was synthesized and its spectral, electrochemical, molecular orbital, and photophysical properties were investigated and the results were compared to the earlier reported zinc porphyrin-fullerene (ZnPo-C60) dyad. The ab initio B3LYP/3-21G(*) computed geometry and electronic structure of the dyad predicted that the HOMO and LUMO are mainly localized on the MgP and C60 units, respectively. In o-dichlorobenzene containing 0.1 M (n-Bu)4NClO4, the synthesized dyad exhibited six one-electron reversible redox reactions within the potential window of the solvent. The oxidation and reduction potentials of the MgP and C60 units indicate stabilization of the charge-separated state. The emission, monitored by both steady-state and time-resolved techniques, revealed efficient quenching of the singlet excited state of the MgP and C60 units. The quenching pathway of the singlet excited MgP moiety involved energy transfer to the appended C60 moiety, generating the singlet excited C60 moiety, from which subsequent charge-separation occurred. The charge recombination rates, k(CR), evaluated from nanosecond transient absorption studies, were found to be 2-3 orders of magnitude smaller than the charge separation rate, k(CS). In o-dichlorobenzene, the lifetime of the radical ion-pair, MgPo*+-C60*-, was found to be 520 ns which is longer than that of ZnPo*+-C60*- indicating better charge stabilization in MgPo-C60. Additional prolongation of the lifetime of MgPo*+-C60*- was achieved by coordinating nitrogenous axial ligands. The solvent effect in controlling the rates of forward and reverse electron transfer is also investigated.     

Modulating charge separation and charge recombination dynamics in porphyrin-fullerene linked dyads and triads: Marcus-normal versus inverted region.

Photoinduced charge separation (CS) and charge recombination (CR) processes have been examined in various porphyrin-fullerene linked systems (i.e., dyads and triads) by means of time-resolved transient absorption spectroscopy and fluorescence lifetime measurements. The investigated compounds comprise a homologous series of rigidly linked, linear donor-acceptor arrays with different donor-acceptor separations and diversified donor strength: freebase porphyrin-C60 dyad (H2P-C60), zincporphyrin-C60 dyad (ZnP-C60), ferrocene-zincporphyrin-C60 triad (Fc-ZnP-C60), ferrocene-freebase porphyrin-C60 triad (Fc-H2P-C60), and zincporphyrin-freebase porphyrin-C60 triad (ZnP-H2P-C60). Most importantly, the lowest lying charge-separated state of all the investigated systems, namely, that of ferrocenium ion (Fc+) and the C60 radical anion (C60.-) pair in the Fc-ZnP-C60 triad, has been generated with the highest quantum yields (close to unity) and reveals a lifetime as long as 16 micros. Determination of CS and CR rate constants, together with the one-electron redox potentials of the donor and acceptor moieties in different solvents, has allowed us to examine the driving force dependence (-DeltaG0ET) of the electron-transfer rate constants (kET). Hereby, the semilogarithmic plots (i.e., log kET versus -DeltaG0ET) lead to the evaluation of the reorganization energy (lambda) and the electronic coupling matrix element (V) in light of the Marcus theory of electron-transfer reactions: lambda = 0.66 eV and V = 3.9 cm(-1) for ZnP-C60 dyad and lambda = 1.09 eV and V = 0.019 cm(-1) for Fc-ZnP-C60, Fc-H2P-C60, and ZnP-H2P-C60 triads. Interestingly, the Marcus plot in Fc-ZnP-C60, Fc-H2P-C60, and ZnP-H2P-C60 has provided clear evidence for intramolecular CR located in both the normal and inverted regions of the Marcus parabola. The coefficient for the distance dependence of V (damping factor: betaCR = 0.58 A(-1) is deduced which depends primarily on the nature of the bridging molecule.     

Face-to-face pacman-type porphyrin-fullerene dyads: design, synthesis, charge-transfer interactions, and photophysical studies

Pacman-type face-to-face zinc-porphyrin-fullerene dyads have been newly synthesized and studied. Owing to the close proximity of the donor and acceptor entities, strong pi-pi intramolecular interactions between the porphyrin and fullerene entities resulted in modulating the spectral and electrochemical properties of the dyads. New absorption and emission bands that correspond to the charge-transfer interactions were observed in the near-IR region. Time-resolved transient absorption studies revealed efficient photoinduced electron transfer from the singlet excited porphyrin to the fullerene entity. The rate constants for photoinduced electron transfer are analyzed in terms of the Marcus theory of electron transfer, which afforded a large electron coupling matrix element (V=140 cm(-1)) for the face-to-face dyads. As a consequence of the large charge-recombination driving force in the Marcus inverted region, a relatively long lifetime of the charge-separated state has been achieved.     

Design, synthesis and photophysical studies of simple fluorescent anion PET sensors using charge neutral thiourea receptors

The synthesis of four fluorescent photoinduced electron transfer (PET) chemosensors 1-4 for anions is described. These are all based on a simple design employing charge neutral aliphatic or aromatic thiourea anion receptors connected to an anthracene fluorophore via a methylene spacer. Here the anion recognition occurred through 1 : 1 hydrogen bonding between the thiourea protons and the anion, as demonstrated by observing the changes in the (1)H NMR in DMSO-d(6) where the two thiourea protons were shifted downfield upon addition of anions. Whereas 1-3 were designed for the detection of anions such as fluoride, acetate or phosphate, 4 was made for the recognition of N-protected amino acids. All the sensors showed 'ideal' behaviour where only the fluorescence emission was quenched upon anion recognition, due to enhanced efficiency of electron transfer quenching from the receptor to the excited state of the fluorophore. By simply varying the nature of the thiourea substituent it was possible to modulate, or tune, the acidity of the thiourea receptor moiety, altering the sensitivity of the anion recognition. For, the anion selectivity and the degree of the fluorescence quenching were in the order of F(-) > AcO(-) > H(2)PO(4)(-), with Cl(-) or Br(-) not being detected.     

Observation of the marcus inverted region of electron transfer reactions at a liquid/liquid interface

Scanning electrochemical microscopy was used to probe the influence of a driving force on the heterogeneous electron transfer (ET) processes at the externally polarized water/1,2-dichloroethane interface. Being a part of the driving force, the Galvani potential difference at the interface, Deltaowphi, can be quantitatively controlled in a wide range, allowing the precise measurements of the rate constants of the ET reactions. Two opposite systems were chosen in this work. One was 5,10,15,20-tetraphenyl 21H,23H-porphyrin zinc (ZnPor, O)/Fe(CN)64- (W), and the other was TCNQ (O)/Fe(CN)63- (W). For both systems studied, the relations between the rate constant and the Deltaowphi were of parabolic shape; that is, the rate constants increased initially with the Deltaowphi until reaching a maximum and then decreased steadily as the Deltaowphi increased further. This is in accordance with the prediction of the Marcus theory. To our knowledge, this is the first report that the Marcus inverted region can be observed electrochemically at an unmodified liquid/liquid interface with only one redox couple at each phase. The effect of the concentrations of the organic supporting electrolyte has also been discussed in detail.     

Molecular simulations for the conformational assessment of a porphyrin-fullerene dyad in different environments

Conformational space of a porphyrin-fullerene dyad with the donor and acceptor connected by a relatively flexible linker is studied by molecular dynamics simulations in both non-polar and polar solvents, as well as in vacuum. The most probable conformations obtained from the vacuum MD simulations were optimized with semi-empirical (SE) and density functional theory (DFT) methods and the extent of the structural changes is assessed. The computational results indicate the co-existence of different conformers in both polar and nonpolar solvents showing agreement with experimental results. The most probable vacuum conformations at 300 K are similar to the ones at 0 K, while the structures most often observed in the solvents show less compact conformations. Optimization with SE and DFT calculations leads to structures, which represent relatively well the folded conformations in solvent, which validates the electronic structure calculations relevant to describing photoinduced electron-transfer in H2P-O34-C60.     

Ab initio description of photoabsorption and electron transfer in a doubly-linked porphyrin-fullerene dyad

Structure, photoabsorption and excited states of two representative conformations obtained from molecular dynamics (MD) simulations of a doubly-linked porphyrin-fullerene dyad DHD6ee are studied by using both DFT and wavefunction based methods. Charge transfer from the donor (porphyrin) to the acceptor (fullerene) and the relaxation of the excited state are of special interest. The results obtained with LDA, GGA, and hybrid functionals (SVWN, PBE, and B3LYP, respectively) are analyzed with emphasis on the performance of used functionals as well as from the point of view of their comparison with wavefunction based methods (CCS, CIS(D), and CC2). Characteristics of the MD structures are retained in DFT optimization. The relative orientation of porphyrin and fullerene is significantly influencing the MO energies, the charge transfer (CT) in the ground state of the dyad and the excitation of ground state CT complex (g-CTC). At the same time, the excitation to the locally excited state of porphyrin is only little influenced by the orientation or cc distance. TD-DFT underestimates the excitation energy of the CT state, however for some cases (with relatively short donor-acceptor separations), the use of a hybrid functional like B3LYP alleviates the problem. Wavefunction based methods and CC2 in particular appear to overestimate the CT excitation energies but the inclusion of proper solvation models can significantly improve the results.     

Electron transfer in supercritical carbon dioxide: ultraexothermic charge recombination at the end of the "inverted region"

Charge-recombination rates in contact radical-ion pairs, formed between aromatic hydrocarbons and nitriles in supercritical CO(2) and heptane, decrease with the exothermicity of the reactions until they reach -70 kcal mol(-1), but from there on an increase is observed. The first decrease in rate is typical of the "inverted region" of electron-transfer reactions. The change to an increase in the rate for ultra-exothermic electron transfer indicates a new free-energy relationship. We show that the resulting "double-inverted region" is not due to a change in mechanism. It is an intrinsic property of electron-transfer reactions, and it is due to the increase of the reorganisation energy with the reaction exothermicity.     

Design,synthesis, characterization,photophysical and pH chemosensor studies of novel 2,4,6-trisubstituted pyridines

For the application in organic electronics as well as pH meters, a series of novel 2,4,6-trisubstituted pyridines have been synthesized by the reaction of substituted aromatic aldehydes and substituted 3-acetylcoumarin with ammonium acetate. The structures of all the new compounds were characterized by IR, NMR, and GC–MS analysis. The important photo physical prerequisites for organoelectronic such as optical absorption and thermal stability were determined for the synthesized molecules. Optical properties were studied by UV–visible absorption and fluorescence spectroscopy. Optical band gaps of the 2,4,6-trisubstituted pyridines were found to be around 3.01–3.06?eV as calculated from their onset absorption edge. The pH-dependent changes in the fluorescence intensity suggest that 2,4,6-trisubstituted pyridines are useful applicants in intracellular pH meters.     

Design, synthesis and photophysical studies of an emissive, europium based, sensor for zinc

The synthesis of the probe complex . and photophysical studies in aqueous media are described. . is designed to be luminescently responsive to Zn(II) in the presence of a competitive ionic mixture at pH 7.4. The structure of the complex is based upon a carboxylate functionalized azamacrocycle and possesses a chromophoric bis-picolyl unit for binding Zn(II). The effect on both ligand fluorescence and Eu(III) phosphorescence was investigated in the presence and absence of Zn(II). The study revealed that binding Zn(II) increased the intensity of ligand fluorescence and modulated the inner sphere hydration number of Eu(III) (q increases from 0 to 2). This modulation in coordination environment induced pronounced changes in the form of the steady state spectra allowing the presence of Zn(II) to be signalled by both changes in emission intensity and lifetime.     

Design, synthesis, and photophysical characterization of water-soluble chlorins

The use of chlorins as photosensitizers or fluorophores in a range of biological applications requires facile provisions for imparting high water solubility. Two free base chlorins have been prepared wherein each chlorin bears a geminal dimethyl group in the reduced ring and a water-solubilizing unit at the chlorin 10-position. In one design (FbC1-PO3H2), the water-solubilizing unit is a 1,5-diphosphonopent-3-yl ("swallowtail") unit, which has previously been used to good effect with porphyrins. In the other design (FbC2-PO3H2), the water-solubilizing unit is a 2,6-bis(phosphonomethoxy)phenyl unit. Two complementary routes were developed for preparing FbC2-PO3H2 that entail introduction of the protected phosphonate moieties either in the Eastern-half precursor to the chlorin or by derivatization of an intact chlorin. Water-solubilization is achieved in the last step of each synthesis upon removal of the phosphonate protecting groups. The chlorins FbC1-PO3H2 and FbC2-PO3H2 are highly water-soluble (>10 mM) as shown by 1H NMR spectroscopy (D2O) and UV-vis absorption spectroscopy. The photophysical properties of the water-soluble chlorins in phosphate-buffered saline solution (pH 7.4) at room temperature were investigated using static and time-resolved absorption and fluorescence spectroscopic techniques. Each chlorin exhibits dominant absorption bands in the blue and the red region (lambda = 398, 626 nm), a modest fluorescence yield (Phi f approximately 0.11), a long singlet excited-state lifetime (tau = 7.5 ns), and a high yield of intersystem crossing to give the triplet state (Phi isc = 0.9). The properties of the water-soluble chlorins in aqueous media are comparable to those of hydrophobic chlorins in toluene. The high aqueous solubility combined with the attractive photophysical properties make these compounds suitable for a wide range of biomedical applications.     

Gold nanoparticles functionalized with deep-cavity cavitands: synthesis, characterization, and photophysical studies

In this report, we present methods of functionalization of AuNP's with deep-cavity cavitands that can include organic molecules. Two types of deep-cavity cavitand-functionalized AuNP's have been synthesized and characterized, one soluble in organic solvents and the other in water. Functionalized AuNP soluble in organic solvents forms a 1:1 host-guest complex where the guest is exposed to the exterior solvents. The one soluble in water forms a 2:1 host-guest complex where the guest is protected from solvent water. Phosphorescence from thiones and benzil included within heterocapsules attached to AuNP was quenched by gold atoms present closer to the guests included within deep-cavity cavitands. During this investigation, we have synthesized four new deep-cavity cavitands. Of these, two thiol-functionalized hosts allowed us to make stable AuNP's. However, AuNP's protected with two amine-functionalized cavitands tended to aggregate within a day.     

Synthesis, cyclic voltammetry, and photophysical properties of a bridged o-phenylenediamine-C(60) dyad

The synthesis, complete spectroscopic characterization, cyclic voltammetry, and photophysical measurements of a new o-phenylenediamine-C(60) dyad are described. By using a tether strategy, only a single regioisomer was obtained. Cyclic voltammetry measurements indicate that the two electroactive groups do not interact in their singlet ground states. Photophysical investigations reveal a rapid photoinduced electron transfer between the singlet excited state of the fullerene acceptor and the o-phenylenediamine donor, yielding a charge-separated radical pair.     

Design and synthesis of a self-assembled photochemical dyad based on selective imidazole recognition

The unique recognition properties of phenanthroline-strapped zinc porphyrin 1, which displays extremely high affinity for N-unsubstituted imidazoles, has been used as the driving force for the assembly of a photochemical dyad involving a zinc(II) porphyrin as energy donor and a free base porphyrin as energy acceptor. The synthesis of the imidazole-substituted porphyrin is described together with the assembly of the dyad. (1)H NMR titrations confirm the formation of a 1/1 complex between 1 and 6, as well as insertion of the imidazole of the acceptor within the phenanthroline strap of the donor. Preliminary fluorescence quenching measurements show that efficient energy transfer occurs between the self-assembled components.     

Design,synthesis, and photophysical characterization of novel pentacyclic red shifted azine dyes

As part of our continuing efforts to develop second generation photodynamic therapeutic agents [1], we synthesized three pentacyclic azine dyes that were designed with the aid of MNDO calculations to absorb visible light having wavelengths longer than 600 nm. Photophysical measurements for the azine dyes 1,4,8,11-tetraethyl-1,2,3,4,8,9,10,11,13-nonahydrodipyrazino[2,3-b:2′, 3′-i] phenazinium acetate, 13 , 1,4,8,11-tetraethyl-2,3,4,8,9,10,11,12,13-octahydro-13-methyldipyrazino[2,3-b:2,3′-i]phenazinium iodide, 14 , and l,4,8,11,13-pentaethyl-2,3,4,8,9,10,11,12,13-octahydrodipyrazino[2,3-b:2′,3′-i]phenazinium iodide, 15 , are highlighted by a 35 nm red shift in their absorption spectra and a 5–7 fold increase in their singlet oxygen quantum yield relative to tricyclic model compounds 3,7-bis(diethylamino)phenazinium chloride, 20 , and 3,7-bis(diethylamino)-5-ethyl-phenazinium iodide, 21 , which were also synthesized for this study. Incorporation of rigid peripheral tetrahydropyrazino ring systems in the pentacyclic azines 13 , 14 , and 15 are responsible for the improved fluorescence and singlet oxygen quantum yields relative to the tricyclic azines 20 and 21 .     

Supramolecular dyad derived from a buckybowl series of O2N2-donor naphthodiaza-crowns coordinated to C60: photophysical,NMR and theoretical studies

Supramolecular complexation of C₆₀ with L¹-L⁵ were studied in toluene, chloroform and 1,2-dichlorobenzene solvents using UV–vis, fluorescence, ¹H, ¹³C NMR spectroscopy as well as density functional theory (DFT) calculations. The Job’s plot of continuous variation method established 1:1 stoichiometry for L¹-L⁵/C₆₀. Binding constants (K) calculated for L¹-L⁵/C₆₀ were also determined employing UV–vis and fluorescence spectroscopy. Both steady-state and time-resolved fluorescence spectroscopic surveys showed remarkable fluorescence quenching phenomenon for L¹-L⁵ in the presence of C₆₀ which was primarily attributed to involvement of a static process. The observed fluorescence quenching in L¹–L⁵ was described in terms of both π–π and n–π interactions of the naphthalene moieties and the nitrogen donor groups on the aza-crown macrocyclic ligands with C₆₀, respectively. Moreover, DFT calculations using B₃LYP/6-31G* basis set confirmed on the aforesaid π–π interaction of naphthalene groups on the aza-crowns with C₆₀. The DFT calculations also established significant distributions of charge between C₆₀ and L¹-L⁵ in according to the electronic structure and geometry of L¹-L⁵/C₆₀, very similar to phthalocycnine/C₆₀ systems.     

Design,synthesis, photophysical,and electrochemical properties of DCM‐based conjugated polymers for light‐emitting devices

A series of conjugated hyperbranched polymers, hyperbranched copolymers, and linear polymers containing 2‐pyran‐4‐ylidenemalononitrile (acceptor) and triphenylamine/fluorene (donor) units were synthesized and characterized by FTIR, ¹H NMR, thermogravimetric analyses, differential scanning calorimetry, gel permeation chromatography, UV–visible, photoluminescence, and cyclic voltammetry measurements. All the polymers show red‐light emission in the range of 566–656 nm both in solution and in solid state. The quantum efficiency of the polymers was in the range of 56–82%. Among the six polymers synthesized, only polymers containing fluorene units show T_g and polymers based on triphenylamine not exhibit T_g. The band gap of these polymers were found to be reasonably low; hyperbranched copolymer containing fluorene unit shows lowest band gap of 2.18 eV due to the stabilization of LUMO energy level by the electron withdrawing ? CN groups. The thermal and solubility behavior of the polymers were found to be good. All the EL spectra of the devices (indium‐tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/polymer/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline/tris(8‐hydroxyquinoline)aluminum)/LiF/Al) show red‐light emission, and the device fabricated with P3 and P4 shows maximum luminance and luminous efficiency of 4104 cd m^?2 and 0.55 cd Å^?1 and 3696 cd m^?2 and 0.47 cd Å^?1, respectively, indicates that they had the best carrier balance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Selective self-assembly of hexameric homo- and heteropolymetallic lanthanide wheels: synthesis, structure, and photophysical studies

A rational approach to the formation of pure heteropolymetallic lanthanide complexes that uses a two-step assembly strategy and exploits the different size requirements of the two metals included in the final structure is described. The investigation of the assembly of [LnL2](Otf) (L = 2,2':6',2' '-terpyridine-6-carboxylate) complexes into hexametallic rings hosting an additional hexacoordinated lanthanide cation was crucial for the development of this strategy. The formation and size of the cyclic assembly are controlled by the ionic radius and by the coordination number of the lanthanides. The rather high luminescence quantum yield of the heptaeuropium complex (25%) indicates that the ring structure is well adapted to include highly luminescent lanthanide complexes in nanosized architecture. The use of a stepwise synthetic strategy leads to the selective assembly of large heteropolymetallic rings. The addition of a smaller lanthanide ion to the [EuL2](Otf) complex in anhydrous acetonitrile leads selectively to heterometallic species with the Eu ions located on the peripheral sites and the smaller ion occupying only the central site. The high selectivity is the result of the different size requirements of the two metal sites present in the cyclic structure. The heterometallic structure of the isolated [Lu subset (EuL2)6](Otf)9 complex was confirmed by X-ray diffraction and by high resolution solid-state photophysical studies. The described synthetic approach allowed us to obtain the first example of selective assembly of two different lanthanide ions in a large polymetallic structure characterized in solution and in the solid state and will make the isolation of planned dimetallic combinations presenting different lanthanide emitters in the peripheral sites possible.     

Nanosecond time-resolved studies of long-lived photoinduced charge separation in the dyad fluorescein-anthraquinone-methyl ester adsorbed on TiO2 colloids

A dyad composed of fluorescein and 2-methyl-anthraquinone (FL-AQ) was synthesized and its photophysical properties were examined by absorption, fluorescence spectroscopy, and fluorescence lifetime. The charge-separated state formed by photoinduced intramolecular electron transfer was detected by nanosecond transient absorption spectroscopy for the first time. When FL is excited in solution, the photoinduced electron transfer from FL to AQ proceeds efficiently. The rate constant and the efficiency of intramolecular electron transfer are 3.95 x 10(9) s(-1) and 95%, respectively. Its charge-separated state lifetime is too short to detect by transient absorption spectroscopy. Adding nanometer colloidal TiO(2) to an FL-AQ ethanol solution prolongs the lifetime of the charge-separated state, so its transient absorption signal is recorded significantly. The lifetimes of FL(+). at 480 nm and AQ(-). at 560 nm in the FL-AQ/TiO(2) colloidal system are 11.1 and 8.93 mivros, respectively.