Intramolecular triplet energy transfer in donor-acceptor molecules linked by a crown ether bridge

Bichromophoric compounds BP-C-NP and BP-C-NBD were synthesized with benzophenone chromophore (BP) as the donor, and 2-naphthyl (NP) and norbornadiene group (NBD) as the acceptor, respectively. Their intramolecular triplet energy transfer was examined. The bridges linking the donor and acceptors in these molecules involve a crown ether moiety complexing a sodium ion. Phosphorescence quenching, flash photolysis and photosensitized isomerization experiments indicate that intramolecular triplet energy transfer occurs with rate constants of about 3.3 x 10(5) and 4.8 x 10(5) s(-1) and efficiencies of about 33 and 42 % for BP-C-NP and BP-C-NBD, respectively. Theoretical calculations indicate that these molecules adopt conformations below room temperature which allow their two-end chromophores conducive to through-space energy transfer.     

Conversion of intramolecular singlet electron transfer at room temperature into triplet energy transfer at 77 K: photoisomerization in norbornadiene- and carbazole-labeled poly(aryl ether) dendrimers

A series of Fréchet-type poly(aryl ether) dendrimers (CZ-Gn-NBD, n = 1-3) with carbazole (CZ) chromophores and a norbornadiene (NBD) group attached to the periphery and the core, respectively, were synthesized, and their photophysical and photochemical properties were investigated. Selective excitation of the carbazole units in CZ-Gn-NBD resulted in a singlet electron transfer from CZ to NBD at room temperature, and an intersystem crossing followed a triplet-triplet energy transfer from CZ to NBD in glassy 2-methyltetrahydrofuran at 77 K. Both singlet electron transfer and triplet energy transfer processes lead to the isomerization of the norbornadiene group into the quadricyclane (CZ-Gn-QC). The efficiencies and the rate constants for singlet electron transfer are approximately 88, 80, and 74% and 1.8 x 10(9), 6.1 x 10(8), and 4.0 x 10(8) s(-1) for generations 1-3, respectively. The quantum yields of the intramolecular photosensitized isomerization are measured to be approximately 0.013, 0.012, and 0.011, and the efficiencies of triplet norbornadiene formation via singlet electron transfer are approximately 0.070, 0.065, and 0.059 for generations 1-3, respectively. The light-harvesting ability of CZ-Gn-NBD increases with the generation due to an increase of the number of peripheral chromophores. In glassy 2-methyltetrahydrofuran at 77 K, the triplet-triplet energy transfer proceeds with efficiencies of approximately 0.86, 0.64, and 0.36 and rate constants of 0.96, 0.25, and 0.08 s(-1) for generations 1-3, respectively. The intramolecular singlet electron transfer and triplet energy transfer in CZ-Gn-NBD proceed mainly via a through-space mechanism involving the proximate donor (folding back conformation) and acceptor groups.     

Direct observation of the intramolecular triplet-triplet energy transfer in poly(aryl ether) dendrimers

A series of benzophenone (BP) and naphthalene (NA) labeled poly(aryl ether) dendrimers (BP-Gn-NA), generations 1-4, were synthesized, and their photophysical properties were examined. Flash photolysis demonstrates that the triplet energy in BP-Gn-NA can be transferred from the peripheral BP chromophores to the core NA group with the efficiencies of ca. 0.97, 0.96, 0.88, and 0.54 and with the rate constants of 1.4x10(8), 1.2x10(8), 9.5x10(7), and 1.3x10(7) s-1 at room temperature for generations 1-4, respectively. The transient absorption spectra of BP-Gn-NA show clearly the formation of the triplet NA absorption along with the decay of the triplet BP one with an isosbestic point at 475 nm, which gives direct evidence of the triplet energy transfer from the periphery BP chromphores to the core NA group. The phosphorescence of the NA group attached to the focal point was observed when the periphery BP chromophores were selectively irradiated in BP-G1-NA at 77 K. The triplet energy transfer occurs at 77 K with the efficiencies of 1.0, 0.16, 0.17, and 0.21 for generations 1-4, respectively. The intramolecular triplet energy transfer is proposed to proceed mainly via a through space mechanism.     

Remote Sensitized Photoisomerization via Through‐Bond Triplet–Triplet Energy Transfer Mediated by a Salt Bridge in a Supramolecular Dyad

A supramolecular dyad, BP‐(amidinium‐carboxylate)‐NBD is constructed, in which benzophenone (BP) and norbornadiene (NBD) are connected via an amidinium‐carboxylate salt bridge. The photophysical and photochemical properties of the assembled BP‐(amidinium‐carboxylate)‐NBD dyad are examined. The phosphorescence of the BP chromophore is efficiently quenched by the NBD group in BP‐(amidinium‐carboxylate)‐NBD via the salt bridge. Time‐resolved spectroscopy measurements indicate that the lifetime of the BP triplet state in BP‐(amidinium‐carboxylate)‐NBD is shortened due to the quenching by the NBD group. Selective excitation of the BP chromophore results in isomerization of the NBD group to quadricyclane (QC). All of these observations suggest that the triplet–triplet energy transfer occurs efficiently in the BP‐(amidinium‐carboxylate)‐NBD salt bridge system. The triplet–triplet energy transfer process proceeds with efficiencies of approximately 0.87, 0.98 and the rate constants 1.8×10³ s^?1, and 1.3×10⁷ s^?1 at 77 K and room temperature, respectively. The mechanism for the triplet–triplet energy transfer is proposed to proceed via a “through‐bond” electron exchange process, and the non‐covalent bonds amidinium‐carboxylate salt bridge can mediate the triplet–triplet energy transfer process effectively for photochemical conversion.     

Benzophenone and zinc(II) phthalocyanine dichromophores-labeled poly (aryl ether) dendrimer: synthesis,characterization and photoinduced energy transfer

A series of benzophenone chromospheres and zinc(II) phthalocyanine dichromophores labeled poly (aryl benzyl ether) dendrimer (G_n-DZnPc(BP)_8n, n = 1?2) were synthesized. Their structures were characterized by elemental analysis, ¹H NMR, IR, UV–vis and matrix-assisted laser desorption/ionization time-of-flight spectrometry (MALDI-TOF MS). Their photophysical properties were examined by steady-state and time-resolved fluorescence methods. Both the poly (aryl benzyl ether) dendrimer and BP terminal chromophores had a significant effect on photophysical properties of the zinc(II) phthalocyanine core. Time-resolved spectroscopic measurements indicated that the lifetime of benzophenone (donor) chromophore was longer than that of the zinc(II) phthalocyanine (acceptor). The fluorescence of the peripheral benzophenone chromophores was quenched by the phthalocyanine group attached to the focal point. All of these observations suggest that an intramolecular singlet energy transfer occurs in G_n-DZnPc(BP)_8n molecules. The light-harvesting abilities of these molecules increased with generations due to an increase in the number of benzophenone chromophores. The energy transfer efficiencies were ca. 0.49 and 0.68 for generations 1 and 2, respectively, and the rate constants of the singlet-singlet energy transfer were ca. 10⁸ s^?1. The rate constants changed inconspicuously with increase of dendron generations. The intramolecular singlet-singlet energy transfer is proposed to proceed mainly via a Förster-type interaction mechanism involving the dendrimer backbone as a scaffold to hold the peripheral benzophenone chromophores and the phthalocyanine core together. This dendrimer was an effective new energy transmission complex with high efficiency and could be used as a potential light-harvesting system.     

Valence isomerization in dendrimers by photo-induced electron transfer and energy transfer from the dendrimer backbone to the core

A series of poly(aryl ether) dendrimers with a norbornadiene (NBD) group attaching to the core (Gn-NBD), generations 1–4, were synthesized and characterized, and their photophysical and photochemical properties were examined. The fluorescence of the dendrimer backbone is quenched by the norbornadiene group as a result of the electron transfer and energy transfer from the dendrimer backbone to the norbornadiene group in Gn-NBD. Selective excitation of the dendrimer backbone results in an isomerization of the norbornadiene group to the quadricyclane (QC) group. The intramolecular electron transfer and energy transfer efficiencies are ca. 0.93, 0.73, 0.54, 0.30 in dichloromethane, and ca. 0.90, 0.70, 0.55, 0.34 in tetrahydrofuran for generations 1–4, respectively, with the rate constant ca. 10¹⁰ s⁻¹. The light-harvesting ability of these dendritic molecules is demonstrated by the enhanced valence isomerization rate of NBD to QC with increasing generation.     

Unveiling the Triplet State of a 4‐Amino‐7‐Nitrobenzofurazan Derivative in Cyclohexane

The nitrobenzofurazan (NBD) moiety has gained tremendous popularity over the last decades due to its fluorogenic nature. Indeed, upon interaction with aliphatic amines, it generates a stable fluorescent adduct, which has been used for protein and lipid labeling. In fact the 4‐amino substituted NBD belongs to the broad family of intramolecular charge transfer molecules, with the amino group acting as an electron donor upon photoexcitation, and the nitro group as an electron acceptor. Although the singlet excited state of 4‐amino NBD derivatives has been abundantly studied, investigation of its triplet manifold is scarce and even the absence of intersystem crossing for this type of molecules has been suggested. However, intramolecular charge transfer molecules are known to undergo intersystem crossing and high phosphorescence quantum yields have been reported in a nonpolar solvent. In the present paper, we have investigated the photophysical and photochemical properties of N‐hexyl‐7‐nitrobenzo[c][1,2,5]xadiazole‐4‐amine. We have shown the existence of a triplet state for this molecule in cyclohexane via nanosecond laser flash photolysis. Interestingly, deactivation of the triplet state leads to photoproducts formation, which are only present in the absence of oxygen.     

降冰片二烯-甾体-二苯酮两元化合物的合成及其光化学研究

本文合成了一个新的降冰片二烯-甾体-二苯酮两元化合物(NBD-S-BP), 并研究了它的光化学反应。NBD-S-BP在λ>350nm光的照射下, BP基团吸收光能, 系间窜越到三线态后将能量传递到NBD基团并使后者异构化为四环烷, 量子效率为21%。     

SENSITIZATION OF THE PHOSPHORESCENCE OF INDOLE THROUGH INTRAMOLECULAR ENERGY TRANSFER FROM THE TRIPLET STATE OF COVALENTLY LINKED ACETOPHENONE IN RIGID MEDIA AT 77 K

Abstract— In an attempt to study the quenching of the triplet state of acetophenone by indole, we have prepared the compounds containing these chromophores intramolecularly. The emission measurements in rigid glasses at 77 K have indicated that the quenching of the triplet acetophenone is due to intramolecular triplet-triplet energy transfer to the indole chromophore, resulting in the sensitization of the indole phosphorescence. The efficiency of the energy transfer has reached ca. 100% in ethanol glasses, while it has been suggested that in methylcyclohexane glasses, the indole chromophore except for 1-methyl derivative is subjected to strong interaction with the acetophenone chromophore other than electronic energy transfer.     

Photoinduced intramolecular electron transfer and triplet energy transfer in a steroid-linked norbornadiene-carbazole dyad

Bichromophoric compound 3 beta-((2-(methoxycarbonyl)bicyclo[2.2.1]hepta-2,5-diene-3-yl)carboxy)androst-5-en-17 beta-yl-[2-(N-carbazolyl)acetate] (NBD-S-CZ) was synthesized and its photochemistry was examined by fluorescence quenching, flash photolysis, and chemically induced dynamic nuclear polarization (CIDNP) methods. Fluorescence quenching measurements show that intramolecular electron transfer from the singlet excited state of the carbazole to the norbornadiene group in NBD-S-CZ occurs with an efficiency (Phi SET) of about 14 % and rate constant (kSET) of about 1.6 x 10(7) s-1. Phosphorescence and flash photolysis studies reveal that intramolecular triplet energy transfer and electron transfer from the triplet carbazole to the norbornadiene group proceed with an efficiency (TET + TT) of about 52 % and rate constant (kTET + kTT) of about 3.3 x 10(5) s-1. Upon selective excitation of the carbazole chromophore, nuclear polarization is detected for protons of the norbornadiene group (emission) and its quadricyclane isomer (enhanced absorption); this suggests that the isomerization of the norbornadiene group to the quadricyclane proceeds by a radical-ion pair recombination mechanism in addition to intramolecular triplet sensitization. The long-distance intramolecular triplet energy transfer and electron transfers starting both from the singlet and triplet excited states are proposed to proceed by a through-bond mechanism.     

双枝芳醚树枝形聚合物构象研究

合成了外围只以一个芘基团修饰、核心为苯胺的双枝芳醚树枝形聚合物Py-[Gn]2-NPh (n＝1～2), 利用分子内电子转移和激基复合物的形成对其折叠构象和折叠程度进行了研究. 二氯甲烷溶液中选择性激发芘基团, 树枝形聚合物Py-[Gn]2-NPh分子内发生从苯胺到芘基团之间的电子转移, 观察到了分子内外围芘基团和核心苯胺基团之间形成激基复合物的发光, 为芳醚树枝形聚合物折叠构象的存在给出了直接实验观察. 二氯甲烷溶液中1～2代Py-[Gn]2-NPh分子内电子转移效率分别为0.87和0.81, 速率常数分别为2.3×108和1.5×108 s－1. 利用电子转移速率常数估算得到1～2代Py-[Gn]2-NPh分子内给、受体之间的距离分别为0.79和0.81 nm, 说明双枝芳醚树枝形聚合物与单枝结构类似, 其外围基团也可以折叠到达分子内部接近核心的位置.     

Bipolar molecules with high triplet energies: synthesis, photophysical, and structural properties

This article sheds new light on the interplay of electronic and conformational effects in luminescent bipolar molecules. A series of carbazole/1,3,4-oxadiazole hybrid molecules is described in which the optoelectronic properties are systematically varied by substituent effects which tune the intramolecular torsion angles. The synthesis, photophysical properties, cyclic voltammetric data, X-ray crystal structures, and DFT calculations are presented. Excited state intramolecular charge transfer (ICT) is observed from the donor carbazole/2,7-dimethoxycarbazole to the acceptor phenyl/diphenyloxadiazole moieties. Introducing more bulky substituents onto the diphenyloxadiazole fragment systematically increases the singlet and triplet energy levels (E(S) and E(T)) and blue shifts the absorption and emission bands. The triplet excited state is located mostly on the oxadiazole unit. The introduction of 2,7-dimethoxy substituents onto the carbazole moiety lowers the value of E(S), although E(T) is unaffected, which means that the singlet-triplet gap is reduced (for 7bE(S) - E(T) = 0.61 eV). A strategy has been established for achieving unusually high triplet levels for bipolar molecules (E(T) = 2.64-2.78 eV at 14 K) while at the same time limiting the increase in the singlet energy.     

Triplet-triplet energy transfer in Langmuir-Blodgett films

The temperature effect on the efficiency of the triplet energy transfer between different molecules included in molecular layers by the Langmuir-Blodgett (LB) procedure was studied. The efficiency of the triplet energy transfer from the LB film of the donor to the LB film of the acceptor is determined by the homogeneous broadening of the energy donor levels.     

Water- and acid-mediated excited-state intramolecular proton transfer and decarboxylation reactions of ketoprofen in water-rich and acidic aqueous solutions

We present an investigation of the decarboxylation reaction of ketoprofen (KP) induced by triplet excited-state intramolecular proton transfer in water-rich and acidic solutions. Nanosecond time-resolved resonance Raman spectroscopy results show that the decarboxylation reaction is facile in aqueous solutions with high water ratios (water/acetonitrile ≥50%) or acidic solutions with moderate and strong acid concentration. These experimental results are consistent with results from density functional theory calculations in which 1) the activation energy barriers for the triplet-state intramolecular proton transfer and associated decarboxylation process become lower when more water molecules (from one up to four molecules) are involved in the reaction system and 2) perchloric acid, sulfuric acid, and hydrochloric acid can shuttle a proton from the carboxyl to carbonyl group through an initial intramolecular proton transfer of the triplet excited state, which facilitates the cleavage of the C-C bond, thus leading to the decarboxylation reaction of triplet state KP. During the decarboxylation process, the water molecules and acid molecules may act as bridges to mediate intramolecular proton transfer for the triplet state KP when KP is irradiated by ultraviolet light in water-rich or acidic aqueous solutions and subsequently it generates a triplet-protonated carbanion biradical species. The faster generation of triplet-protonated carbanion biradical in acidic solutions than in water-rich solutions with a high water ratio is also supported by the lower activation energy barrier calculated for the acid-mediated reactions versus those of water-molecule-assisted reactions.     

Light-harvesting in carbonyl-terminated phenylacetylene dendrimers: The role of delocalized excited States and the scaling of light-harvesting efficiency with dendrimer size

The photophysics of a family of conjugated phenylacetylene (PA) light-harvesting dendrimers are studied using steady-state and time-resolved optical spectroscopy. The dendrimers consist of a substituted PA core surrounded by meta-branched PA arms. The total number of PA moieties ranges from 3 (first generation) to 63 (fifth generation). By using an alcohol/ketone substituent at the dendrimer core, we avoid through-space Forster transfer from the peripheral PA donors to the core acceptor (in this case, the carbonyl group), which simplifies the analysis of these molecules relative to the perylene-terminated molecules studied previously. The delocalized excited states previously identified in smaller dendrons are seen in these larger dendrimers as well, and their influence on the intersite electronic energy transfer (EET) is analyzed in terms of a point-dipole Forster model. We find that these new delocalized states can both enhance EET (by decreasing the spatial separation between donor and acceptor) and degrade it (by lowering the emission cross section and shifting the energy, resulting in poorer spectral overlap between donor and acceptor). The combination of these two effects leads to a calculated intersite transfer time of 6 ps, in reasonable agreement with the 5-17 ps range obtained from experiment. In addition to characterizing the electronic states and intersite energy transfer times, we also examine how the overall light-harvesting efficiency scales with dendrimer size. After taking the size dependence of other nonradiative processes, such as excimer formation, into account, the overall dendrimer quenching rate k(Q) is found to decrease exponentially with dendrimer size over the first four generations. This exponential decrease is predicted by simple theoretical considerations and by kinetic models, but the dependence on generation is steeper than expected based on those models, probably due to increased disorder in the larger dendrimers. We discuss the implications of these results for dendrimeric light-harvesting structures based on PA and other chemical motifs.     

Tailoring Excited State Properties and Energy Levels Arrangement via Subtle Structural Design on D‐π‐A Materials

The donor‐π‐conjugated‐acceptor (D‐π‐A) structure is an important design for the luminescent materials because of its diversity in the selections of donor, π‐bridge and acceptor groups. Herein, we demonstrate two examples of D‐π‐A structures capable to finely modulate the excited state properties and arrangement of energy levels, TPA‐AN‐BP and CZP‐AN‐BP , which possess the same acceptor and π‐bridge but different donor. The investigation of their photophysical properties and DFT calculation revealed that the D‐π‐A structure with proper donor, π‐bridge and acceptor can result in separation of frontier molecular orbitals on the corresponding donor and acceptor with an obvious overlap on the π‐bridge, resulting in a hybridized local and charge‐transfer (HLCT ) excited state with high photoluminescent (PL ) efficiencies. Meanwhile, their singlet and triplet states are arranged on corresponding moieties with large energy gap between T₂ and T₁ , and a small energy gap between S₁ and T₂ , which favor the reverse intersystem crossing (RISC ) from high‐lying triplet levels to singlet levels. As a result, the sky‐blue emission non‐doped OLED based on the TPA‐AN‐BP reached maximum external quantum efficiency (EQE ) of 4.39% and a high exciton utilization efficiency (EUE ) of 77%. This study demonstrates a new strategy to construct highly efficient OLED materials.     

SINGLET AND TRIPLET ENERGY TRANSFER IN α-DIKETONE DERIVATIVES OF URACIL and THYMINE

Irradiation of 1-(3,4-dioxopentyl)uracil (UPD) and 1-(3.4-dioxopentyl)thymine (TPD) in acetonitrile solution at 25°C, at the wavelength (280 nm) where only the pyrimidine absorbs the light, sensitizes both fluorescence and phosphorescence of the diketone chromophore in the sidechain. From comparison of the intensity in the corrected excitation spectra with the absorption spectra in acetonitrile solution, it was estimated that the yield of singlet energy transfer in UPD was 0.17 and in TPD was 0.44. It was also observed that the ratio of phosphorescence to fluorescence was greater in the sensitized emission than in that from direct excitation of the diketone chromophore. The yield of triplet energy transfer thus measured corresponds to minimum values for the yields of intersystem crossing from singlet excited state to triplet excited state of 0.075 in the uracil chromophore of UPD and of 0.14 in the thymine chromophore of TPD. These are in agreement with other recent values for these quantities. The value of this type of system as an intramolecular triplet counter is discussed.     

Donor-acceptor interaction and intramolecular proton transfer in aminopolyenes

The influence of donor and acceptor substituents at chain termini on the geometry of the chain and charge distribution on atoms was studied for the ground and lower triplet electronically excited state of model ω-dimethylaminopolyene molecules (CH₃)₂N(CH=CH) _n CH=C(CN)₂, n = 1–3. Calculations were performed by the B3LYP/6-31+G** method. The influence of substituents on bond lengths and the amplitude of deviations from the equilibrium carbon-carbon bond length in unsubstituted polyenes increased as the conjugation chain grew longer. The deviations of the effects of both donor and acceptor groups from additivity, however, decreased. In the lower triplet electronically excited state of the molecule, the effect of substituents on changes in C-C bond lengths along the chain was not damped. The section of the potential energy surface for intramolecular proton shift from the donor amino to the acceptor nitrile group in “cyclic” (cis) conformers of the H₂N-CH=CH-CN and H₂N-CH=CH-CH=CH-CN molecules was analyzed. The structure of the reaction transition state and the height of the barrier to proton transfer were calculated.     

Side chain variations on a series of dicyanovinyl-terthiophenes: a photoinduced absorption study

We characterize a series of dicyanovinyl-terthiophenes with different alkyl side chains. Variations of side chain substitution patterns and length mainly affect the morphology of the evaporated thin films, which in turn sensitively influences properties like absorption, energy levels, and thin film roughness. To investigate changes in transfer processes between electron donor (D) and acceptor (A) molecules due to side chain variations, we use photoinduced absorption spectroscopy (PIA). PIA probes the long-living photoexcited species at the D-A interface: triplet excitons, cations, and anions. For a blend layer of dicyanovinyl-terthiophene and the electron acceptor fullerene C(60), an energy transfer via the singlet and triplet manifold of C(60) occurs. The recombination dynamics of the triplet excitons reveal two components that differ in their lifetime and generation rate by 1 order of magnitude. By comparing the dynamics of triplet excitons in neat and blend layers, we estimate the energy transfer efficiency in dependence of the type of side chain. The compound with methyl side chains shows remarkable properties regarding thin film absorption, surface roughness, and energy transfer efficiency, which we attribute to the specific nanomorphology of the thin film.     

Asymptotic quantum yield of triplet sensitized decomposition

The asymptotic quantum yield of triplet energy transfer is found by calculating the fraction of acceptor molecules with energy above the minimum energy for decomposition. This is done by allowing for a statistical energy distribution among the internal modes in the collision complex. It is found that for a monatomic triplet donor most of the triplet energy is transferred to the acceptor molecule, while for a polyatomic donor molecule only a fraction of it is available for future decomposition of the acceptor.