Logic circuits with plug and play solid-state molecular chips

Abstract

A logic circuit for performing a logic operation comprising a plurality of predetermined solid-state molecular chips, each molecular chip having multiple states obtained after application of a corresponding input. After applying predetermined inputs on the molecular chips, reading the states of the molecular chips produces a logical output according to the logic operation.

Claims

1. A logic circuit for performing a logic operation such that predetermined inputs to the logic circuit produce a logical output according to said logic operation, comprising: a plurality of predetermined solid-state molecular chips, each molecular chip comprising a layer of an active compound confined to a solid support, each molecular chip having multiple states, each state being obtained after application of a corresponding input, each state being read electrically, optically, electro-chemically or any combination thereof; wherein said active compound on at least one of said molecular chips is different from said active compound on at least another of said molecular chips; a plurality of predetermined inputs, such that after applying said predetermined inputs on said predetermined molecular chips, reading the states of said plurality of molecular chips produces a logical output according to said logic operation.

2. The logic circuit of claim 1, wherein each of said plurality of molecular chips comprises one or more layers of one or more active compounds coupled to said layer of an active compound.

3. The logic circuit of claim 1, wherein the states of the plurality of the molecular chips are read optically, magnetically, electrically, or electrochemically, based on changes in conductivity, magnetism, current, absorption, refractive index readout, Infra-Red (IR) readout or Near IR (NIR) readout.

4. The logic circuit of claim 1, wherein said input comprises application of an electric current, application of an electric/magnetic field, immersion in a solution, or any combination thereof.

5. The logic circuit of claim 4, wherein said input comprises immersion in a solution and wherein said solution is (i) an acidic solution of organic or mineral acid or oxoacid; (ii) a basic solution of organic or inorganic base; (iii) a solution comprising an oxidizing or reducing agent; or (iv) a solution comprising a metal ion, an anion, an organic cation, or a gas.

6. The logic circuit of claim 5, wherein said input comprises immersion in a solution and wherein said solution is (i) an acidic solution of organic or mineral acid or oxoacid; (ii) a basic solution of organic or inorganic base; (iii) a solution comprising an oxidizing or reducing agent; or (iv) a solution comprising a metal ion, an anion, an organic cation, or a gas, and wherein: (i) said organic acid is selected from the group consisting of acetic acid, propionic acid, butyric acid, formic acid, oxalic acid, glycolic acid, citric acid, succinic acid, ascorbic acid, lactic acid, salicylic acid, pivalic acid, diethylacetic acid, malonic acid, benzoic acid, phenylpropionic acid, pimelic acid, fumaric acid, maleic acid, malic acid, gluconic acid, isonicotinic acid, sulfaminic acid, adipic acid, para-toluenesulfonic acid, naphthalenedisulfonic acid, uric acid, oxalic acid, sulfonic acid, tartaric acid, and a mixture thereof; (ii) said mineral acid or oxoacid is selected from the group consisting of HCl, HBr, HI, HNO.sub.3, H.sub.2SO.sub.4, H.sub.3PO.sub.4, HClO.sub.4, HBrO.sub.4, HIO.sub.4, HBF.sub.4, H.sub.3BO.sub.3, and HPF.sub.6; a derivative of aforesaid selected from the group consisting of HNO.sub.2, H.sub.3PO.sub.2, H.sub.2SO.sub.3, H.sub.2SO.sub.2, HClO.sub.3, HClO.sub.2, HClO, HBrO.sub.3, HBrO.sub.2, HBrO, HIO.sub.3, HIO.sub.2, HIO, and HBO.sub.2; and an acid solution of PCl.sub.5 or PO.sub.5; (iii) said organic base is selected from the group consisting of a pyridine, imidazole, benzimidazole, amine, and hystidine; (iv) said inorganic base is selected from the group consisting of: an alkali hydroxide selected from the group consisting of LiOH, NaOH, KOH, and CsOH; a metal hydroxide selected from the group consisting of aluminium hydroxide, beryllium hydroxide, cobalt(II) hydroxide, copper(II) hydroxide, gold(III) hydroxide, iron(II) hydroxide, mercury(II) hydroxide, nickel(II) hydroxide, tin(II) hydroxide, zinc hydroxide, and zirconium(IV) hydroxide; a metal oxide/hydroxide including FeOOH; a carbonate selected from the group consisting of lithium carbonate, sodium carbonate, and potassium carbonate; a bicarbonate selected from the group consisting of lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate; ammonia; and a metal amide selected from the group consisting of lithium amide, sodium amide, and potassium amide; (v) said oxidizing agent is selected from the group consisting of K.sub.2CrO.sub.4, KMnO.sub.4, NaMnO.sub.4, OsO.sub.4, NOBF.sub.4, FeCl.sub.3, H.sub.2SO.sub.5, H.sub.2SO.sub.8, N.sub.2O, HNO.sub.3, Ag.sub.2O, oxygen, ozone, H.sub.2O.sub.2, sodium perborate, F.sub.2, Br.sub.2, Cl.sub.2, I.sub.2, ClO.sub.2.sup., ClO.sub.3.sup., and HClO.sub.4; (vi) said reducing agent is selected from the group consisting of sodium sulfide, dithiothreitol, lithium aluminium hydride, sodium borohydride, sodium amalgam (Na(Hg)), zinc-mercury amalgam (Zn(Hg)), diisobutylaluminum hydride (DIBAH), Sn.sup.2+, and Fe.sup.2+; (vii) said metal ion is selected from the group consisting of an ion of Li, Na, K, Rb, Cs, Fr, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Ge, Sn, Pb, As, Sb, Bi, Se, and Te; (viii) said anion is selected from the group consisting of cyanide, carbonate, nitrate, nitrite, phosphate, phosphite, sulfide, sulfphate, sulphite, chloride, bromide, iodide, fluoride, and a derivative thereof; (ix) said organic cation is a quaternary ammonium compound of the formula N(R).sub.4.sup.+, wherein R each independently is H, or (C.sub.1-C.sub.10)alkyl; and (x) said gas is selected from the group consisting of CO, CO.sub.2NO, Cl.sub.2, Br.sub.2, He, Ne, and Ar.

7. The logic circuit of claim 1, wherein said active compound each independently comprises: an organic, metal-organic, inorganic, polymeric, or coordination compound, or metal-organic framework/network/polymer.

8. The logic circuit of claim 7, wherein said active compound comprises metal-organic compound and wherein said metal-organic compound is a polypyridyl complex of the general formula I: ##STR00007## wherein M is Os, Fe, Ru, Mn, Cu, Zn, Ni, Cr, Ti, V, Ir, or Rh; n is the formal oxidation state of M, wherein n is 0 to 4; m is the positive charge of the tris-bipyridyl ligand, wherein m is an integer from 0 to 24, X is a counter anion selected from the group consisting of Br.sup., Cl.sup., F.sup., F.sup., I.sup., PF.sub.6.sup., BF.sub.4.sup., OH.sup., ClO.sub.4.sup., SO.sub.3.sup., CF.sub.3COO.sup., CN.sup., alkylCOO.sup., arylCOO.sup. and a combination thereof; and R.sub.5 to R.sub.28 each independently is selected from the group consisting of hydrogen, halogen, hydroxyl, azido, nitro, cyano, amino, substituted amino, thiol, C.sub.1-C.sub.10 alkyl, cycloalkyl, heterocycloalkyl, haloalkyl, aryl, heteroaryl, alkoxy, alkenyl, alkynyl, carboxamido, substituted carboxamido, carboxyl, protected carboxyl, protected amino, sulfonyl, substituted aryl, substituted cycloalkyl and substituted heterocycloalkyl, wherein at least one of said R.sub.5 to R.sub.28 is a group A linked to the ring structure of the compound of general formula I via R.sub.4, or B linked to the ring structure of the compound of general formula I via the oxygen: ##STR00008## wherein R.sub.4 is selected from the group consisting of cis/trans CC, CC, NN, CN, NC, CN, NC, alkylene, arylene and a combination thereof; R.sub.3 is C or N; R.sub.2 is absent or is selected from the group consisting of hydrogen, alkyl, alkylene, aryl, arylene, OH, O-alkyl, O-alkylene and a combination thereof; and R.sub.1 is absent or is selected from the group consisting of hydrogen, trialkoxysilane, trihalidesilane, thiol, COOH, COO, Si(OH).sub.3, Si(OEt).sub.3, Si(OMe)(Me).sub.2, SiCl.sub.3, SiMe.sub.2Cl, zirconate, sulfate, and phosphonate; and p is an integer from 9 to 12; and R.sub.29 is selected from the group consisting of hydrogen, trialkoxysilane, trihalidesilane, thiol, COOH, COO, Si(OH).sub.3, Si(OEt).sub.3, Si(OMe)(Me).sub.2, SiCl.sub.3, SiMe.sub.2Cl, zirconate, sulfate, and phosphonate; and any two vicinal R.sub.5-R.sub.28 substituents, together with the carbon atoms to which they are attached, may form a fused ring system selected from the group consisting of cycloalkyl, heterocycloalkyl, heteroaryl and aryl, wherein said fused system may be substituted by one or more groups selected from the group consisting of C.sub.1-C.sub.10 alkyl, aryl, azido, cycloalkyl, halogen, heterocycloalkyl, alkoxy, hydroxyl, haloalkyl, heteroaryl, alkenyl, alkynyl, nitro, cyano, amino, substituted amino, carboxamido, substituted carboxamido, carboxyl, protected carboxyl, protected amino, thiol, sulfonyl and substituted aryl; and said fused ring system may also contain at least one heteroatom selected from the group consisting of N, O and S.

9. The logic circuit of claim 8, wherein said active compound comprises metal-organic compound and wherein said metal-organic compound is a polypyridyl complex and wherein said polypyridyl complex is the compound of the general formula I, wherein M is Os, n is 2, m is 1, X is PF.sub.6.sup. or I.sup., R.sub.5, R.sub.7 to R.sub.26 and R.sub.28 each is hydrogen, R.sub.6 is methyl, and R.sub.27 is A, wherein R.sub.4 is CC, R.sub.3 is N, R.sub.2 is propyl, and R.sub.1 is trimethoxysilane, herein identified compounds 1a and 1b, respectively ##STR00009##

10. The logic circuit of claim 7, wherein said active compound comprises metal-organic compound and wherein said metal-organic compound is [M.sub.1.sup.II(2,2-bipyridine).sub.3].sup.2+ or [M.sub.1.sup.II(2,2-bipyridine).sub.2(4-methyl-2,2-bipyridine-pyridine)].sup.2+, wherein M.sub.1 is Os, Fe, Ru, Mn, Cu, Co, Zn, Ni, Cr, Ti, V, Ir, or Rh.

11. The logic circuit of claim 7, wherein said active compound comprises an organic compound and wherein said organic compound is selected from the group consisting of (i) viologen (4, 4-bipyridylium salts); (ii) azole compounds; (iii) azo compounds including azobenzenes; (iv) aromatic amines; (v) carbazoles; (v) cyanines; (vi) methoxybiphenyls; (vii) quinones; (viii) thiazines; (ix) pyrazolines; (x) tetracyanoquinodimethanes (TCNQs); (xi) tetrathiafulvalene (TTF); (xii) porphyrins; (xiii) corroles; (xiv) phthalocyanines; (xv) diarylethenes including stilbenes; (xvi) dithienylethenes, (xvii) fulgides; (xviii) spiropyrans; (xix) phenoxynaphthacene quinines; and (xx) derivatives of compounds defined in (i)-(xix).

12. The logic circuit of claim 11, wherein said active compound comprises an organic compound and wherein said organic compound is a porphyrin and wherein said porphyrin is of the general formula II or III: ##STR00010## wherein M is Os, Fe, Ru, Mn, Cu, Zn, Ni, Cr, Ti, V, Ir, or Rh; n is the formal oxidation state of M, wherein n is 0 to 4; q is the overall positive charge of the R.sub.30 to R.sub.41 groups, wherein q is an integer from 0 to 12; X is a counter anion selected from the group consisting of Br.sup., Cl.sup., F.sup., I.sup., PF.sub.6.sup., BF.sub.4.sup., OH.sup., ClO.sub.4.sup., SO.sub.3.sup., CF.sub.3COO.sup., CN.sup., alkylCOO.sup., arylCOO.sup., and a combination thereof; and R.sub.30 to R.sub.41 each independently is selected from the group consisting of hydrogen, halogen, hydroxyl, azido, nitro, cyano, amino, substituted amino, thiol, C.sub.1-C.sub.10 alkyl, cycloalkyl, heterocycloalkyl, haloalkyl, aryl, heteroaryl, alkoxy, alkenyl, alkynyl, carboxamido, substituted carboxamido, carboxyl, protected carboxyl, protected amino, sulfonyl, substituted aryl, substituted cycloalkyl and substituted heterocycloalkyl, wherein at least one of said R.sub.30 to R.sub.41 is a group A linked to the porphyrin of general formula II or III via R.sub.4, or B linked to the porphyrin of general formula II or III via the oxygen: ##STR00011## wherein R.sub.4 is absent or selected from the group consisting of cis/trans CC, CC, NN, CN, NC, CN, NC, alkylene, arylene and a combination thereof; R.sub.3 is C or N; R.sub.2 is absent or is selected from the group consisting of hydrogen, alkyl, alkylene, aryl, arylene, OH, O-alkyl, O-alkylene and a combination thereof; and R.sub.1 is absent or is selected from the group consisting of hydrogen, trialkoxysilane, trihalidesilane, thiol, COOH, COO, Si(OH).sub.3, Si(OEt).sub.3, Si(OMe)(Me).sub.2, SiCl.sub.3, SiMe.sub.2Cl, zirconate, sulfate, and phosphonate; p is an integer from 9 to 12; R.sub.29 is selected from the group consisting of hydrogen, trialkoxysilane, trihalidesilane, thiol, COOH, COO, Si(OH).sub.3, Si(OEt).sub.3, Si(OMe)(Me).sub.2, SiCl.sub.3, SiMe.sub.2Cl, zirconate, sulfate, and phosphonate; and any two vicinal R.sub.30-R.sub.41 substituents, together with the carbon atoms to which they are attached, may form a fused ring system selected from the group consisting of cycloalkyl, heterocycloalkyl, heteroaryl and aryl, wherein said fused system may be substituted by one or more groups selected from the group consisting of C.sub.1-C.sub.10 alkyl, aryl, azido, cycloalkyl, halogen, heterocycloalkyl, alkoxy, hydroxyl, haloalkyl, heteroaryl, alkenyl, alkynyl, nitro, cyano, amino, substituted amino, carboxamido, substituted carboxamido, carboxyl, protected carboxyl, protected amino, thiol, sulfonyl and substituted aryl; and said fused ring system may also contain at least one heteroatom selected from the group consisting of N, O and S.

13. The logic circuit of claim 12, wherein said porphyrin is the compound of the general formula II, wherein R.sub.30, R.sub.31, R.sub.33, R.sub.34, R.sub.36, R.sub.37, R.sub.39 and R.sub.40 each is H; R.sub.32, R.sub.38 and R.sub.41 each is 4-pyridyl; and R.sub.35 is A, wherein R.sub.4 is absent, R.sub.3 is N, R.sub.2 is CH.sub.2-phenyl and R.sub.1 is Si(Cl).sub.3, herein identified compound 2: ##STR00012##

14. The logic circuit of claim 7, wherein said active compound comprises an inorganic compound and wherein said inorganic compound comprises tungsten oxide, iridium oxide, vanadium oxide, nickel oxide, molybdenum oxide, titanium oxide, manganese oxide, niobium oxide, copper oxide, tantalum oxide, rhenium oxide, rhodium oxide, ruthenium oxide, iron oxide, chromium oxide, cobalt oxide, cerium oxide, bismuth oxide, tin oxide, praseodymium, bismuth, lead, silver, lanthanide hydrides (LaH.sub.2/LaH.sub.3), nickel doped SrTiO.sub.3, indium nitride, ruthenium dithiolene, phosphotungstic acid, ferrocene-naphthalimides dyads, organic ruthenium complexes, or any mixture thereof.

15. The logic circuit of claim 7, wherein said active compound comprises a polymeric compound and wherein said polymeric compound comprises a conducting polymer selected from the group consisting of a polypyrrole, polydioxypyrrole, polythiophene, polyaniline, poly(acetylene), poly(p-phenylene sulfide), poly(p-phenylene vinylene) (PPV), polyindole, polypyrene, polycarbazole, polyazulene, polyazepine, poly(fluorene), polynaphthalene, polyfuran, a metallopolymeric film based on a polypyridyl complex and a polymeric viologen system comprising pyrrole-substituted viologen pyrrole, disubstituted viologen, N,N-bis(3-pyrrol-1-ylpropyl)-4,4-bipyridylium, or a derivative of said conducting polymer.

16. The logic circuit of claim 1, wherein the solid support is a material selected from the group consisting of glass, a doped glass, indium tin oxide (ITO)-coated glass, silicon, a doped silicon, Si(100), Si(111), SiO.sub.2, SiH, silicon carbide mirror, quartz, a metal, metal oxide, a mixture of metal and metal oxide, group IV elements, mica, a graphite comprising intercalated metal cations, a polymer selected from the group consisting of polyacrylamide and polystyrene, a plastic, a zeolite, a clay, a membrane, an optical fiber, a ceramic, a metalized ceramic, an alumina, an electrically-conductive material, a semiconductor, steel, and a stainless steel.

17. The logic circuit of claim 1, wherein said plurality of molecular chips (n.sub.1) are applied a plurality of inputs (n.sub.2), producing one or more output information streams (n.sub.3) representing the predetermined logical output of said logic circuit, such that n.sub.1<n.sub.2 and n.sub.3n.sub.1.

18. The logic circuit of claim 1, wherein said plurality of molecular chips perform one or more of the following logic operations: AND, OR, NOT, XOR, NAND, NOR, XNOR, or any combination thereof.

19. The logic circuit of claim 1, wherein said plurality of molecular chips operate using Boolean Logic, Sequential Logic, a combination of Boolean Logic and Sequential Logic.

20. The logic circuit of claim 1, wherein said plurality of molecular chips operate as a sensor, an encoder, a decoder, a set/reset latch, a memory element or a multistate memory element.

21. The logic circuit of claim 1, wherein said plurality of molecular chips operate using base 2, base 3, base 4, base 5, base 6, base 7, base 8, base 9, base 10, base 16 or any combination thereof.

22. The logic circuit of claim 1, wherein said plurality of molecular chips operate using light.

23. The logic circuit of claim 1, wherein said plurality of molecular chips operate using organic electronics, molecular electronics or a combination thereof.

24. A logic circuit performing a logic operation, for the detection of inputs to the logic circuit, comprising: a plurality of predetermined solid-state molecular chips, each molecular chip comprising a layer of an active compound confined to a solid support, each molecular chip having multiple states, each state being obtained after application of a corresponding input, each state being read electrically, optically, electro-chemically or any combination thereof; wherein said active compound on at least one of said molecular chips is different from said active compound on at least another of said molecular chips; a logical output obtained by reading the states of said plurality of molecular chips after application of said inputs, such that knowing the logical output which can only be obtained after application of predetermined inputs on said plurality of molecular chips produces the detection of said inputs.

25. The logic circuit of claim 24, wherein said inputs comprise an electric current, an electric/magnetic field, or immersion in a solution, or any combination thereof.

26. The logic circuit of claim 25, wherein said input comprises immersion in a solution and wherein said solution is (i) an acidic solution of organic or mineral acid or oxoacid; (ii) a basic solution of organic or inorganic base; (iii) a solution comprising an oxidizing or reducing agent; or (iv) a solution comprising a metal ion, an anion, an organic cation, or a gas.

27. The logic circuit of claim 26, wherein said input comprises immersion in a solution and wherein said solution is (i) an acidic solution of organic or mineral acid or oxoacid; (ii) a basic solution of organic or inorganic base; (iii) a solution comprising an oxidizing or reducing agent; or (iv) a solution comprising a metal ion, an anion, an organic cation, or a gas and wherein: (i) said organic acid is selected from the group consisting of acetic acid, propionic acid, butyric acid, formic acid, oxalic acid, glycolic acid, citric acid, succinic acid, ascorbic acid, lactic acid, salicylic acid, pivalic acid, diethylacetic acid, malonic acid, benzoic acid, phenylpropionic acid, pimelic acid, fumaric acid, maleic acid, malic acid, gluconic acid, isonicotinic acid, sulfaminic acid, adipic acid, para-toluenesulfonic acid, naphthalenedisulfonic acid, uric acid, oxalic acid, sulfonic acid, tartaric acid, and a mixture thereof; (ii) said mineral acid or oxoacid is selected from the group consisting of HCl, HBr, HI, HNO.sub.3, H.sub.2SO.sub.4, H.sub.3PO.sub.4, HClO.sub.4, HBrO.sub.4, HIO.sub.4, HBF.sub.4, H.sub.3BO.sub.3, and HPF.sub.6; a derivative of the aforesaid selected from the group consisting of HNO.sub.2, H.sub.3PO.sub.2, H.sub.2SO.sub.3, H.sub.2SO.sub.2, HClO.sub.3, HClO.sub.2, HClO, HBrO.sub.3, HBrO.sub.2, HBrO, HIO.sub.3, HIO.sub.2, HIO, and HBO.sub.2; and an acid solution of PCl.sub.5 or PO.sub.5; (iii) said organic base is selected from the group consisting of a pyridine, imidazole, benzimidazole, amine, and hystidine; (iv) said inorganic base is selected from the group consisting of: an alkali hydroxide selected from the group consisting of LiOH, NaOH, KOH, and CsOH; a metal hydroxide selected from the group consisting of aluminium hydroxide, beryllium hydroxide, cobalt(II) hydroxide, copper(II) hydroxide, gold(III) hydroxide, iron(II) hydroxide, mercury(II) hydroxide, nickel(II) hydroxide, tin(II) hydroxide, zinc hydroxide, and zirconium(IV) hydroxide; a metal oxide/hydroxide including FeOOH; a carbonate selected from the group consisting of lithium carbonate, sodium carbonate, and potassium carbonate; a bicarbonate selected from the group consisting of lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate; ammonia; and a metal amide selected from the group consisting of lithium amide, sodium amide, and potassium amide; (v) said oxidizing agent is selected from the group consisting of K.sub.2CrO.sub.4, KMnO.sub.4, NaMnO.sub.4, OsO.sub.4, NOBF.sub.4, FeCl.sub.3, H.sub.2SO.sub.5, H.sub.2SO.sub.8, N.sub.2O, HNO.sub.3, Ag.sub.2O, oxygen, ozone, H.sub.2O.sub.2, sodium perborate, F.sub.2, Br.sub.2, Cl.sub.2, I.sub.2, ClO.sub.2.sup., ClO.sub.3.sup., and HClO.sub.4; (vi) said reducing agent is selected from the group consisting of sodium sulfide, dithiothreitol, lithium aluminium hydride, sodium borohydride, sodium amalgam (Na(Hg)), zinc-mercury amalgam (Zn(Hg)), diisobutylaluminum hydride (DIBAH), Sn.sup.2+, and Fe.sup.2+; (vii) said metal ion is selected from the group consisting of an ion of Li, Na, K, Rb, Cs, Fr, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Ge, Sn, Pb, As, Sb, Bi, Se, and Te; (viii) said anion is selected from the group consisting of cyanide, carbonate, nitrate, nitrite, phosphate, phosphite, sulfide, sulfphate, sulphite, chloride, bromide, iodide, fluoride, and a derivative thereof; (ix) said organic cation is a quaternary ammonium compound of the formula N(R).sub.4.sup.+, wherein R each independently is H, or C.sub.1-C.sub.10 alkyl; and (x) said gas is selected from the group consisting of CO, CO.sub.2NO, Cl.sub.2, Br.sub.2, He, Ne, and Ar.

28. A method for performing a logic operation in a logic circuit such that predetermined inputs to the logic circuit produce a logical output according to said logic operation, the method comprising the steps of: selecting a plurality of predetermined solid-state molecular chips, each molecular chip comprising a layer of an active compound confined to a solid support, each molecular chip having multiple states, each state being obtained after application of a corresponding input, each state being read electrically, optically, electro-chemically or any combination thereof; wherein said active compound on at least one of said molecular chips is different from said active compound on at least another of said molecular chips; applying a plurality of predetermined inputs, such that after applying said predetermined inputs on said predetermined molecular chips, reading the states of said plurality of molecular chips produces a logical output according to said logic operation.

29. A method for the detection of inputs to a logic circuit performing a logic operation, the method comprising the steps of: selecting a plurality of predetermined solid-state molecular chips, each molecular chip comprising a layer of an active compound confined to a solid support, each molecular chip having multiple states, each state being obtained after application of a corresponding input, each state being read electrically, optically, electro-chemically or any combination thereof; wherein said active compound on at least one of said molecular chips is different from said active compound on at least another of said molecular chips; reading the states of said plurality of molecular chips after application of said inputs; and calculating a logical output based on the states of said plurality of molecular chips, such that knowing the logical output which can only be obtained after application of predetermined inputs on said plurality of molecular chips produces the detection of said inputs.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A-1B show representative molecular structures of the molecular chips M1 (FIG. 1A) and M2 (FIG. 1B). FIG. 1A shows a monolayer of Os(bpy).sub.2(mbpy-py)][PF.sub.6].sub.2 (M1) covalently attached to a quartz surface through iodopropyltrimethoxysilane; and FIG. 1B shows a monolayer of 5,10,15,20-tetra(4-pyridyl)porphyrin (M2) covalently attached to quartz surface through 4-(chloromethyl)-phenyltrichlorosilane.

(2) FIG. 2 shows a logic circuit of a 4:2 encoder, operating with four inputs (In.sub.1-In.sub.4), according to truth-table in Table 1, herein after.

(3) FIG. 3 shows an optical response of monolayers M1 and M2 after immersing monolayer M1 (FIG. 3A) into a saturated solution of NOBF.sub.4 in dichloromethane for 3 minutes (blue trace, noted as b), and monolayer M2 (FIG. 3B) in a 2 M aqueous solution of H.sup.+ for 3 minutes (b). The traces noted as a show the absorption spectra of the monolayers M1 and M2 in its reduced (Os.sup.2+) state and un-protonated form, respectively. The dashed gray lines indicate the wavelength (495 and 465 nm) that was monitored for assignment of the logic 1 or 0, based on the A of the M1- and M2-based monolayers.

(4) FIGS. 4A-4B show a response (A) of the molecular chip M1 (FIG. 4A) or M2 (FIG. 4B) after applying the four different inputs (In.sub.1-In.sub.4 defined hereinafter) required for operating a molecular encoder. Table 1 hereinafter summarizes which reagent (input) is present, where 1 signifies present and 0 signifies absent.

(5) FIG. 5 shows absorption of the monolayer M1 upon applying Input 1: Cl.sup., Input 2: H.sup.+ (blue trace), Input 3: NO.sup.+ and Input 4: Cr.sup.6+ for 3 min. The two reset traces show the reset of the M1-based monolayer after applying inputs 3 and 4, respectively. The initial trace shows the initial absorption of monolayer M1.

(6) FIG. 6 shows absorption of the M2-based monolayer upon applying Input 1: Cl.sup., Input 2: H.sup.+, Input 3: NO.sup.+ and Input 4: Cr.sup.6+ for 3 minutes. The two reset traces show the reset of the monolayer after applying inputs 2 and 4, respectively. The initial red trace shows the initial absorption of monolayer M2.

(7) FIG. 7 shows a graphical illustration of the Plug and Play concept with molecular chips M1 and M2. Only upon combining (plugging in) monolayers M1 and M2 with inputs In.sub.1-In.sub.4, does a molecular encoder result. Each monolayer independently does not result in an encoder.

(8) FIG. 8 shows a logic circuit of a half-subtractor operating with two inputs (X-Y), according to truth-table in Table 2.

DETAILED DESCRIPTION OF THE INVENTION

(9) The present invention relates to a logic circuit for performing a logic operation. For each logic operation it is defined a set of predetermined multiple solid-state molecular chips. The molecular chips used are characterized by having multiple, stable states. The state of the molecular chips is read electrically, optically, electro-chemically or any combination thereof. The state of a molecular chip can be changed by applying an appropriate input. Each specific state of a molecular chip is obtained by applying a corresponding input. Each molecular chip can be sensitive to (affected by) one or more inputs that can change its state, as can be observed in Examples 1, 2 and 3 below. Also, the molecular chip may be insensitive to (neutral) one or more inputs that will never change its state.

(10) In order to perform a given logical operation, a plurality of predetermined inputs is applied to a plurality of the predetermined molecular chips (as defined for the logical operation). Before applying the inputs, each of the molecular chips can be in any of its multiple states. After the inputs are applied, the state of the molecular chips is read electrically, optically, electro-chemically (or any combination of modes) in order to produce the logical output. The state of the multiple chips is thus interpreted (calculated) in view of the given logic operation to produce the logical output of the logic circuit.

(11) The logic operation is defined by the selection of the solid-state molecular chips to be used and the inputs to be applied, thus producing a logical output in accordance with the logic operation.

(12) The same molecular chips can be used for various logic operations by varying the inputs applied thus producing different logical outputs.

(13) A detection of multiple states at the same operation can serve different purposes. In some embodiments, the logic circuit performs a predetermined logic operation such that a given input produces a predetermined output according to the specific logic circuit designed (a truth table is one way to express for a given logical operation what is the output for any input parameters). In some embodiments, the input and output of the logic circuit is determined by reading the initial state of the molecular chips (i.e. before inputs are applied) and their later state after inputs are applied. Each molecular chip is designed to be read in a particular electrical, optical, or electro-chemical way. It is possible to read the same molecular chip in multiple electrical ways and/or multiple optical ways and/or multiple electro-chemical ways. In the same logic circuit, each molecular chip can be read in a different way, for example, one molecular chip can be read electrically, while another molecular chip being read electro-chemically and other molecular chips are read optically. Each molecular chip can thus be read using a particular device or method. Alternatively, a particular device or method can be used for reading multiple different molecular chips. The molecular chips are both small in size and in a solid state so they can be reused conveniently. After a molecular chip is applied an input and its new state read, the molecular chip can be reinitialized back to its initial state (ground state) according to the nature of the molecular chip.

(14) In a logic-circuit implementation the aim is to design a logic operation such that a given input will determine a given output, all in accordance with the rules of the logic operation (as can be defined in a truth table). Alternatively, in another aspect, the logic circuit of the invention can be looked at as an input detection mechanism (sensor). In these implementations the state of the input is unknown and reading the output of the logic circuit, i.e. the states of the molecular chips after being applied inputs, will reveal the nature of the input, for example, the pH levels, presence of heavy metals etc.

(15) The logic circuit of the invention can be looked as containing three parameters: inputs, molecular chips and logical output. The relationship between these three parameters is known in advance: a predetermined input to predetermined molecular chips will yield a known logical output in accordance with the truth table of the logical operation. If we apply predetermined inputs to predetermined molecular chips the logic circuit provides us with the logical output as defined by the logic operation. When we know the logical output of the logic operation and the molecular chips known, the logic circuit functions as a detector (sensor) for detecting the inputs used.

(16) The term pyridyl complex, as used herein, refers to a metal having one or more pyridyl ligands, e.g., OS.sup.2+, Fe.sup.2+, Ru.sup.2+, Mn.sup.2+, Cu.sup.2+, Zn.sup.2+, Ni.sup.2+, Cr.sup.3+, Ti.sup.2+, V.sup.2+, Ir.sup.3+, or Rh.sup.3+ is coordinated to one or more pyridyl ligands. In certain embodiments, the active compound of the invention is a polypyridyl complex of the general formula I as defined above.

(17) In some embodiments, the polypyridyl complex is the compound of the general formula I as defined above, wherein M is Os, n is 2, m is 1, X is Br.sup., Cl.sup., F.sup., I.sup., PF.sub.6.sup., BF.sub.4.sup., OH.sup., ClO.sub.4.sup., SO.sub.3.sup., CF.sub.3COO.sup., CN.sup., alkylCOO.sup., arylCOO.sup. or a combination thereof, R.sub.5, R.sub.7 to R.sub.26 and R.sub.28 each is hydrogen, R.sub.6 is methyl, and R.sub.27 is A, wherein R.sub.4 is CC, R.sub.3 is N, R.sub.2 is propyl, and R.sub.1 is Si(OMe).sub.3, Si(OEt).sub.3, Si(OMe)(Me).sub.2, SiCl.sub.3, or SiMe.sub.2Cl. In some particular embodiments the polypyridyl complex is compound 1a or compound 1b.

(18) In some embodiments, the states of the molecular chips comprising the polypyridyl complex of the general formula 1 are read optically, electrically, electro-chemically or any combinations thereof.

(19) In some embodiments, the metal-organic compound is [M.sub.1.sup.II(2,2-bipyridine).sub.3].sup.2+ or [M.sub.1.sup.II(2,2-bipyridine).sub.2(4-methyl-2,2-bipyridine-pyridine)].sup.2+, wherein M.sub.1 is Os, Fe, Ru, Mn, Cu, Co, Zn, Ni, Cr, Ti, V, Ir, or Rh.

(20) In some embodiments, the states of the molecular chips comprising the metal organic compounds are read optically, electrically, or electro-chemically.

(21) In some embodiments, the organic compound is selected from (i) viologen (4,4-bipyridylium salts); (ii) azole compounds; (iii) azo compounds including azobenzenes; (iv) aromatic amines; (v) carbazoles; (v) cyanines; (vi) methoxybiphenyls; (vii) quinones; (viii) thiazines; (ix) pyrazolines; (x) tetracyanoquinodimethanes (TCNQs); (xi) tetrathiafulvalene (TTF); (xii) porphyrins; (xiii) corroles; (xiv) phthalocyanines; (xv) diarylethenes including stilbenes; (xvi) dithienylethenes, (xvii) fulgides; (xviii) spiropyrans; (xix) phenoxynaphthacene quinines; or (xx) derivatives of compounds defined in (i)-(xix).

(22) In some embodiments, the active compound of the invention is a porphyrin of the general formula II as defined above. Specific such embodiments are those wherein the porphyrin is the compound of the general formula II, wherein R.sub.30, R.sub.31, R.sub.33, R.sub.34, R.sub.36, R.sub.37, R.sub.39 and R.sub.40 each is H; R.sub.32, R.sub.38 and R.sub.41 each is 4-pyridyl; R.sub.35 is A, wherein R.sub.4 is absent, R.sub.3 is N, R.sub.2 is CH.sub.2-phenyl and R.sub.1 is Si(Cl).sub.3, compound 2.

(23) In certain embodiments, the metallated porphyrins are porphyrins of the general formula III as defined above.

(24) In some embodiments, the states of the molecular chips comprising the organic compound are read optically.

(25) In some embodiments, the states of the molecular chips comprising the inorganic compound are read optically and/or electrically.

(26) The term alkyl, as used herein, typically means a straight or branched hydrocarbon radical having preferably 1-10 carbon atoms, and includes, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like. The alkyl may further be substituted. The term alkylene refers to a linear divalent hydrocarbon chain having preferably 1-10 carbon atoms and includes, e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene and the like.

(27) The term alkenyl typically means a straight or branched hydrocarbon radical having preferably 2-10 carbon atoms and one or more double bonds. Non-limiting examples of such alkenyls are ethenyl, 3-buten-1-yl, 2-ethenylbutyl, 3-octen-1-yl, and the like. The term alkenylene refers to a linear divalent hydrocarbon chain having preferably 2-10 carbon atoms and one or more double bonds, and includes, e.g., 1-propylene, 1-butylene, 2-butylene, 3-hexylene and the like.

(28) The term alkynyl refers to a straight or branched hydrocarbon radical having preferably 2-10 carbon atoms and containing at least one triple bond.

(29) The term cycloalkyl typically means a saturated aliphatic hydrocarbon in a cyclic form (ring) having preferably 3-10 carbon atoms. Non-limiting examples of such cycloalkyl ring systems include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclodecyl and the like. The cycloalkyl may be fused to other cycloalkyls, such in the case of cis/trans decalin. The term heterocycloalkyl refers to a cycloalkyl, in which at least one of the carbon atoms of the ring is replaced by a heteroatom selected from N, O or S.

(30) The term alkylCOO refers to an alkyl group substituted by a carboxyl group (COO) on any one of its carbon atoms. Preferably, the alkyl has 1-10 carbon atoms, more preferably CH.sub.3COO.sup..

(31) The term aryl typically means any aromatic group, preferably having 6-14 carbon atoms such as phenyl and naphtyl. The aryl group may be substituted by any known substituents. The term arylCOO refers to such a substituted aryl, in this case being substituted by a carboxylate group.

(32) The term heteroaryl refers to an aromatic ring system in which at least one of the carbon atoms is replaced by a heteroatom selected from N, O or S. Non-limiting examples of heteroaryl include pyrrolyl, furyl, thienyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl thiazolyl, isothiazolyl, pyridyl, 1,3-benzodioxinyl, pyrazinyl, pyrimidinyl, 1,3,4-triazinyl, 1,2,3-triazinyl, 1,3,5-triazinyl, thiazinyl, quinolinyl, isoquinolinyl, benzofuryl, isobenzofuryl, indolyl, imidazo[1,2-a]pyridyl, pyrido[1,2-a]pyrimidinyl, benz-imidazolyl, benzthiazolyl and benzoxazolyl.

(33) The term halogen includes fluoro, chloro, bromo, and iodo. The term haloalkyl refers to an alkyl substituted by at least one halogen.

(34) The term alkoxy refers to the group OR, wherein R is an alkyl group. The term azido refers to N.sub.3. The term nitro refers to NO.sub.2 and the term cyano refers to CN. The term amino refers to the group NH.sub.2 or to substituted amino including secondary, tertiary and quaternary substitutions wherein the substituents are alkyl or aryl. The term protected amino refers to such groups which may be converted to the amino group. The term carboxamido refers to the group CONH.sub.2 or to such a group substituted, in which each of the hydrogens is replaced by an alkyl or aryl group.

(35) The term carboxyl refers to the group COOH. The term protected carboxyl refers to such groups which may be converted into the carboxyl group, e.g., esters such as COOR, wherein R is an alkyl group or an equivalent thereof, and others which may be known to a person skilled in the art of organic chemistry.

(36) The term trialkoxysilane refers to a group of the general formula Si(OR).sub.3, wherein each of the three R groups is an alkyl group, and may be the same or different, preferably, trimethoxysilane or triethoxysilane. Similarly, the term trihalidesilane refers to SiX.sub.3, wherein X is a halogen, each X may be same or different.

(37) The expression any two vicinal R.sub.5-R.sub.28 substituents refers to any two substituents on the benzene rings, being ortho to one another. The expression fused ring system refers to at least two rings sharing one bond, such as in the case of naphthalene, phenanthrene, benzindole, benzpyridine and others. The fused ring system contains at least one benzene ring, being the ring of the compound of general formula I and another ring being formed by the ring closure of the any two vicinal R.sub.4-R.sub.27 substituents. The other ring may be saturated or unsaturated, substituted or unsabstituted and may be heterocylic.

(38) The term oxidation state, as used herein, refers to the electrically neutral state or to the state produced by the gain or loss of electrons to an element, compound or chemical substituent/subunit. In a preferred embodiment, this term refers to states including the neutral state and any state other than a neutral state caused by the gain or loss of electrons (reduction or oxidation).

(39) The term coordination compound as used herein refers to any kind of compound that contains a coordination entity, i.e., an ion or neutral molecule that is composed of a central atom, usually of a metal, to which a surrounding array of atoms or groups of atoms, each of which is called a ligand, is attached (see e.g., Batten et al., 2012). Each one of ligands attached to said coordination entity may be a simple ion such as Cl.sup., a small molecule such as H.sub.2O or NH.sub.3, a larger molecule such as H.sub.2NCH.sub.2CH.sub.2NH.sub.2, N(CH.sub.2CH.sub.2NH.sub.2).sub.3 or pyridyl, or a macromolecule, such as proteins. Non-limiting examples of coordination compounds include the above listed polypyridyl complexes, the metal-organic compounds of the formula [M.sub.1.sup.II(2,2-bipyridine).sub.3].sup.2+ or [M.sub.1.sup.II(2,2-bipyridine).sub.2(4-methyl-2,2-bipyridine-pyridine)].sup.2+, wherein M.sub.1 is Os, Fe, Ru, Mn, Cu, Co, Zn, Ni, Cr, Ti, V, Ir, or Rh, metallated corroles, and metallated porphyrins such as porphyrins of the general formula III as defined above.

(40) The term coordination polymer as used herein refers to any system that forms 1D straight chain polymer network with carbon containing ligands bridging mononuclear, polynuclear or 1D coordination entities (see e.g., Batten et al., 2012).

(41) The terms metal-organic frameworks (MOFs), metal-organic polymers and metal-organic networks, as used herein interchangeably, refer to any system that forms a 2D or 3D network with carbon containing ligands bridging mononuclear, polynuclear or 1D coordination entities (see e.g., Batten et al., 2012). The metal-organic framework materials as such are described in, for example, U.S. Pat. No. 5,648,508; U.S. Pat. No. 7,637,983; U.S. Pat. No. 6,624,318; U.S. Pat. No. 7,799,120; EP-A-0 709 253; M. O'Keeffe et al., J Sol. State Chem., 152 (2000) p. 3-20; H. Li et al., Nature 402 (1999) p. 276 seq.; M. Eddaoudi et al., Topics in Catalysis 9 (1999) p. 105-111; B. Chen et al., Science 291 (2001) p. 1021-23; Givaja et al, Chem Soc Rev., 41, p. 115-147, (2012). An inexpensive way for the preparation of said materials is the subject of DE 10111230.0.

(42) The term organic electronics, plastic electronics or polymer electronics as used herein refers to a branch of electronics dealing with conductive polymers and conductive small molecules, which are carbon-based. Organic electronics relate to an area of technology that comprises applications as diverse as illuminants, photovoltaics, printed electronics and batteries, by replacing inorganic materials by organic materials, in particular conversion of light to electrical current (photovoltaics) and electrical current to light (light diodes).

(43) The term molecular electronics as used herein refers to the design and construction of electronic devices consisting of a single molecule or small groups of molecules. These devices include components such as wires, rectifiers, switches, and memory devices.

(44) The solid-state molecular chip can be prepared according to any present or future procedure of the art, for example, as disclosed by International Patent Applications published as WO 2011/141913 and WO 2009/095924.

(45) The invention will now be illustrated by the following non-limiting Examples.

EXAMPLES

(46) Materials and Methods

(47) Monolayers M1 and M2 (FIGS. 1A-1B) were prepared according to known procedures (Gupta et al, 2006; Li et al, 1993; Yerushalmi et al, 2004). p-Chloromethyl-phenyltrichlorosilane and 5,10,15,20-tetra(4-pyridyl)porphyrin were used as received and purchased from Gelest, Inc. and Sigma Aldrich, respectively. Solvents (AR grade) were purchased from Bio-Lab (Jerusalem), Frutarom (Haifa) or Mallinckrodt Baker (Phillipsburg, N.J.). Toluene was dried and purified using an M. Braun solvent purification system. Single-crystal silicon (100) substrates (2.0 cm1.0 cm) were purchased from Wafernet (San Jose, Calif.) and Indium Tin Oxide (ITO) coated glass substrates (7.5 cm0.8 cm) were purchased from Delta Technologies (Loveland, Colo.). The ITO and silicon substrates were cleaned by sonication in dichloromethane followed by sonication in toluene, then in acetone and ethanol, and subsequently dried under an N.sub.2 stream; thereafter, they were cleaned for 30 min with an ultra violet ozone cleaning systems (UVOCS) (Montgomery, Pa.). Quartz (Chemglass, Inc.) substrates (2.0 cm1.0 cm) were cleaned by immersion in a piranha solution (7:3 (v/v) H.sub.2SO.sub.4/30% H.sub.2O.sub.2) for 1 h. Subsequently, the substrates were rinsed with deionized (DI) water followed by the RCA cleaning protocol: 1:5:1 (v/v) NH.sub.4OH/H.sub.2O/30% H.sub.2O.sub.2 at 80 C. for 45 min. The substrates were washed with DI water and were dried under an N.sub.2 stream. All substrates were then dried in an oven for 2 h at 130 C. The siloxane-based chemistry was carried out in a glovebox or by using standard schlenk-cannula techniques. Ultra/visible (UV/Vis) spectra were recorded on a Cary 100 spectrophotometer.

(48) Nature of the Molecular Inputs (In.sub.1-In.sub.4)

(49) In.sub.1 is a 0.1 mM solution of KCl in DI water (15 mL).

(50) In.sub.2 is a solution of 2 M HCl in DI water (15 mL).

(51) In.sub.3 is a solution of saturated NOBF.sub.4 (20 mg) in dichloromethane (15 mL). Sonication for 2 min improved solubility. The solution was prepared inside a N.sub.2-filled glove-box.

(52) In.sub.4 is a solution of 50 ppm (w/w) K.sub.2Cr.sub.2O.sub.7 in 15 mL DI water, acidified with HCl to pH=0.

Example 1

Logic Operations with Monolayer M1

(53) Monolayer M1 is able to respond to various oxidizing agents. The consequent change in oxidation state from Os.sup.2+.fwdarw.Os.sup.3+ is optically visible by bleaching of the metal-to-ligand charge-transfer (MLCT) band at =495 nm. Thus, monolayer M1 was operated using the four above-mentioned inputs. The total volume of the solutions was 15 mL. The successive application of any of those afore-mentioned inputs yieldedin combination with the output of the monolayer M2an output equivalent to the output of a molecular logic encoder (Table 1 and FIG. 2), as demonstrated next. The inputs were applied by immersing monolayer M1 for 3 min in each solution of inputs. After each input, the monolayer was carefully dried under a stream of N.sub.2. If necessary, before applying the next input, the monolayer M1 was reduced to its original state by immersion in H.sub.2O (pH=7.5) for 5 min. FIG. 3A shows the oxidation of the monolayer M1 after immersing the monolayer in a saturated solution of NOBF.sub.4 (In.sub.3) in dichloromethane for 3 min. In these experiments the logical 1 was defined as the difference in absorptionbefore and after applying the inputof the metal-to-ligand charge-transfer (MLCT) band at =496 nm; A=A.sub.before-A.sub.after, exceeded a threshold value of 210.sup.2 (FIG. 4A). This eliminates noise and ensures high ON/OFF ratios, and hence only occurs if the metal centers in M1 are in the higher oxidation state (Os.sup.3+).

(54) Similar results were obtained when the monolayer M1 was immersed in a solution of K.sub.2CrO.sub.4 at pH=0. However, since M1 was only responsive to changes in the oxidation state, it did not respond to changes in pH. Immersing this monolayer in an acidic solution (pH=0), did not lead to changes in the intensity of the MLCT band. Accordingly, the monolayer is in state 1 only if inputs In.sub.3 and In.sub.4 are applied. This is summarized in FIG. 4A and FIG. 5.

Example 2

Logic Operations with Monolayer M2

(55) In contrast to monolayer M1, monolayer M2 is able to respond to changes in the pH. This was recently exploited by Gulino et al. (2006) for the fabrication of a pH sensor on solid support. The inner core of the utilized porphyrin in M2, requires strongly acidic conditions in order to be protonated; pH<1. Monolayer M2 was operated using the four above-mentioned inputs. The total volume of the solutions was 15 mL. The successive application of any of those afore-mentioned inputs, yieldedin combination with the output of the monolayer M1an output equivalent to the output of a molecular logic encoder (Table 1 and FIG. 2), as demonstrated next. The inputs were applied, by immersing monolayer M2 for 3 min in each solution of inputs. After each input, the monolayer was carefully dried under a stream of N.sub.2. If necessary, before applying the next input, monolayer M2 was restored to its original state by immersion in H.sub.2O (pH=7.5) for 5 min. FIG. 3B shows the consequent change in the optical absorption upon protonation of M2after immersion in a 2 M aqueous solution of H.sup.+ (In.sub.2) for 3 min. In these experiments the logical 1 was defined as the difference in absorptionbefore and after applying the inputof the Soret band at =465 nm; A=A.sub.red-A.sub.ox, exceeded a threshold value of 410.sup.2 (FIG. 4B). This eliminates noise, and ensures high ON/OFF ratios, and hence the output 1 will only occur if the monolayer M2 is protonated. This behavior pin-points the orthogonality of M1 and M2, where the latter monolayer is responsive to strongly acidic solutions and not to the here applied oxidizing agents, as is the case with M1 (FIGS. 5, 6). As a result the monolayer M2 only exhibited a logic 1, when inputs In.sub.2 and In.sub.4 were applied.

(56) For In.sub.1 and In.sub.3 no change in the Soret band was observed. The output of the M2-based monolayer upon applying In.sub.1-In.sub.4 is shown in FIG. 4B and FIG. 6.

Example 3

Formation of a Molecular Encoder

(57) The key idea was to regard the molecular monolayers, e.g. M1 and M2, as universal chips that act as individual logic gates, which can easily be combined into meaningful logic arrangements. This has many advantages because monolayers are physically separated from each other, do not show interference, can be read-out independently, are highly stable, and are robust to a wide variety of environmental conditions. We demonstrated that a combination of two orthogonal addressable monolayers can be used as molecular chips for mimicking a functional logic circuit, with subsequent control over the individual logic gates therein. The monolayers M1 and M2 were generated by covalently anchoring 5,10,15,20-tetra(4-pyridyl)porphyrin and [Os(bpy).sub.2(mbpy-py)][PF.sub.6].sub.2 from solution to a quartz surface (FIGS. 1A-1B) (Gupta et al., 2006; Li et al., 1993). These molecular chips can be addressed chemically and behave as individual parts of the logic arrangement. Combining the optical output of these monolayers defines the overall operation as such. This set-up enabled, for the first time, to mimic the in/output behavior of a molecular encoder on solid support.

(58) The plug and play principle and the universality of the molecular chips was demonstrated since individually they do not mimic any useful logic function, although if desired, upon combination, they can be used for applications in molecular logic, which we demonstrated.

(59) To accomplish the feature of combining different molecular logic gates into meaningful logic schemes, monolayers M1 and M2 were used for demonstrating the plug and play principle in a molecular encoder, which is illustrated in FIG. 7. A molecular encoder is a device that can compress information, effectively storing the same amount of information in fewer bits. For instance, a 4:2 encoder converts the same amount of information present in four bits into an output of only 2 bits. Therefore, an encoder has four different inputswith the restriction that they cannot be active at the same timeand two outputs A and B (Out.sub.A and Out.sub.B, respectively). In addition, there was also extra output that is called the validation output. This validated the active operation of encoder when one of the inputs was active, i.e. it gave a logic 1 when one encoder is ON, and a logic 0 when encoder is OFF. This output, generated by the OR gate did not take part in the actual encoding of the information itself, but merely resulted from applying the inputs (Mano et al., 2000). For correct operation of the 4:2 molecular encoder, the order in which the inputs are applied does not affect the operation of the molecular encoder. In our case this was evident as the monolayers that constitute the encoder were reset to their original state before applying the next input. The truth-table and logic circuit of an encoder are shown in Table 1 and FIG. 2, respectively. The inputs used are In.sub.1-In.sub.4, listed above.

(60) TABLE-US-00001 TABLE 1 Truth-table of a molecular 4:2 encoder consisting M1 and M2 operating with four inputs (In.sub.1-In.sub.4). Inputs Output Entry In.sub.1 In.sub.2 In.sub.3 In.sub.4 Out.sub.A Out.sub.B V 1 1 0 0 0 0 0 1 2 0 1 0 0 0 1 1 3 0 0 1 0 1 0 1 4 0 0 0 1 1 1 1

(61) The outputs A and B correspond to the outputs of the two different logic gates in the logic circuit of the encoder (FIG. 2).

(62) Since reactivity of the monolayers M1 and M2 is orthogonal, with respect to certain stimuli (In.sub.1-In.sub.4), the monolayers will respond differently to the four applied inputs.

(63) The Os metal-centers in M1 ensure that this monolayer will be operated according to its redox chemistry, whereas the porphyrin in M2 can be addressed by (de)protonation of the pyridine moieties attached to the porhyrin-core. For example, monolayer M1 is able to respond to various oxidizing agents, while M2 is only responsive to strongly acidic solutions and not to oxidizing agents.

(64) To ensure that both monolayers are responsive to In.sub.4, (K.sub.2CrO.sub.4), we use the fact that the oxidation of Os.sup.2+ occurs predominantly at low pH values. Protonation of the inner core's nitrogen atoms of M2 occurs under the strong acidic conditions as well (pH<1) (Yerushalmi et al., 2004). Although one might argue in this case that In.sub.3 will be active as well, the system responds in such a way that In.sub.4 receive priority only over In.sub.3, resulting in logic 1 for M1 and M2. The output of monolayer M2 upon applying In.sub.1-In.sub.4 is shown in FIG. 4B and FIG. 6.

(65) As monolayers M1 and M2 are operated selectively with four identical inputs and can be addressed independently, the outputs of M1 and M2 (FIGS. 4A-4B) correspond to the outputs (Out.sub.A) and (Out.sub.B) of the 4:2 encoder (Table 1). Note that there is no special sequence or order in which the monolayer is read-out. Each monolayer M1 or M2 was addressed individually and read-out individually. As a result each monolayer performed a single simple logic operation in the logic circuit of the encoder. Thus, by plugging two independent molecular monolayers into an arrangement of four inputs; a fully functional and playable logic function results. The entire system can be reset by washing M1 and M2 with H.sub.2O (pH=7.5) for 5 min.

(66) The orthogonal reactivity of the chips of the invention to the applied chemical inputs allowed specific addressing of M1 and M2 with an independent and interference-free read-out. It is reasonable to assume that the method presented here can be expanded to a plethora of different molecular chips that can be designedwhen combined with other molecular chipsto produce functional logic schemes. The advantage of this is a large variety and degree of freedom in designing the logic function, without the need for synthesizing new molecules. Just combining two chips can lead to interesting integrated molecular logic. In addition, the siloxane-based monolayers such as M1, are thermally, chemically, electrochemically robust, stable towards pH gradients and to a wide variety of environmental conditions.

(67) In conclusion, we have shown a new method for fabricating functional logic schemes with a solid state setup. The formation of the logic scheme depends on the combination of different self-assembled monolayers on surfaces. Monolayers of M1 and M2 were able to respond to four different inputs and, by doing so, were able to mimic collectively the first molecular encoder on solid support.

(68) A half-subtractor is a logic circuit which is used for subtracting one single bit binary number from another single bit binary number. The half-subtractor is a combinational circuit which is used to perform subtraction of two bits. It has two inputs, X (minuend) and Y (subtrahend) and two outputs D (difference) and B (borrow). The truth-table and logic circuit of a half-substractor is shown in Table 2 and FIG. 8, respectively.

(69) TABLE-US-00002 TABLE 2 Truth-table of a half-subtractor operating with two inputs (X and Y). X Y D B 0 0 0 0 0 1 1 1 1 0 1 0 1 1 0 0

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