Pyromellitimide Research Articles

Long-Lived Charge-Transfer State in Spiro Compact Electron Donor-Acceptor Dyads Based on Pyromellitimide-Derived Rhodamine: Charge Transfer Dynamics and Electron Spin Polarization.

We observed a long‐lived charge transfer (CT) state in a novel orthogonal compact electron donor–acceptor dyads, with closed form of rhodamine (Rho) as electron donor and pyromellitimide (PI),or thionated PI, as electron acceptor. The two parts in the dyads are connected via a spiro quaternary carbon atom, thus the torsion between the donor and acceptor is completely inhibited, which is beneficial to reduce the reorganization energy and to exploit the Marcus inverted region effect to prolong the CT state lifetime. Femtosecond transient absorption spectra show that the charge separation is rather fast, while nanosecond transient absorption spectra confirmed the formation of long‐lived CT state (2.6 μs). Time‐resolved electron paramagnetic resonance (TREPR) spectra determined the spin multiplicity of the long living state and assigned it to a 3CT state. Replacement of an oxygen atom in the PI part with a sulfur atom favoring classical intersystem crossing processes, causes a consistently shortening of the lifetime of the 3CT state (0.29 μs).

Long‐Lived Charge‐Transfer State in Spiro Compact Electron Donor–Acceptor Dyads Based on Pyromellitimide‐Derived Rhodamine: Charge Transfer Dynamics and Electron Spin Polarization

AbstractWe observed a long‐lived charge transfer (CT) state in a novel orthogonal compact electron donor–acceptor dyads, with closed form of rhodamine (Rho) as electron donor and pyromellitimide (PI),or thionated PI, as electron acceptor. The two parts in the dyads are connected via a spiro quaternary carbon atom, thus the torsion between the donor and acceptor is completely inhibited, which is beneficial to reduce the reorganization energy and to exploit the Marcus inverted region effect to prolong the CT state lifetime. Femtosecond transient absorption spectra show that the charge separation is rather fast, while nanosecond transient absorption spectra confirmed the formation of long‐lived CT state (2.6 μs). Time‐resolved electron paramagnetic resonance (TREPR) spectra determined the spin multiplicity of the long living state and assigned it to a 3CT state. Replacement of an oxygen atom in the PI part with a sulfur atom favoring classical intersystem crossing processes, causes a consistently shortening of the lifetime of the 3CT state (0.29 μs).

Controlling the Dynamics of Three Electron Spin Qubits in a Donor-Acceptor-Radical Molecule Using Dielectric Environment Changes.

Photogenerated entangled electron spin pairs provide a versatile source of molecular qubits. Here, we examine the spin-dependent dynamics of a covalent donor-acceptor-radical molecule, D-A-R•, where the donor chromophore (D) is peri-xanthenoxanthene (PXX), the acceptor (A) is pyromellitimide (PI), and the radical (R•) is α,γ-bisdiphenylene-β-phenylallyl (BDPA). Selective photoexcitation of D within D-A-R• in butyronitrile/propionitrile at 140 K and butyronitrile at 105 K results in the spin-selective reactions D-A-R• → D•+-1(A•--R•) and D•+-3(A•--R•). Subsequently, at 140 K, D•+-1(A•--R•) → D•+-A-R-, whereas D•+-3(A•--R•) → D-A-R•. In contrast, at 105 K, D•+-3(A•--R•) → 3*D-A-R• and D-A-R•. Time-resolved EPR spectroscopy shows that 3*D-A-R• is highly spin-polarized, where the ms = ±1/2 spin sublevels of the doublet-quartet manifolds are selectively populated. These results demonstrate dielectric environment control over different spin states in the same molecule.

CNOT gate operation on a photogenerated molecular electron spin-qubit pair.

Implementation of the two-qubit controlled-NOT (CNOT) gate is necessary to develop a complete set of universal gates for quantum computing. Here, we demonstrate that a photogenerated radical (spin qubit) pair within a covalent donor-chromophore-acceptor molecule can be used to successfully execute a CNOT gate with high fidelity. The donor is tetrathiafulvalene (TTF), the chromophore is 8-aminonaphthalene-1,8-dicarboximide (ANI), and the acceptor is pyromellitimide (PI). Selective photoexcitation of ANI with a 416 nm laser pulse results in subnanosecond formation of the TTF•+-ANI-PI•- radical (spin qubit) pair at 85 K having a 1.8 µs phase memory time. This is sufficiently long to execute a CNOT gate using a sequence of five microwave pulses followed by a sequence of two pulses that read out all the elements of the density matrix. Comparing these data to a simulation of the data that assumes ideal conditions results in a fidelity of 0.97 for the execution of the CNOT gate. These results show that photogenerated molecular spin qubit pairs can be used to execute this essential quantum gate at modest temperatures, which affords the possibility that chemical synthesis can be used to develop structures to execute more complex quantum logic operations using electron spins.

Effect of Electron-Nuclear Hyperfine Interactions on Multiple-Quantum Coherences in Photogenerated Covalent Radical (Qubit) Pairs.

Ultrafast photodriven electron transfer reactions starting from an excited singlet state in an organic donor-acceptor molecule can generate a spin-correlated radical pair (RP) with an initially entangled spin state that may prove useful as a two-qubit pair in quantum information protocols. Here we investigate the effects of modulating electron-nuclear hyperfine coupling by rapidly transferring an electron between two equivalent sites comprising the reduced acceptor of the RP. A covalent electron donor-acceptor molecule including a tetrathiafulvalene (TTF) donor, a 4-aminonaphthalene-1,8-imide (ANI) chromophoric primary acceptor, and an m-xylene bridged cyclophane having two equivalent pyromellitimides (PI2), TTF-ANI-PI2, as a secondary acceptor was synthesized along with an analogous molecule having one pyromellitimide (PI) acceptor, TTF-ANI-PI. Photoexcitation of ANI within each molecule results in sub-nanosecond formation of TTF+•-ANI-PI-• and TTF+•-ANI-PI2-•. The effect of reducing electron-nuclear hyperfine interactions in TTF+•-ANI-PI2-• relative to TTF+•-ANI-PI-• on decoherence of multiple-quantum coherences has been measured by pulse-EPR spectroscopy. This contribution is especially relevant in the absence of modulation of exchange or dipolar interactions, as with the RP at a fixed distance in the molecules in this work. The theoretical prediction of the contribution from an ensemble of hyperfine interactions to decoherence in these RPs is shown to be less than the full width at half-maximum of the quantum beat frequencies measured experimentally. Pulse bandwidth and off-resonant excitation by square microwave pulses are proposed as larger contributors to decoherence in these molecules than the hyperfine interactions, and specific pulse shapes relevant to arbitrary waveform generation are introduced.

X-Shaped Oligomeric Pyromellitimide Polyradicals.

The synthesis of stable organic polyradicals is important for the development of magnetic materials. Herein we report the synthesis, isolation, and characterization of a series of X-shaped pyromellitimide (PI) oligomers (Xn-R, n = 2-4, R = Hex or Ph) linked together by single C-C bonds between their benzenoid cores. We hypothesize that these oligomers might form high-spin states in their reduced forms because of the nearly orthogonal conformations adopted by their PI units. 1H and 13C nuclear magnetic resonance (NMR) spectroscopies confirmed the isolation of the dimeric, trimeric, and tetrameric homologues. X-ray crystallography shows that X2-Ph crystallizes into a densely packed superstructure, despite the criss-crossed conformations adopted by the molecules. Electrochemical experiments, carried out on the oligomers Xn-Hex, reveal that the reductions of the PI units occur at multiple distinct potentials, highlighting the weak electronic coupling between the adjacent redox centers. Finally, the chemically generated radical anion and polyanion states, Xn-Hex•- and Xn-Hexn(•-), respectively, were probed extensively by UV-vis-NIR absorption, EPR, and electron nuclear double resonance (ENDOR) spectroscopies. The ENDOR spectra of the radical monoanions Xn-Hex•- reveal that the unpaired electron is largely localized on a single PI unit. Further reductions of Xn-Hex•- yield EPR signals (in frozen solutions) that can be assigned to spin-spin interactions in X2-Hex2(•-), X3-Hex3(•-), and X4-Hex4(•-). Taken together, these findings demonstrate that directly linking the benzene rings of PIs with a single C-C bond is a viable method for generating stabilized high-spin organic anionic polyradicals.

Excited-State Properties of Radical Anions of C70 and Its Derivatives: Significant Differences from the Case of C60

Excited-state dynamics of the C70 radical anion (C70•–*) were investigated for the first time by applying femtosecond laser flash photolysis to reduced C70 and its derivatives, including C70•–, C70H•–, C70•–-pyromellitimide (PI), and C70•–-naphthalenediimide (NDI)•–. The transient absorption spectra of C70•– and C70H•– upon near-infrared laser excitation revealed the relaxation processes of the D1 and vibrational hot ground (D0hot) states. Chemical modification of C70 was found to decrease the excited-state lifetimes. In the cases of dyad molecules (C70•–*-PI and C70•–*-NDI•–), the deactivation occurring through dual intramolecular electron transfer (ET) pathways from both C70•– (D1) and C70•– (D0hot) was revealed by spectroscopic analysis. Furthermore, the ET pathways for C70•–*-NDI•– generating NDI2– were proposed based on the energetically preferred products. The differences observed between the dyad systems of C70•–* and C60•–* can be explained by the lower geometric symmetry of C70. The current findi...

Toward Efficient Solid-State p-Type Dye-Sensitized Solar Cells: The Dye Matters

Photoelectrochemical devices based on p-type nanostructured semiconducting materials show strong potentialities for various applications, such as photovoltaics and photocatalysis. While only one study was reported on the use of the reference dye P1 for solid-state p-type dye-sensitized solar cells (DSSC), in this work we have systematically investigated two diketopyrrolopyrrole (DPP) derivatives as sensitizers for solid-state p-type DSSC based on NiO and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as solid-state electron transporter material. We report on the performance in solid-state p-type DSSC of a simple DPP dye bearing a thienyl carboxylic acid as the binding group and a parent compound substituted by a pyromellitimide (PYRO) playing the role of a secondary inner electron acceptor. By focusing on the dye/PCBM interface, we specifically show using transient photoluminescence measurements that the presence of a secondary electron acceptor unit can efficiently favor the formation of the (dye+/PCB...

Unprecedented Intramolecular Electron Transfer from Excited Perylenediimide Radical Anion

Radical anions in the excited states can be treated as stronger reductants than those in the ground states. In this study, the intramolecular electron transfer (ET) processes from the excited perylene-3,4,9,10-tetracarboxydiimide radical anion (PDI•–*) were examined for the first time by applying the femtosecond laser flash photolysis to the dyads of PDI and acceptors (PDI-A). Efficient intramolecular ET from PDI•–* was detected upon the excitation of PDI•–-pyromellitimide (PI) and PDI•–-naphthalenediimide (NDI) because of the sufficient driving forces. In particular, unprecedented ET processes were confirmed in a PDI-PDI dimer. Excitation of PDI•–-PDI gave the shortest PDI•–* lifetime due to the fastest intramolecular ET. Surprisingly, an intramolecular disproportionation reaction generating the dianion of PDI and neutral PDI was confirmed upon the excitation of PDI•–-PDI•–. These processes successfully simulated the photocarrier (polaron and bipolaron) generations in PDI-based n-type semiconducting mate...

Photoinitiated Electron Transfer in Zinc Porphyrin–Perylenediimide Cruciforms and Their Self-Assembled Oligomers

Two X-shaped, cruciform electron donor(2)-acceptor-acceptor'(2) (D(2)-A-A'(2)) molecules, 1 and 2, in which D = zinc 5-phenyl-10,15,20-tripentylporphyrin (ZnTPnP) or zinc 5,10,15,20-tetraphenylporphyrin (ZnTPP), respectively, A = pyromellitimide (PI), and A' = perylene-3,4:9,10-bis(dicarboximide) (PDI), were prepared to study self-assembly motifs that promote photoinitiated charge separation followed by electron and hole transport through π-stacked donors and acceptors. PDI secondary electron acceptors were chosen because of their propensity to form self-ordered, π-stacked assemblies in solution, while the ZnTPnP and ZnTPP donors were selected to test the effect of peripheral substituent steric interactions on the π-stacking characteristics of the cruciforms. Small- and wide-angle X-ray scattering measurements in toluene solution reveal that 1 assembles into a π-stacked structure having an average of 5 ± 1 molecules, when [1] =/~ 10(-5) M, while 2 remains monomeric. Photoexcitation of the π-stacked structure of 1 results in formation of ZnTPnP(•+)-PI-PDI(•-) in τ(CS1) = 0.3 ps, which is nearly 100-fold faster than the formation of ZnTPnP(•+)-PI(•-) in a model system lacking the PDI acceptor. The data are consistent with a self-assembled structure for 1 in which the majority of the intermolecular interactions have the ZnTPnP donor of one monomer cofacially π-stacked with the PDI acceptor of a neighboring monomer in a crisscrossed fashion. In contrast, 2 remains monomeric in toluene, so that photoexcitation of ZnTPP results in the charge separation reaction sequence: (1*)ZnTPP-PI-PDI → ZnTPP(•+)-PI(•-)-PDI → ZnTPP(•+)-PI-PDI(•-), where τ(CS1) = 33 ps and τ(CS2) = 239 ps. The perpendicular orientation of ZnTPnP and ZnTPP relative to PDI in 1 and 2 is designed to decrease the porphyrin-PDI distance without greatly decreasing the overall number of bonds linking them. This serves to decrease the Coulomb energy penalty required to produce D(•+)-PI-PDI(•-) relative to the corresponding linear D-PI-PDI array, while retaining the weak electronic coupling necessary to achieve long-lived charge separation, as evidenced by τ(CR) = 24 ns for ZnTPP(•+)-PI-PDI(•-).

Synthesis and characterization of star-shaped imide compounds

Novel star-shaped imide compounds containing electron-donating triphenylamine and/or electron-withdrawing bis(trifluoromethyl)phenyl side groups were synthesized via a two-step process. First, 3,6-dibromo-benzene-1,2,4,5-tetracarboxylic acid (2B4BA) was reacted with 4-aminophenyl (diphenylamine) (ATPA) or 3,5-bis(trifluoromethyl)aniline (6FA) by imide reaction. Then, Suzuki coupling reaction was carried out on these compounds with 4-(N,N-diphenylamino)-1-phenyl boronic acid (BTPA) or 3,5-bis(trifluoromethyl)phenyl boronic acid (6FBB), resulting in 3,6-bis[4-(diphenylamino)phenyl]-N,N'-bis[4-(diphenylamino) phenyl]-pyromellitimide (TPTPPI), 3,6-bis[3,5-bis(trifluoro methyl) phenyl]-N,N'-bis[3,5-bis(trifluoromethyl) phenyl]-pyro mellitimide (6F6FPI) or 3,6-bis[4-(diphenylamino)phenyl]-N,N'-bis[3,5-bistrifluoromethyl)phenyl]-pyromellitimide (6FTPPI). The imide compounds obtained were characterized by NMR, FT-IR, DSC, TGA, melting point analyzer, EA, and solubility measurements. In addition, their optical and electrical properties were evaluated by fluorescence spectroscopy, UV-vis spectroscopy, and cyclic voltammetry (CV). 6F6FPI exhibited deep blue emission (443 nm), along with high <TEX>$T_m$</TEX> (<TEX>$382^{\circ}C$</TEX>) and relatively high <TEX>$T_g$</TEX> (<TEX>$148^{\circ}C$</TEX>).

Electron Transfer within Self-Assembling Cyclic Tetramers Using Chlorophyll-Based Donor–Acceptor Building Blocks

The synthesis and photoinduced charge transfer properties of a series of Chl-based donor-acceptor triad building blocks that self-assemble into cyclic tetramers are reported. Chlorophyll a was converted into zinc methyl 3-ethylpyrochlorophyllide a (Chl) and then further modified at its 20-position to covalently attach a pyromellitimide (PI) acceptor bearing a pyridine ligand and one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) secondary electron acceptors to give Chl-PI-NDI and Chl-PI-NDI(2). The pyridine ligand within each ambident triad enables intermolecular Chl metal-ligand coordination in dry toluene, which results in the formation of cyclic tetramers in solution, as determined using small- and wide-angle X-ray scattering at a synchrotron source. Femtosecond and nanosecond transient absorption spectroscopy of the monomers in toluene-1% pyridine and the cyclic tetramers in toluene shows that the selective photoexcitation of Chl results in intramolecular electron transfer from (1*)Chl to PI to form Chl(+•)-PI(-•)-NDI and Chl(+•)-PI(-•)-NDI(2). This initial charge separation is followed by a rapid charge shift from PI(-•) to NDI and subsequent charge recombination of Chl(+•)-PI-NDI(-•) and Chl(+•)-PI-(NDI)NDI(-•) on a 5-30 ns time scale. Charge recombination in the Chl-PI-NDI(2) cyclic tetramer (τ(CR) = 30 ± 1 ns in toluene) is slower by a factor of 3 relative to the monomeric building blocks (τ(CR) = 10 ± 1 ns in toluene-1% pyridine). This indicates that the self-assembly of these building blocks into the cyclic tetramers alters their structures in a way that lengthens their charge separation lifetimes, which is an advantageous strategy for artificial photosynthetic systems.

Intersystem Crossing Involving Strongly Spin Exchange-Coupled Radical Ion Pairs in Donor–bridge–Acceptor Molecules

Intersystem crossing involving photogenerated strongly spin exchange-coupled radical ion pairs in a series of donor-bridge-acceptor molecules was examined. These molecules have a 3,5-dimethyl-4-(9-anthracenyl)-julolidine (DMJ-An) donor either connected directly or connected by a phenyl bridge (Ph), to pyromellitimide (PI), 1 and 2, respectively, or naphthalene-1,8:4,5-bis(dicarboximide) (NI) acceptors, 3 and 4, respectively. Femtosecond transient optical absorption spectroscopy shows that photodriven charge separation produces DMJ(+•)-PI(-•) or DMJ(+•)-NI(-•) quantitatively in 1-4 (τ(CS) ≤ 10 ps), and that charge recombination occurs with τ(CR) = 268 and 158 ps for 1 and 3, respectively, and with τ(CR) = 2.6 and 10 ns for 2 and 4, respectively. Magnetic field effects (MFEs) on the neutral triplet state yield produced by charge recombination were used to measure the exchange coupling (2J) between DMJ(+•) and PI(-•) or NI(-•), giving 2J > 600 mT for 1-3 and 2J = 170 mT for 4. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy revealed that the formation of (3)*An upon charge recombination occurs by spin-orbit charge transfer intersystem crossing (SOCT-ISC) and/or radical-pair intersystem crossing (RP-ISC) mechanisms with the magnitude of 2J determining which triplet formation mechanism dominates. SOCT-ISC is the exclusive triplet formation mechanism in 1-3, whereas both RP-ISC and SOCT-ISC are active for 4. The triplet sublevels populated by SOCT-ISC in 1-4 depend on the donor-acceptor geometry in the charge separated state. This is consistent with the fact that the SOCT-ISC mechanism requires the relevant donor and acceptor orbitals to be nearly perpendicular, so that electron transfer results in a large orbital angular momentum change that must be compensated by a fast spin flip to conserve overall system angular momentum.

Solvent-Polarity Dependence of Electron-Transfer Kinetics in a CdSe/ZnS Quantum Dot−Pyromellitimide Conjugate

Photoinduced electron transfer (ET) to and from semiconductor quantum dots (QDs) is of intense interest because of its important roles in QD-based devices, such as detectors, light-emitting diodes, and solar cells. In this study, we have investigated the solvent dependence of the interfacial ET between ZnS-capped CdSe (CdSe/ZnS) QDs and pyromellitimide (PI) at the ensemble and single-particle levels. The steady-state and time-resolved photoluminescence (PL) and absorption measurements revealed that the rates of ET from the excited CdSe/ZnS to the adsorbed PI-CA molecules in nonpolar solvents, such as octane and toluene, are higher than aprotic polar solvents, such as benzonitrile. Furthermore, it was found that two pathways are included in the ET processes between CdSe/ZnS and PI, that is, ET from the excited CdSe core to PI-CA molecules adsorbed on the surface of the CdSe or ZnS. The former process proceeds on the picosecond time scale, while the latter proceeds on the nanosecond time scale. The interfac...

Preparation and structure of poly(4,4′-oxydiphenylene)pyromellitimide asymmetric ultrafiltration membranes

A process was developed for preparing asymmetric ultrafiltration poly(4,4′-oxydiphenylene)pyromel litimide membranes, involving wet forming of the membranes from the prepolymer, followed by catalytic solidphase thermal transformation of the prepolymer into the polyimide. The influence exerted on the structure and characteristics of the membranes by the compositions of the forming solution and precipitation bath, and also by thermal imidization conditions was examined. The optimal conditions were determined for preparing asymmetric ultrafiltration poly(4,4′-oxydiphenylene)pyromellitimide membranes exhibiting the water permeability coefficient of (10−500) × 10−6 m3 m−2 s−1 atm−1 and molecular weight cut-off in the range (5−100) × 103 g mol−1.

Photoinduced electron-transfer within osmium(II) and ruthenium(II) bis-terpyridine donor acceptor dyads

The synthesis and photophysical characterization of two different series of electron donor-acceptor dyads containing Ru(II) and Os(II) bis-terpyridines (M(tpy)(2)(2+)) were prepared and studied in order to compare the oft-studied Ru(tpy)(2)(2+) chromophore with the less studied Os(tpy)(2)(2+) chromophore. The first series of dyads incorporates a benzoquinone (BQ) group as the electron acceptor, whereas the second contains a substituted pyromellitimide (PI) group as the electron acceptor. Steady-state emission experiments indicated efficient quenching of the 3MLCT emission of the electronically excited Os(II)-BQ complexes (7-8) compared to both model complexes (3-4) and the Os(II)-PI complex 10. Femtosecond pump-probe absorption experiments on 7-8 yielded ultrafast electron transfer rate constants (kET) of approximately 2.0 x 10(11) s(-1) (7) and 1.3 x 10(10) s(-1) (8) that were in good agreement with the low emission quantum yield results. Charge-recombination (kCR) in these complexes was also quite rapid, with rate constants of approximately 6.7 x 10(10) s(-1) (7) and 1.2 x 10(10) s(-1) (8). The analogous Ru(II) complexes underwent charge separation with rate constants of 7.6 x 10(10) s(-1) (5) and approximately 2.3 x 10(10) s(-1) (6), while charge recombination in these complexes occurred with rate constants of approximately 2.1 x 10(10) s(-1) (5) and approximately 5.3 x 10(10) s(-1) (6). Electron transfer in the pyromellitimide-containing complexes occurred only for Os(II)-PI (10), which exhibited significantly slower electron transfer (approximately 4.3 x 10(6) s(-1)) and charge recombination (approximately 7.7 x 10(6) s(-1)) rate constants. The nearly thermoneutral free energy of electron transfer and short excited state lifetime in the case of Ru(II)-PI (9) presumably prevents electron transfer in this compound.

Spin Dynamics of Photogenerated Triradicals in Fixed Distance Electron Donor−Chromophore−Acceptor−TEMPO Molecules

The stable free radical 2,2,6,6-tetramethylpiperidinoxyl (TEMPO, T*) was covalently attached to the electron acceptor in a donor-chromophore-acceptor (D-C-A) system, MeOAn-6ANI-Phn-A-T*, having well-defined distances between each component, where MeOAn = p-methoxyaniline, 6ANI = 4-(N-piperidinyl)naphthalene-l,8-dicarboximide, Ph = 2,5-dimethylphenyl (n = 0,1), and A = naphthalene-1,8:4,5-bis(dicarboximide) (NI) or pyromellitimide (PI). Using both time-resolved optical and EPR spectroscopy, we show that T* influences the spin dynamics of the photogenerated triradical states 2,4(MeOAn+*-6ANI-Phn-A-*-T*), resulting in modulation of the charge recombination rate within the triradical compared with the corresponding biradical lacking T*. The observed spin-spin exchange interaction between the photogenerated radicals MeOAn+* and A-* is not altered by the presence of T*, which interacts most strongly with A-* and accelerates radical pair intersystem crossing. Charge recombination within the triradicals results in the formation of 2,4(MeOAn-6ANI-Phn-3*NI-T*) or 2,4(MeOAn-3*6ANI-Phn-PI-T*) in which T* is strongly spin polarized in emission. Normally, the spin dynamics of correlated radical pairs do not produce a net spin polarization; however, the rate at which the net spin polarization appears on T* closely follows the photogenerated radical ion pair decay rate. This effect is attributed to antiferromagnetic coupling between T* and the local triplet state 3NI, which is populated following charge recombination. These results are explained using a switch in the spin basis set between the triradical and the three-spin charge recombination product having both T* and 3*NI or 3*6ANI present.

New base-soluble positive-working photosensitive polyimides havingo-nitrobenzyl ester group

A new positive-working polyimide having photosensitive o-nitrobenzyl ester group as side substituent, poly{1,4-phenyleneoxy-1,4-phenylene-3,6-di[4-(o-nitrobenzyloxy)carbonylphenyl]pyromellitimide} (ODA-PI-Nb), was prepared and its aqueous alkali-developability and photosensitivity were investigated. ODA-PI-Nb was synthesized by the esterification reaction of poly[1,4-phenyleneoxy-1.4-phenylene-3,6-di(4-carboxylphenyl)pyromellit imide] (ODA-PI) with o-nitrobenzyl bromide in the presence of triethylamine (Et3N). ODA-PI-Nb obtained was characterized by FT-IR and 1H-NMR spectroscopy. The degree of esterification reaction was found from 1H-NMR absorption of CH2 proton to be over 95 mol%. Upon photo-irradiation ODA-PI-Nb transformed to the freely aqueous alkali-soluble ODA-PI under formation of o-nitrosobenzaldehyde. The thickness loss of thin ODA-PI-Nb films upon post-baking at 400°C was in the 10–15% range. ODA-PI-Nb showed positive-tone behavior in characteristic sensitivity curve and positive patterns were obtained using a typical lithographic process using aqueous tetramethylammonium hydroxide developer. The patterns with excellent resolution were observed and evaluated by optical microscopy and scanning electron microscopy. Copyright © 2005 John Wiley & Sons, Ltd.

Using Three-Pulse Femtosecond Spectroscopy to Probe Ultrafast Triplet Energy Transfer in Zincmeso-Tetraarylporphyrin−Perylene-3,4-dicarboximide Dyads

Linear arrays of zinc meso-tetraarylporphyrin (ZnP), perylene-3,4-dicarboximide (PMI), and either naphthalene-1,8:4,5-bis(dicarboximide) (NI) or pyromellitimide (PI) were synthesized and studied by ultrafast transient absorption spectroscopy. PMI was covalently linked in one of two orientations relative to ZnP. In one set of molecules, the 9 position of the perylene core is connected to the para position of a meso-phenyl in ZnP to give ZnP−PMI−N−X, where X = NI or PI is attached to the imide nitrogen atom of PMI. In the second set of compounds, the imide nitrogen atom of PMI is connected to the meso-phenyl in ZnP to give ZnP−N−PMI−X, where X = PI or H. Selective excitation of ZnP using 420 nm, 110 fs laser pulses in each molecule in toluene produces 1*ZnP, which intersystem crosses (ISC) to 3*ZnP with τ = 2.3 ns. For ZnP−PMI−N−X, triplet energy transfer (TET) from 3*ZnP to PMI is much faster than ISC, so that 3*ZnP is not observed by one-pump−one-probe transient absorption spectroscopy. Following its form...

Competitive Electron Transfer from the S2 and S1 Excited States of Zinc meso-Tetraphenylporphyrin to a Covalently Bound Pyromellitimide: Dependence on Donor−Acceptor Structure and Solvent

Zinc meso-tetraphenylporphyrin (ZnTPP) is known to have a relatively slow S2 → S1 internal conversion rate, (1−3 ps)-1, so that electron transfer from S2 to a nearby acceptor is possible. We have synthesized two zinc porphyrins in which a pyromellitimide (PI) acceptor is attached to the para position of a meso-phenyl group of the porphyrin (ZnTPP−PI) or to that of a β-phenyl group of the porphyrin (ZnTPP−β-PhPI). We report here on competitive electron transfer from the S2 (excitation at 420 nm) and S1 states (excitation at 550 nm) of these zinc porphyrins to PI in 2-methyltetrahydrofuran (MTHF) and toluene. Our transient absorption studies show that efficient electron transfer occurs from S2 of ZnTPP to PI in these porphyrins despite the presence of the intervening phenyl between the zinc porphyrin macrocycle and the PI acceptor. Moreover, the results show that while charge separation from S1 is about 6 times faster for PI attached to the meso-phenyl than for PI attached to the β-phenyl, the opposite is observed for charge separation from S2. Subsequent charge recombination is 2.6−2.8 times faster for PI attached to the meso-phenyl relative to that of the β-phenyl. Comparisons of rates between MTHF and toluene show that the ordering of rates is the same for both solvents, although the rate ratios are larger in MTHF than in toluene.