Photonic modulation of electron transfer with switchable phase inversion.

Photochromes may be reversibly photoisomerized between two metastable states and their properties can influence, and be influenced by, other chromophores in the same molecule through energy or electron transfer. In the photochemically active molecular tetrad described here, a porphyrin has been covalently linked to a fullerene electron acceptor, a quinoline-derived dihydroindolizine photochrome, and a dithienylethene photochrome. The porphyrin first excited singlet state undergoes photoinduced electron transfer to the fullerene to generate a charge-separated state. The quantum yield of charge separation is modulated by the two photochromes: one isomer of each quenches the porphyrin excited state, reducing the quantum yield of electron transfer to near zero. Interestingly, when the molecule is illuminated with white light, the quantum yield decreases as the white light intensity is increased, generating an out-of-phase response of the quantum yield to white light. However, when the same experiment is performed in the presence of additional, steady-state UV illumination, a phase inversion occurs. The quantum yield of electron transfer now increases with increasing white light intensity. Such effects illustrate emergent complexity in a relatively simple system and could find applications in molecular logic, photochemical labeling and drug delivery, and photoprotection for artificial photosynthetic molecules. The photochemistry leading to this behavior is discussed.

A systematic method for the targeted discovery of chemical attribution signatures: application to isopropyl bicyclophosphate production.

Potential attribution signatures for the synthesis of a highly toxic bicyclophosphate, 4-isopropyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide (Isopropyl Bicyclophosphate or IPBCP) were discovered using a trilateral synthetic, analytical, and statistical approach. Initially, five synthetic routes were confirmed to successfully produce IPBCP using a range of reaction solvents, reactant ratios, and reaction temperatures. Experimental design principles were subsequently used to guide a formal study specifically aimed at discovering attribution signatures that could be used to differentiate forensic samples. A comparison of three-dimensional scatter plots comprised of the detected ions, their relative retention times (RRTs) and intensities (from LC-MS analyses) identified: (1) signatures that were unique to a synthetic route; (2) signatures associated with a combination of synthetic route and reaction solvent; (3) signatures related to reaction solvent, and (4) signatures associated with reagent source. Top level analysis revealed that the majority of the signatures are related to the synthetic route or a combination of the synthetic route and reaction solvent. Deeper analysis utilizing high resolution mass spectrometry (HRMS) and MS(n) revealed that most of the signatures stem from impurities in the reagents or byproducts formed from incomplete reactions between the reagents used in a given synthetic route. Finally, a subsequent validation study was performed to assess the presence and absence of the key route dependent signatures.

All-photonic multifunctional molecular logic device.

Photochromes are photoswitchable, bistable chromophores which, like transistors, can implement binary logic operations. When several photochromes are combined in one molecule, interactions between them such as energy and electron transfer allow design of simple Boolean logic gates and more complex logic devices with all-photonic inputs and outputs. Selective isomerization of individual photochromes can be achieved using light of different wavelengths, and logic outputs can employ absorption and emission properties at different wavelengths, thus allowing a single molecular species to perform several different functions, even simultaneously. Here, we report a molecule consisting of three linked photochromes that can be configured as AND, XOR, INH, half-adder, half-subtractor, multiplexer, demultiplexer, encoder, decoder, keypad lock, and logically reversible transfer gate logic devices, all with a common initial state. The system demonstrates the advantages of light-responsive molecules as multifunctional, reconfigurable nanoscale logic devices that represent an approach to true molecular information processing units.

Photochemical "triode" molecular signal transducer.

A molecular "hexad" in which five bis(phenylethynyl)anthracene (BPEA) fluorophores and a dithienylethene photochrome are organized by a central hexaphenylbenzene unit has been prepared. Singlet-singlet energy transfer among the BPEA units occurs on the 0.4 and 60 ps time scales, and when the dithienylethene is in the open form, the BPEA units fluoresce in the 515 nm region with a quantum yield near unity. When the dithienylethene is photoisomerized by UV light to the closed form, which absorbs in the 500-700 nm region, the closed isomer strongly quenches all of the excited singlet states of BPEA via energy transfer, causing the fluorescence quantum yield to drop to near zero. This photochemical behavior permits the hexad to function in a manner analogous to a triode vacuum tube or transistor. When a solution of the hexad is irradiated with steady-state light at 350 nm and with red light (>610 nm) of modulated intensity, the BPEA fluorescence excited by the 350 nm light is modulated accordingly. The fluorescence corresponds to the output of a triode tube or transistor and the modulated red light to the grid signal of the tube or gate voltage of the transistor. Frequency modulation, amplitude modulation, and phase modulation are all observed. The unusual ability to modulate intense, shorter-wavelength fluorescence with longer-wavelength light could be useful for the detection of fluorescence from probe molecules without interference from other emitters in biomolecular or nanotechnological applications.

An all-photonic molecular keypad lock.

Off and on: A molecular triad, consisting of a porphyrin linked to two different, independently addressable photochromic moieties, functions as a molecular keypad lock with all-photonic inputs and output. The porphyrin correlates the responses of the two inputs to light of different wavelengths and provides an appropriate output as fluorescence, which results only when one of eight possible input combinations has been applied (see figure).

Self-regulation of photoinduced electron transfer by a molecular nonlinear transducer.

Organisms must adapt to survive, necessitating regulation of molecular and subcellular processes. Green plant photosynthesis responds to potentially damaging light levels by downregulating the fraction of excitation energy that drives electron transfer. Achieving adaptive, self-regulating behaviour in synthetic molecules is a critical challenge that must be met if the promises of nanotechnology are to be realized. Here we report a molecular pentad consisting of two light-gathering antennas, a porphyrin electron donor, a fullerene electron acceptor and a photochromic control moiety. At low white-light levels, the molecule undergoes photoinduced electron transfer with a quantum yield of 82%. As the light intensity increases, photoisomerization of the photochrome leads to quenching of the porphyrin excited state, reducing the quantum yield to as low as 27%. This self-regulating molecule modifies its function according to the level of environmental light, mimicking the non-photochemical quenching mechanism for photoprotection found in plants.

Molecular all-photonic encoder-decoder.

In data processing, an encoder can compress digital information for transmission or storage, whereas a decoder recovers the information in its original form. We report a molecular triad consisting of a dithienylethene covalently linked to two fulgimide photochromes that performs as an all-photonic single-bit 4-to-2 encoder and 2-to-4 decoder. The encoder compresses the information contained in the four inputs into two outputs. The inputs are light of four different wavelengths that photoisomerize the fulgimide, dithienylethene, or both. The outputs are absorbance at two wavelengths. The two decoder inputs are excitation at two wavelengths, whereas the four outputs, which recover the information compressed into the inputs, are absorbance at two wavelengths, transmittance at one wavelength, and fluorescence emission. The molecule can be cycled through numerous encoder and decoder functions without significant photodecomposition. Molecular photonic encoders and decoders could potentially be used for labeling and tracking of nano- and microscale objects as well as for data manipulation.

All-photonic molecular half-adder.

One molecule acts as both an AND and an XOR Boolean logic gate that share the same two photonic inputs. The molecule comprises a half-adder, adding two binary digits with only light as inputs and outputs, and consists of three covalently linked photochromic moieties, a spiropyran and two quinoline-derived dihydroindolizines. The AND function is based on the absorption properties of the molecule, whereas the XOR function is based on an off-on-off response of the fluorescence to the inputs that results from interchromophore excited-state quenching interactions. The half-adder is simple to operate and can be cycled many times.

Molecular AND and INHIBIT gates based on control of porphyrin fluorescence by photochromes.

A molecular triad consisting of a porphyrin (P) covalently linked to two photochromes-one from the dihydroindolizine family (DHI) and one from the dihydropyrene family (DHP)-has been synthesized and found to act as either a molecular AND logic gate or an INHIBIT gate, depending on the inputs and initial state of the photochromes. The basis of these functions is quenching of porphyrin fluorescence (output of the gates) by the photochromes. The spiro form of DHI does not quench porphyrin fluorescence, whereas its betaine isomer strongly quenches by photoinduced electron transfer. DHP also quenches porphyrin fluorescence, but its cyclophanediene isomer does not. The triad has been designed using suitable energetics and electronic interactions, so that although these quenching phenomena may be observed, independent isomerization of the attached photochromes still occurs. This makes it possible to switch porphyrin fluorescence on or off by isomerization of the photochromes using various combinations of inputs such as UV light, red light, and heat.

Photochromic control of photoinduced electron transfer. Molecular double-throw switch.

A molecular double-throw switch that employs a photochromic moiety to direct photoinduced electron transfer from an excited state donor down either of two pathways has been prepared. The molecular triad consists of a free base porphyrin (P) linked to both a C(60) electron acceptor and a dihydroindolizine (DHI) photochrome. Excitation of the porphyrin moiety of DHI-P-C(60) results in photoinduced electron transfer with a time constant of 2.3 ns to give the DHI-P(*)(+)-C(60)(*)(-) charge-separated state with a quantum yield of 82%. UV (366 nm) light photoisomerizes the DHI moiety to the betaine (BT) form, which has a higher reduction potential than DHI. Excitation of the porphyrin of BT-P-C(60) is followed by photoinduced electron transfer with a time constant of 56 ps to produce BT(*)(-)-P(*)(+)-C(60) in 99% yield. Isomerization of BT-P-C(60) back to DHI-P-C(60) may be achieved with visible light, or thermally. Thus, photoinduced charge separation originating from the porphyrin is reversibly directed down either of two different pathways by photoisomerization of the dihydroindolizine. The switch may be cycled many times.