Optical waveguides – With optical coupler
Reexamination Certificate
2001-03-30
2004-11-30
Healy, Brian M. (Department: 2883)
Optical waveguides
With optical coupler
C385S016000, C385S024000, C385S147000, C365S215000, C365S225500, C365S234000, C365S243500
Reexamination Certificate
active
06826321
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates generally to the effects of magnetic fields on the lifetimes of radical pairs formed generally by photoinduced electrons transfer and the corresponding yields of the products of radical pair decay and more particularly to the magnetic switching of charge separation lifetimes in artificial photosynthetic reaction centers.
BACKGROUND ART
The effects of magnetic fields on the lifetimes of radical pairs formed by photoinduced electron transfer and the corresponding yields of the products of radical pair decay have been studied for many years. (Steiner, U. E. et al.
Chem. Rev
. 1989, 89, 51-147.; Steiner, U. E. et al.
Photochemistry and Photophysics
, Vol IV; Rabek, J. F., Ed.; CRC: Boca Raton, Fla., 1991; pp 1-130.; Hayashi, H. In
Photochemistry and Photophysics
, Vol I; Rabek, J. F., Ed.; CRC: Boca Raton, Fla., 1990; pp 59-136.; Grissom, C. B.
Chem. Rev
. 1995, 95, 3-24). These effects arise because the field can affect the rates of interconversion among the singlet radical pair and the three sublevels of the triplet radical pair. The observation of such effects requires two apparently contradictory conditions. In order for photoinduced electron transfer to occur from an excited singlet state, the electronically excited electron donor (acceptor) and the ground-state acceptor (donor) must experience relatively strong electronic coupling so that electron transfer can compete kinetically with the other decay pathways available to the excited state. However, such strong coupling generally precludes the interconversion of the singlet and triplet radical pair states necessary for the development of magnetic field effects. Both conditions may be satisfied sequentially by allowing diffusional processes to bring together the donor and acceptor, thus promoting rapid photoinduced electron transfer. Diffusion can then separate the radical pairs, reducing coupling and allowing singlet-triplet interconversion. Thus, magnetic field effects are generally observable in radical pair systems wherein the donors and acceptors freely diffuse in solution, or in biradicals where the radicals are linked by flexible chains such as polymethylene groups so that large-scale internal motions are facile.
Because of these restrictions, rigid donor-acceptor assemblies, or those in media such as low-temperature glasses or plastics where molecular motions are restricted, typically do not demonstrate magnetic field effects on radical pairs originating from excited singlet state precursors. This hinders the use of such effects in the design of molecular-scale electronic components that must function in rigid media. The conundrum can be avoided by employing a multistep electron transfer strategy whereby the electron is moved from the primary donor to the ultimate acceptor via intermediate donor-acceptor species. In this way, the electronic coupling between adjacent donor-acceptor pairs is strong enough so that each electron transfer step is rapid and can compete with other decay pathways, resulting in a high yield of the final charge-separated state. At the same time, the electronic coupling between the donor and the ultimate acceptor is small, and this can allow rapid singlet-triplet interconversions and consequently magnetic field effects.
The preeminent example of this phenomenon is photosynthesis, where a number of different magnetic field effects on reaction yields and rates have been observed. (see: Blankenship, R. E. et al.
Biochim. Biophys. Acta
1977, 461, 297-305.; Blankenship, R. E.
Acc. Chem. Res
. 1981, 14, 163-170.; Hoff, A. J. et al.
Biochim. Biophys. Acta
1977, 460, 547-554.; Hoff, A. J.
Photochem. Photobiol
. 1986, 43, 727-745.; Boxer, S. G. et al.
J. Am. Chem. Soc
. 1982, 104, 1452-1454.; Boxer, S. G. et al.
J. Am. Chem. Soc
. 1982, 104, 2674-2675.; van Dijk, B. et al.
J. Phys. Chem. B
1998, 102, 464-472). In the case of photosynthetic model systems, magnetic-field-dependent nonexponential decays of biradical states at room temperature have been reported in diporphyrin-imide triad molecules. (see: Werner, U. et al.
J. Phys. Chem
1995, 99, 13930-13937). Small magnetic fields increased the initial rate of decay of the biradical to the ground state by charge recombination. Magnetic field effects have also been reported in dyads consisting of porphyrins linked to viologen electron acceptors by flexible chains. (Saito, T. et al.
Bull. Chem. Soc. Jpn
. 1988, 61, 1925-1931.; Nakamura, H. et al.
Chem. Lett
. 1 987, 543-546). In these reported cases, the photoinduced electron transfer originates from the porphyrin excited triplet state, rather than the singlet.
Recently reported (see: Liddell, P. A. et al.
J. Am. Chem. Soc
. 1997, 119, 1400-1405.; Carbonera, D. et al.
J. Am. Chem. Soc
. 1998, 120, 4398-4405; Gust, D. et al. In
Recent Adavances in the Chemistry and Physics of Fullerenes and Related Materials
; Kadish, K. M., Rutherford, A. W., Eds.; The Electrochemical Society: Pennington, N.J., 1997; pp 9-24) is the preparation and study of a carotenoid (C) porphyrin (P) fullerene (C
60
) triad artificial photosynthetic reaction center (1), shown below, that demonstrates photoinduced electron transfer behavior ideally suited for the observation of unusual magnetic field effects. Excitation of the porphyrin moiety yields C-
1
P-C
60
, which decays by photoinduced electron transfer to give C-P
+
-C
60
*
−
. Secondary electron transfer from the carotenoid to the porphyrin radical cation produces the C*
+
-P-C
60
*
−
charge-separated state. This process occurs even in low-temperature organic glasses where molecular motions and some electron spin relaxation processes are slowed. In addition, charge recombination yields only the carotenoid triplet state,
3
C-P-C
60
, rather than the molecular ground state. As discussed below, this combination of properties results in a lifetime for the C*
+
-P-C
60
*
−
charge-separated state on tile microsecond time scale that is increased by 50% upon application of a weak magnetic field.
DISCLOSURE OF INVENTION
The magnetically activated optoelectronic switch as herein described and illustrated can be used in several applications. For example, it can be configured as an AND logic gate, AND logic gate, or other form of logic gate. In this configuration, it is used as a molecular-scale logic element in an optoelectronic computer processor. AND gates, either alone or in combination, can perform all logic operations necessary for computer data processing. By using a gate of molecular dimensions, the size, cost and power requirements of computer processors could be reduced, and their speed increased.
Such molecular-scale switches can also be used in optical or optoelectronic communications applications. In this case, the light which forms one of the inputs of the device can be from a fiber optic communication line, and the magnetic input provided by conventional electronic means.
A unique feature of this switch is that it is sensitive to inputs having different physical properties. One input is electromagnetic radiation in the ultraviolet or visible wavelength range and the other input is a magnetic field. This allows information transmitted in different media to be combined and processed.
Alternatively, the device can be configured as a computer memory element that can be switched between “on” and “off” binary states using a combination of light and magnetic fields. The density of data storage in such molecular-scale memories will be much higher than in conventional electronic memories, and the access speed will be extremely high. Such memories would have to be refreshed as a function of the lifetime of the charge-separated state.
REFERENCES:
patent: 3870397 (1975-03-01), Dillon et al.
patent: 3990776 (1976-11-01), Tseng et al.
patent: 4689793 (1987-08-01), Liu et al.
patent: 4806995 (1989-02-01), Day et al.
patent: 5331183 (1994-07-01), Sariciftci et al.
patent: 5512193 (1996-04-01), Shirai et al.
patent: 5698048 (1997-12-01), Friend et al.
patent: 5707845 (1998-01-01), U
Gust, Jr. John D.
Moore Ana L.
Moore Thomas A.
Arizona Board of Regents
Healy Brian M.
Luther Barbara J.
Quarles & Brady Streich & Lang LLP
LandOfFree
Magnetic switching of charge separation lifetimes in... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Magnetic switching of charge separation lifetimes in..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Magnetic switching of charge separation lifetimes in... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3325974