KR100808966B1 - Programmable molecular device - Google Patents

Abstract

A programmable molecular device 10 is provided that includes a randomized nano-network 20 that includes a plurality of molecular circuit components 14. Preferred molecular circuit components 14 include molecular diodes exhibiting negative differential resistance. The method of programming the molecular device 10 may comprise constructing the molecular component 14. Configuring the molecular component 14 may include applying a voltage across the input and output leads connecting the nano-network 20. The voltage may be determined according to a self-adaptive algorithm that programs the device to function as, for example, a logic unit or a memory unit. Molecular compositor 66 may include a plurality of programmable molecular elements 62 interconnected by metallic wires 65.

Description

Programmable Molecular Devices {PROGRAMMABLE MOLECULAR DEVICE}

Work on the present invention was funded by DARPA through Office of Naval Research Authorization No. ONR N00014-99-1-0406.

Reference to CD-ROM Addendums and Statements Under US 37 C.F.R §1,52 (e) (5)

Attached herein and incorporated by reference as copies of the IBM-PC format (“Copy 1” and “Copy 2”) that are MS-Windows and MS-DOS compatible according to US 37 CFR §1.52 (e) (5). . Copy 1 and Copy 2 are identical and contain 269 files in one main directory and two subdirectories, as identified by the following output from the MS-DOS command "dir e: / s", where the output is each file. Contains a line in the standard format [month / date / year time bytes filename.extension], one line that allows a person skilled in the computer arts to identify the creation date, size, file name, and type of each file:

FIELD OF THE INVENTION The present invention relates generally to programmable electronic devices, and more particularly to programmable nanoscale devices based on molecular circuit components.

Basic functions of a computer include information processing and information storage. In von Neumann (serial) architecture, arithmetic, logic and memory operations are performed by devices that can be reversibly switched between two states, commonly referred to as "0" and "1". Semiconductor devices that perform many of these functions must be able to switch between the two states at very high speeds with minimal electrical energy in order to allow the computer to perform basic operations. In computers, transistors perform those basic switching functions.                 

While the design and manufacture of energy-efficient state-of-the-art electronic devices is increasingly dependent on the ability to fabricate higher density circuit devices in integrated circuits, semiconductor-based computer technologies and architectures have developed to the near quantum mechanical limits of such configurations. . In the near future, the growth of high performance computers in terms of size and price will be limited. The main component that controls the characteristics of these high performance computers is the memory, in particular the memory circuit density. The enormous data storage requirements for these devices require new compact, low cost, ultra high capacity, and high speed memory circuit configurations. A more detailed discussion of the problem of miniaturization of electronic devices can be found in US Pat. Nos. 6,259,277, 6,219,833, 5,589,692, and 5,475,341, each of which is incorporated herein by reference.

Molecular scale electronics is a field of research that proposes the use of single molecules or groups of molecules as possible components in future computer devices. In particular, molecules with a strategically charged charge barrier could act as a switch. In addition to substantial dimensional reduction, the response time of molecular devices can fall into the femto-second range, while the fastest current devices operate in the nanosecond range. Thus, a 10 ⁵ to 10 ⁶ fold increase in speed may be achieved, especially if other circuit elements do not limit operating performance.

Optimizing the size of a conventional base unit (typically a transistor) and its speed (limited by the unit's inherent temporal response) is a conflicting design goal. Therefore, there must be a balance of both. The most important compromise in computer technology is hardware-software duality, which is implemented in the requirements of wired logic (CPU dominant or hardware dominant) over programmed logic (memory dominant or software dominant). Components of programmed logic are smaller than wired logic and can handle more tasks, but wired logic is faster than programmed logic. In one extreme case, it may be a bit adder (the smallest logical unit that can be summed) with a few logic gates that require large memory to get the result, while in the other extreme the input and output It could be a large CPU with all the specific functions wired into a system that can handle the entire task with only a small memory for the data. Current technology is leaned toward programmed logic, for example computers with large memory and high speed but simple CPUs.

The ongoing challenge to implementing molecular electronics is to pursue an approach for arranging molecular components within structures with logic functions. Accordingly, research has been conducted on architectures that enable the use of molecular components as basic switching devices in building logic devices. Any gate can be constructed from a complete set of one or more basic gates. A plurality of these basic gates can be arranged in series or in parallel, or a combination of the two to form other logic functions. Thus, the emphasis has been on demonstrating the functionality of the basic gate. N and gate are one basic gate which forms a complete set by themselves, and NOR gate is another basic gate which forms a complete set by itself. Other complete sets include and combinations of gates and XOR gates, combinations of OR gates and XOR gates, and combinations of gates and NOT (also called inverter) gates, and combinations of OR gates and NOT gates.

In one approach, basic logic functions have been proposed that use a single molecule with relatively small accumulations of small molecules bound together. Each small molecule is designed to simulate the function of a conventional circuit element. Such speculative molecules are presented in the March 2000 IEEE Bulletin, James C. Ellenbogen and J. Christopher Love, FIGS. 12-14 of pages 386-426. This article is incorporated herein by reference. The molecules shown in Figures 12, 13 and 14 of this reference are proposed to function as and gates, OR gates and half adders, respectively. The disadvantage of this approach is that it is difficult to synthesize the proposed molecule. In addition, dynamic morphological changes in molecular segments tend to cause shorts between the molecular segments.

In another approach, a basic logic function is illustrated in which a switch containing a monolayer of hundreds of molecular diodes between leads and a mixture of conventional circuit components are arranged. The switching function is illustrated in a device consisting of a single layer of molecular diodes oriented between two conventional metal plates, such as a capacitor plate. A monolayer is a layer of molecules with a thickness of one molecule. In a single layer, molecules are oriented side by side with functional groups at both ends that allow them to bind to the metal and hence are termed molecular alligator clips. Both ends having the functionality are bonded to the metal plate. Examples of circuits containing switching devices based on molecular monolayers that have been shown to have N and and NOR functionality are described in Proc, SPIE 2001, vol. 4236 pp. 80-88 by David P. Nackashi and Paul D. Franzon. The paper "Moletronics: A circuit design perspective" is presented in FIG. 5. This article is incorporated herein by reference in its entirety. In addition, a circuit containing an oriented molecular monolayer is described in a paper, filed April 18, 2000, US Patent Application No. OCR 1049, entitled "Molecular Scale Electronic Devices," which is herein incorporated by reference. Included by reference.

In each of these approaches, molecular class devices implement wired logic. This is in opposition to recent technological trends towards programmed logic. Wired logic also tends to be less resistant to defects than programmed logic. In order for industrial scale manufacturing of molecular class devices to be cost effective and effective, such devices must be durable against defects that may occur during chemical assembly.

Molecular-level electronics offer the possibility of computational processing that hinders the improvement of our current capacity. Therefore, there is a need for techniques that generate logic programmed from molecular components in an effective, robust and reproducible manner.

In one preferred embodiment, the present invention features programmed logic using molecular components. Alternatively, the present invention provides a programmed memory using molecular components. Molecular components are arranged in nanocells that form small programmable units. Nanocells contain trillions of molecules, many of which preferably have a suitable orientation for switching. This creates a balance between the desire for miniaturization realized by single molecular logic and the desire for robust programmable functionality. The nanocells of the present invention have the advantage that a single nanocell assembled by direct wet chemical technology is initially programmed to run as one logical unit and then optionally reprogrammed to function as another logical unit. The nanocells are also adapted to suitably position the conventional logic units within a standard computer, while providing the same functionality on a smaller scale than currently available in conventional silicon-based logic.

The versatility, robustness and ease of manufacture of the nanocells of the present invention are realized by constructing the nanocells from molecular components that allow self-assembly into one structure. Unless guided by a scaffold, the molecular components are assembled in a random array such as a random network. Since the network preferably extends in size from about 1 nm to about 2 μm, it is referred to herein as a nano-network. Random arrays have the advantage that little or no effect on the function of the nanocells occurs when a particular molecular component is not present at a particular location. That is, the nanocells are programmable regardless of the precise arrangement of the molecular components. The nanocells are programmable by an iterative method called a self-adaptive algorithm in which the algorithm is fitted to an array of molecular components.                 

As such, the present invention combines features and advantages that enable the overcoming of various problems of conventional devices. Various features and other features described above will be readily apparent to those skilled in the art by referring to the following detailed description of the preferred embodiment of the present invention and the accompanying drawings.

Reference will now be made to the accompanying drawings for a more detailed description of the preferred embodiments of the invention:

1 is a schematic diagram of a nanocell according to an embodiment of the present invention;

2A and 2B are schematic views of arrangement of leads in accordance with an embodiment of the present invention;

3 is a schematic representation of a molecular component in accordance with an embodiment of the invention;

4A and 4B are graphs of the I (V) response of the molecule shown in FIG. 3;

5 is a schematic diagram of a molecular computer according to an exemplary embodiment of the present invention;

FIG. 6 is a schematic representation of molecular devices containing pyridyl groups as "alligator clips"; FIG.

7 is a schematic diagram of a simulated nanocell according to an exemplary embodiment of the present invention, in which solid lines represent high conductivity molecules as "on" and dotted lines represent low conductivity molecules as "off";

8 is a schematic diagram of the simulated nanocell of FIG. 7 programmed to function as an inverter gate;

9 is a schematic of the simulated nanocell of FIG. 7 programmed to function as N and gate;

FIG. 10 is a schematic diagram of the simulated nanocell of FIG. 7 programmed to function as an inverse half adder gate.

Nanocell

First, referring to FIG. 1, the molecular electronic device 10 includes a nanocell 12. Nanocell 12 includes at least one, preferably a plurality of molecular circuit components 14. Nanocell 12 preferably has a linear dimension 16 of about 2 μm or less, more preferably about 1 nm to about 2 μm. Linear dimension 16 may be the length of side 18 of nanocell 12. The side 18 surrounds and defines the border of the molecular circuit component 14. Nanocell 12 may comprise any number of sides and may be one-dimensional to three-dimensional. In FIG. 1 nanocell 12 is shown as a square. It will be appreciated that other shapes may be contemplated, such as round, rectangular, or any other suitable shape.

Referring back to FIG. 1, the nanocell 12 preferably further includes at least one input lead 20 and at least one output lead 22. The number of input leads and output leads is not critical. The number of leads is preferably limited only by the technique of forming the leads 20, 22, as in conventional lithography, and by the size of the nanocell 20. Although leads 20 and 22 are shown at the edge of nanocell 12 in FIG. 1, it will be appreciated that other arrangements of leads may be contemplated. For example, as shown in FIG. 2A, the input lead 23 and the output lead 25 may extend from an edge of the nanocell 27 and may be inserted into each other. Alternatively, as shown in FIG. 2B, input lead 29 and output lead 33 may extend from concentric circumference 37 that defines the edge of nanocell 39.

Nano-network 20 preferably spans each input lead 20 and each output lead 22. Leads 20 and 22 may be metallic and are designed to connect to the interconnections of conventional lithography, such as metal wires. The molecular circuit component 24 at the edge is connected to the leads 20, 22 via a molecular alligator clip 26. Molecular alligator clips include tacky end groups based on components such as sulfur, oxygen, selenium, phosphorus, isonitrile, pyridine and carboxylate and which bind to the metal. Particularly preferred sulfur-based molecular alligator clips are thiol groups. It will be appreciated that the molecular circuit component 14 may include two, three, four, five, six or more terminus, and references therein for reference. Included as Tour, JM; Kozaki, M .; And Seminario, J.M. "Molecular Scale Electronics: A Synthetic / Computational Approach to digital Computing," J. Am. Chem. Soc. 120,8486-8493 (1998) and US Pat. No. 6,259,777. Each end is preferably an end that includes a molecular alligator clip.

With continued reference to FIG. 1, the nanocell 12 is preferably a nano-network 28 having a network structure in which molecular circuit components form at least part of the network. Nano-network 28 is preferably a random nano-network. In particular, the nano-network 28 preferably has at least one random element as follows. The x-ray crystal structure of the nano-network 28 may not include distinct peaks indicating periodic or semi-periodic arrangement of the molecular circuit components, preferably for lengths on the order of about 1 nm to 2 μm. Alternatively, the x-ray crystal structure of nano-network 28 may include at least one peak indicating no characteristic length on the order of about 1 nm to 2 μm. As another case, the nano-network 28 may have a structure exhibiting scaling behavior, multi-scaling behavior, fractal characteristics, and the like. As another case, the nano-network 28 may orient the molecular circuit component 14 about any axis along a known random distribution, such as the Poisson distribution of several molecules between nanoparticles in the network. It may have a structure including. As another case, the nano-network 28 may have a structure that includes the location of the center of mass of the molecular circuit component 14 along a known random distribution such as the nature of an amorphous or amorphous solid. It will be understood that the term "random" as used herein may include any other conventional definition and may be used interchangeably with the terms "chaotic" and "irregular." It will also be appreciated that randomness can occur for any given length level. In particular, the term random network herein includes a network with little long-range alignment. Long distance may mean a long distance with respect to the length level of the components constituting the network. An advantage of the random arrangement of the molecular circuit components 14 in the molecular electronic device 10 is that the device 10 can be tolerant to faults.

With continued reference to FIG. 1, in one preferred embodiment of the present invention nano-network 28 is self-assembled. As is known in the art, self-assembled networks are those that generate themselves from components that make up themselves in response to stimulants such as changes in reaction conditions. Self-assembled nano-networks preferably have a structure that is not predetermined. In addition, the self-assembled nano-networks of this embodiment preferably have only a short range level between adjacent nanoparticles, and are disordered over relatively long length levels.

Nano-networks suitable for use in the present invention include, but are not limited to, nano-networks made as in the following description. Metal nanoparticles are deposited on an oxide grid. The oxide grating can be a semiconductor substrate from which material has been removed to partition holes that provide the boundaries of the nano-network. Molecular self-assembled monolayers that coat each of the nanoparticles can be used to control the spacing between the nanoparticles. Through the above-described process, the molecular switch is inserted into an inert self-assembled monolayer barrier surrounding each of the nanoparticles, thereby interconnecting adjacent nanoparticles. The process is Dunbar, TD, which is incorporated herein by reference; Cygan, MT; Bumm, LA; McCarty, GS; Burgin, TP; Reinerth, WA; Jones, II, L .; Jackiw, JJ; Tour, JM; Weiss, PS; Allara, DL J. Phys. Chem. B. 2000 , 104 , 4880-4893.

With continued reference to FIG. 1, a nano-network 28 can be contemplated that is trainable and includes any suitable conventional molecular circuit components. Thus, the molecular circuit component 14 can be selected from molecular wires, molecular rectifiers, molecular diodes, molecular switches, molecular resistors, molecular transistors, and the like, and combinations thereof. Molecular wires, rectifiers, diodes, switches, resistors, or transistors are any molecules that can function the same as conventional wires, rectifiers, diodes, switches, resistors, or transistors, respectively, in a circuit. Examples of molecular wires include oligo (phenyleneethynylene) and the like. Examples of molecular rectifiers include hexadecquinquinolinium tricyanoquinodimethide and the like.

With continued reference to FIG. 1, the molecular circuit element 14 preferably includes a conjugated molecular segment. The conjugated molecular segment is preferably substituted at the end with a group that functions as a molecular alligator clip. Examples of conjugated molecules that serve as molecular conjugated segments for molecular circuit devices and examples of conjugated molecules functionalized with molecular alligator clips are described in the following documents, each of which is incorporated herein by reference: Tour, JM "Molecular Electronics. Synthesis and Testing of Components," Accounts of Chemical Research, volume 33, number 11, pages 791-804 (2000); Tour, JM; Kozaki, M .; And Seminario, JM "Molecular Scale Electronics: A Synthetic / Computational Approach to digital Computing," J. Am. Chem. Soc. 120, 8486-8493 (1998); dirk, SM, et al. "Accoutrements of a molecular computer; switches, memory components and alligator clips," Tetrahedron 57, pp. 5109-5121 (2001). Molecular circuit components 14 are also described in US patent application Ser. No. 18,2000, incorporated herein by reference. And any molecule, conductive organic material or conductive pathway described in Agent List No. OCR 1049, titled “Molecular scle Electronic Devices”.

The molecular circuit component 14 preferably exhibits negative differential resistance. Conventional resonant tunneling diodes also exhibit negative differential resistance. However, conventional resonant tunneling diodes are based on gallium arsenide. Negative differential resistance is a particularly useful property in the design of logic because it allows negation.

Referring to FIG. 3, the molecular circuit component 14 may be a molecular diode 30. Examples of molecular diodes are mononitro substituted oligophenylenes (32), in particular 4,4'-diphenyleneethynylene-2'-nitro-1-benzenethiol and dinitro substituted oligophenylenes (34). As examples are 2 ', 5'-dinitro-4,4'-diphenyleneethynylene-1-benzenethiol.

Other molecular diodes include the dithiol substituted homologs of molecules 32 and 34, in particular 4,4'-diphenyleneethynylene-2'-nitro-1,4 "-benzenedithiol and 2 ', 5'-dinitro-4,4'-diphenyleneethynylene-1,4 "-benzenedithiol is included, respectively. Each of these molecules contains a thiol group at each end. Such a structure is preferred for the molecular circuit component 14 where each end contacts gold. The term molecular switch as used herein means including these molecules when they are in an electrical environment that enables them to function as switches. The electrical environment can be formed by adding or modifying substituents, coupling other molecules to the molecular diode, or by connecting the molecular diode to a circuit element, for example by a molecular alligator clip.

Nanocell 12 may further include a nanoscale component 40. Nanoscale component 40 is preferably arranged as part of nano-network 28. The nanoscale component can have the functionality of an electrical connector to assist in forming the molecular component 14 into a conductive network. In addition, nanoscale components can have the functionality of electrical circuit components such as conductance, capacitance, resistance, impedance, and the like. Examples of nanoscale components include nanotubes, nanoparticles, nanorods, and combinations thereof. Examples of nanoparticles and nanotubes are described in Reed, M.A. And Tour, J.M. Scientific American 282, pp. 86-93 (2000). Examples of nanorods are described in Martin, B.R., et al. "Orthogonal self-assemble on colliodal gold-platinum nanorods," Adv. Mater. 11, pp. 1021-1025 (1999).

It will be appreciated that a plurality of molecular circuit components 14 may be substituted where one molecular circuit component 14 is shown in solid lines in FIG. 1. For example, a plurality of molecular circuit components 14 may contact each of the pair of nanoscale components 40 to connect the nanoscale components.

With continued reference to FIG. 1, in an exemplary arrangement, nanocell 10 includes a molecular switch 52 and nanoparticles 54. It is preferable that the nanoparticle 54 is metallic, More preferably, it is gold. The molecular switch 52 is preferably a switch having thiol molecular alligator clips at both ends, more preferably 2,5-dinitro-4,4'-diphenyleneethynylene-1,4 -Benzenedithiol. The edge molecular switch 56 is connected to the input lead 20 and the output lead 22. The molecular switch 52 interconnects the nanoparticles 54. Here, the term interconnect is used in the sense of enabling electrical continuity. In this sense, from another angle, nanoparticles 54 interconnect molecular switches 52. In addition, the electrical continuity provided by the molecular switch 52 need not be permanent and can be broken by configuring the molecular switch 54.

Nano-network 28 is preferably formed by molecular switch 52 and nanoparticle 54. In particular, the nanoparticles 54 are preferably arranged in little or no order. The molecular switch 52 also interconnects the nanoparticles 54. Not all nanoparticles 54 are connected to other nanoparticles 54 and some nanoparticles 54 are connected to one or more, or two or more other nanoparticles, such connections may be randomly distributed. .

Impedance characteristics of the nanocells 12 include metals of the nanoparticles 54, conjugated backbone structures of the molecular circuit components 14, components for the alligator clips of the molecular circuit components 14, leads 20, 22. It will be appreciated that one can optimize by changing any one or combination of geometries, and other suitable properties for adjusting impedance.                 

It will also be appreciated that the molecular circuit component 14 can be a multi-state molecule, such as three, four, five or six state molecules. C _60, for example, has six independent states obtained by taking six electrons incrementally. Thus, the molecular circuit component 14 is not limited to binary logic of "0" and "1" or "on" and "off", for example ternary and ternary logic are conceivable.

Referring to FIG. 5, a plurality of programmable electronic devices 62, preferably nanocells 64, may be interconnected by metal wires manufactured in a standard lithographic manner to form a molecular computer 66. . Nanocell 64 is preferably configured as described above with respect to FIG. 1, more preferably as shown in FIG. 4, for example. Any conventional architecture can be envisioned for interconnection by wire 65.

Programmability

Referring again to FIG. 1, the molecular electronic device 10 is preferably programmable. More specifically, the molecular electronic device 10 may be programmed with a self-adaptive algorithm. Self-adaptive algorithm as used herein means that the algorithm can "evolve" using an iterative process of querying and adjusting the system to move the system to a desired state. More specifically, self-adaptive algorithms are a class of algorithms that include a set of rules that compare the actual results of the system to the target results and adjust the input to the system based on the difference function between the actual and target results. The next actual result is related to the input adjusted according to the operation of the system. By adjusting the input repeatedly, the actual result converges with the target result. In this way the self-adaptive algorithm trains the system.

The molecular element 10 may preferably be programmed by a self-adaptive algorithm for constructing the molecular circuit component 14.

In a preferred embodiment, the molecular circuit component 14 may be configured by applying a voltage across the leads 20, 22. For example, the molecular circuit component 14 can include molecules whose properties affecting conductivity can be controlled by applying a voltage across the leads 20, 22. The property affecting the controlled conductivity is preferably selected from the group consisting of charge, conformalal state, electronic state, and combinations thereof.

It will be appreciated that the molecular circuit component 14 can be constructed in other ways.

Oligophenylene-based molecular wires and switches are examples of molecules whose conductivity is affected by charge, electronic state and steric state. It is believed that applying a voltage across these molecules can cause transitions between electronic states. Voltage can cause an increase in charge by causing molecules to attract electrons. In addition, when charged, the molecule transitions to the excited electronic state. Phenyl rings rotate relative to one another to align electron orbits, such as pi orbits, to form molecular orbits extending to the molecular length. It is believed that the molecule is conductive by establishing electronic continuity through the molecular orbits in the presence of an applied voltage. A description of molecular instruments with switching functions is provided in Donhauser, Z.J. et al., Science 292, pp. 2303-2307 (2001).

In a preferred embodiment, the electrical properties of the material used to make the lead in contact with the molecule are consistent with the energy theory of molecular electron transitions. In particular, the Fermi energy of the metal in contact with the conjugated molecular circuit device is close in energy to the lowest unoccupied molecular orbital (LUMO) energy of the molecular circuit device. This has the advantage of optimizing the impedance characteristics of the metal and intermolecular connection.

The operation of molecular switches is different from molecular wires. The conductivity of the switch can be changed to a stable state for a relatively long time by lowering and then removing the voltage. Referring to FIG. 3, stability time of at least 24 hours was obtained using the molecule 34. In addition, improved sealing of systems with molecular switches; The use of similar oligophenylene-based molecules having a plurality of nitro groups; Alternatively, the use of new classes of molecules is expected to allow longer settling times, such as days or months. Preferred molecular switches can be constructed by applying a switching voltage and operated in either a high conductivity state or a low conductivity state by applying an operating voltage below the switching voltage.                 

Referring to FIG. 3, the operation of the molecular switch is illustrated by the operation of molecule 34. When a switching voltage of 2.0 V or higher is applied to the molecule 34, the molecule 34 is brought into a high conductivity state. When a corresponding voltage of -2.0 V or less is applied to the molecule 34, the molecule 34 is brought into a low conductivity state. Will change. The switching voltage is preferably about 0.2 to 3.0 V in the high conductivity state and -0.2 to -3.0 V in the low conductivity state. In FIG. 4, the high conductivity state relates to the I (V) curve tracked by the black point, and the low conductivity state relates to the lower I (V) curve tracked by the white point. The degree of differentiation between high and low conductivity states is measured by the difference between these two curves. When an operating voltage of -2 V to 2 V is applied to the molecule 36, the molecule conducts according to its high or low conductivity, which it has recently switched. Molecules in a high conductivity state will also exhibit low conductivity when a voltage is applied that exceeds the negative differential resistance (NDR) limit. The degree of differentiation between high and low conductivity of molecules in high conductivity states due to NDR effects is determined by the ratio between the highest and lowest points on the I (V) curve tracked by black dots. Preferably, the absolute value of the operating voltage is about 0.2 V to about 2.0 V.

Referring again to FIG. 1, the nanocell 12 is preferably programmable by an algorithm for setting the molecular switch 54. The molecular switch 54 is preferably settable by applying a voltage across the leads 20, 22. Self-adaptive algorithm for programming nanocell 10 can be applied to leads 20, 22 that constitute a remote molecular switch, which is a molecular switch that is not directly connected to leads 20, 22. It is desirable to be able to learn.

It will be appreciated that the form of the self-adaptive algorithm is not important. Any suitable conventional self-adaptive algorithm capable of training a network such as nano-network 28 may be used. Examples of self-adaptive algorithms include genetic algorithms, simulated annealing algorithms, reinforcement learning algorithms, time difference algorithms, go with the winner algorithm, and the like. The principles of self-adaptive algorithms are described in Goldberg, DE, Genetic algorithms in Search, Optimization, and Machine learning, (Addison Wesley, Reading, MA, 1989), pp. 1-15, 221-229, incorporated herein by reference. It is described.

Self-adaptive algorithms have the advantage of error-resilient. In addition, the use of self-adaptive algorithms provides the advantage of fault tolerance. Accordingly, the molecular electronic device 10 can be manufactured by a self-assembly method that can be implemented on an industrial scale with cost-effective reliability. Self-adaptive algorithms can be coded in the secondary computer.

An advantage of the present invention is that the programmability of the molecular electronic device 10 means that the first assembled device does not have to function as a particular logic device. Thus, the molecular electronic device 10, nanocell 12 and nano-network 28 need not have a predetermined structure. Nanocell 12 and particularly nano-network 28 may be self-assembled into an intermediate structure that may be random. Self-adaptive algorithms can be used to program the device 10 to function as the desired device.

In a preferred embodiment, element 10 may be programmed to function as a logic unit selected from the group consisting of and gate, OR gate, XOR gate, NOR gate, NOT gate and N and gate and the like. Thus, when device 10 is programmed in this embodiment, it is a programmed logic device having a logic device selected from the group consisting of AND, OR, XOR, NOR, NOT and N, and the like.

In another preferred embodiment, element 10 may be programmed to function as a logical unit selected from the group consisting of adders, semiadders, multiplexers, decoders, and the like. Thus, when device 10 is programmed in this embodiment, it is a programmed logic device having a logic element selected from the group consisting of an adder, a half adder, a multiplexer, a decoder, and the like. In another preferred embodiment, element 10 may be programmed to function as a memory unit.

It will be appreciated that element 10 preferably functions as any gate having a truth table supported by input / output pins.

The device 10 is preferably programmable. In particular, the element 10 initially programmed to function as one of the logical units or memory units described above may be programmed to function as the other of the logical elements or memory elements described above. Thus, element 10 has the advantage of versatility.

The programmability described above is achieved using the preferred topology of the nanocell structure described above in combination with the preferred programming method described below.

Programming method

Preferred methods of making electronic components include providing self-assembled nanocells and programming the nanocells to function as electronic components. The nanocell is preferably a nanocell according to any one of the embodiments described above.

Programming of the nanocells preferably includes constructing molecular circuit components. Configuring the molecular circuit components preferably includes adjusting physical properties that affect the conductivity of the at least one molecular circuit component by applying a voltage across the input leads and the output leads. Physical properties that affect conductivity may be selected from the above-described conductivity influence properties.

The programming of the nanocells preferably further comprises testing the performance of the nanocells. For example, the performance can be tested by comparing the input / output operating voltage relationship of the nanocell with a target truth table, such as a desired logic truth table.

The programming of the nanocells further preferably includes repeating the construction of the molecular circuit components and the performance testing of the nanocells until the nanocells function as desired electronic components. For example, the above steps may be repeated until the input / output operating voltage relationship matches the target truth table described above within the desired error. Once programmed, the electronic component serves as one of the logical units or memory units described above or other similar elements.

Methods of providing self-assembled nanocells include self-assembling a plurality of nanocell components into a random array, self-assembling the plurality of molecular circuit components into a network interconnected between nanoscale components, and molecular circuit components. It is preferred to include the step of binding to the nanoscale component with a molecular alligator clip. The random array may be an array with short-range order and long-range disorder. The molecular alligator clip may comprise any component useful as the molecular alligator clip described above. Preferred components are thiol groups. The nanoscale component can be any of the nanoscale components described above, for example. The molecular circuit component can be any of the molecular circuit components described above, for example.

Any of the embodiments described above for programming or training nanocells can be used to assemble a computer from a plurality of nanocells. One method of making a computer is to provide a plurality of trained self-assembled nanocells, interconnecting the trained nanocells to a plurality of untrained nanocells, and the trained nanocells to which the trained nanocells are not trained. It is preferable to include the step of training the training. The advantage of the method is that the trained nanocells are used for bootstrap training of untrained nanocells. Thus, the method may include hierarchically repeating the interconnection of nanocells and using recently trained nanocells for training untrained nanocells. In this way, molecular computers can be made quickly and efficiently from a plurality of nanocells.

EXAMPLE                 

Example 1 Synthesis of Conjugated Molecules

Switch and memory components

Synthesis targets 1 and 2 were selected in an effort to improve electronic memory time by adding more nitro groups. SAc groups are readily decomposed into free thiols (SH) when treated with acids or bases. The synthesis scheme of compound 1 is shown in scheme 1.

Synthesis of Compound 1 began with Sonogashira coupling reaction of 2,5-dibromo-4-nitroaniline (3) with phenylacetylene to obtain Compound 4 , which was subjected to HOF oxidation to form Compound 5 . The final coupling reaction gave the desired compound 1 in 24% yield. Low yields in this coupling reaction may mean that the thiol is readily deprotected, or it may mean that the Paladacycle intermediate formed during the coupling reaction is stable.

Scheme 1

In order to conduct electrons, preferably all phenyl rings in the conjugated molecules must be planar to each other. When a phenyl group substitutes for a terminal phenylethynyl group, the system cannot achieve planarity. In an effort to measure the effect of the rotating barrier (ie, the conducting barrier), the synthesis of Compound 2 involves the step of Suzuki coupling 2,5-dibromo-4-nitroacetanilide ( 6 ) to phenylboronic acid. Started through to form Compound 7. The acetyl group was removed to provide aniline ( 8 ) functionality, followed by HOF oxidation to prepare compound 9 in near quantitative yield. Finally, Compound 2 was prepared by Sonogashira coupling reaction.

Scheme 2

Scheme 3

Compound 13 was synthesized for the purpose of studying the electrochemical properties of quinone containing molecular systems. Scheme 3 shows the process of synthesizing compound 13 from 1,4-dimethoxybenzene ( 10 ). Bromine and glacial acetic acid were used to convert compound 10 to compound 11 in good yield. Compound 11 is then cross-coupled with excess phenylacetylene to yield compound 12 , which is then oxidized to quinone to give the desired compound 13 . Since quinone compounds are known to oxidize palladium (0) to form palladium (II) to terminate the catalyst cycle, the synthesis route has to be used because quinone compounds are generally not available in palladium-catalyzed couplings. . Ceric ammonium nitrate (CAN) was the inevitable choice for this process because it is a mild neutral oxidant known to produce quinones from dimethoxybenzene ¹⁸ . This oxidation reaction yielded the desired quinone compound in a yield of 47%. Optimal conditions for the oxidation reaction have not yet been obtained in these systems.

Scheme 4

Scheme 4 illustrates the synthesis of a quinone containing molecular system with one thioacetate group that acts as a protected alligator clip. Compound 11 was cross-coupled with phenylacetylene to yield compound 14 , with a yield of 33% which was statistically expected at a moderate level due to the same reactivity of the bilateral aryl bromide of compound 11 under Sonogashira coupling conditions. Compound 15 was prepared by cross coupling of compound 14 and trimethylsilylacetylene, and then compound 15 was obtained by deprotection of alkyne. Subsequently, compound 16 was obtained by cross coupling using palladium as a catalyst with 4-iodobenzenethioacetate. Through CAN oxidation, the final compound 17 was obtained in a yield of 74%. However, this yield was a rarely obtained result. In other trials a much lower yield (-20%) was obtained. Further work is underway to optimize the conditions of the CAN oxidation reaction.

Scheme 5

Scheme 5 illustrates the synthesis of a quinone-containing molecular system with an alligator clip at both ends (5) . This compound can be used to crosslink metallic nanoparticles to mediate connections in future molecular electronic devices. Diyne compound 18 was obtained in good yield by cross-coupling compound 11 with excess trimethylsilylacetylene and then deprotecting. This compound was then cross-coupled with 2 equivalents of 4-iodobenzenethioacetate to give compound 19 . Finally, compound 20 was produced in normal yield by oxidizing compound 19 using the CAN procedure.

Alligator clips

The synthesis of various compounds containing pyridine alligator clips for binding to molecular electronic devices began with compound 21 . Synthesis of Compound 22 was accomplished by coupling pyridine 21 with 2,5-dibromonitrobenzene as shown in Scheme 1 below. The low yield is considered to be due to the stable cupper acetylide formed after the TMS group was separated. In the absence of deprotection in situ, pyridine alkyne has proved unstable.

Compound 24 was synthesized according to scheme 6. The synthesis started by coupling 1 equivalent of compound 21 to 2,5-dibromonitrobenzene but optionally coupling to the ortho position relative to the nitro group to yield compound 23 . Synthesis was completed by coupling compound 23 to phenylacetylene to produce compound 24 .

Scheme 6

Synthesis of Compound 26 was initiated to study the effect of nitro groups on the chemisorbed pyridine alligator clip. To this end, compound 24 was synthesized in the same manner as the synthesis of compound 23 as shown in scheme 7. Synthesis was completed by coupling one equivalent of phenylacetylene selectively to 2,5-dibromonitrobenzene to form compound 25 , then coupling to compound 21 to obtain compound 26 in good yield.

Scheme 7

Linker 28 was synthesized according to scheme 8. The synthesis begins by coupling 2,5-dibromo-4-nitroacetanilide with excess trimethylsilylacetylene to obtain compound 27 , which is then deprotected in situ and coupled with 4-iodopyridine Compound 28 was prepared in low yield. The low yield of the coupling reaction can be due to the cyclization process between the nitro unit and the alkyne unit.

Scheme 8

Compound 31 was synthesized to form a SAM via a protected benzenethiol end group that, when the pyridyl end of the molecule is bound to the device, serves as a top contact with a metal better than phenyl. Synthesis of compound 31 was carried out by coupling 2,5-dibromo-4-nitroacetanilide with compound 21 to give compound 29 in low yield, followed by coupling compound 29 with trimethylsilylacetylene, followed by potassium carbonate. Compound 30 was obtained by deprotection, and compound 30 was finally couple | coupled with 4-iodobenzenethioacetate, and the molecular type device 31 was obtained in favorable yield (75%).

Scheme 9

Compound 32 was synthesized to study the effect of the same rotational barrier as described for compound 2 . Synthesis of compound 32 was accomplished by starting with compound 7 synthesized above and coupling to compound 21 in good yield as shown in Scheme 2.

Compound 34 was synthesized according to Scheme 3 using Compound 33 described above. Compound 34 is a homologue with nitroaniline having a thiol terminus that exhibited negative differential resistance (NDR) in the device examples above.

In addition to the pyridine containing system, three potential memory and switching components with diazonium salts at the ends were synthesized. Compound 38 is homologous to NDR with thioacetyl terminus and Memory 24 with memory component ¹ and pyridyl terminus. Synthesis of compound 38 began with coupling compound 35 ⁷ to 2,5-dibromonitrobenzene in normal yield to afford compound 36 , which was coupled to phenylacetylene to produce compound 37 . Completed molecule 38 in good yield was obtained by diazotization of compound 37 .

Scheme 10

Compound 40 is similar to compound 26 except that the pyridyl group is structurally substituted with an aryl diazonium salt. Synthesis of compound 40 is shown in scheme 11. Aniline 35 was coupled to nitro compound 25 to prepare a diazonium precursor 39 in normal yield. The aniline 42 was diazotized to obtain the desired product 37 .

Scheme 11

Nanoparticle linker 43 was synthesized according to scheme 12. Starting from dinitro 41 , aniline 35 was coupled to obtain dinitroaniline 42, which was then diazotized to obtain product 43 in good yield.

Scheme 12

Experiment

General procedure. All reactions were carried out under a dry nitrogen atmosphere unless otherwise noted. Reagent grade diethyl ether and tetrahydrofuran (THF) were distilled from sodium benzophenone ketyl under nitrogen atmosphere. Reagent grade dichloromethane (CH ₂ Cl ₂ ) was distilled from calcium hydride (CaH ₂ ) under nitrogen atmosphere. Triethylamine and N, N-diisopropylamine (Huenig's base) were distilled over CaH ₂ under a nitrogen atmosphere. Bulk hexanes were distilled before use. Gravity column chromatography and flash chromatography were performed using 230-400 mesh silica gel manufactured by EM Science. Thin layer chromatography (TLC) was performed on a 0.25 mm thickness using Merck 40 F ₂₅₄ .

General Pd / Cu Coupling Reaction Procedure. In a glass tube with an oven dried screw cap was placed all solids containing aryl halides (bromide or iodide), alkyne, copper iodide, triphenylphosphine and palladium catalyst. The air was removed in vacuo and replaced with dry nitrogen (3 ×). THF, residual liquid, and Huenig base or triethylamine were added and the reaction heated with stirring in an oil bath. The reaction mixture was cooled and filtered through gravity filtration to remove solids and diluted with CH ₂ Cl ₂ . The reaction mixture was extracted (3 ×) with an aqueous solution of ammonium chloride (NH ₄ Cl). The organic layer was dried over magnesium sulfate and filtered, and then the solvent was removed in vacuo.

General procedure for deprotecting alkyne protected with trimethylsilyl. Into a round bottom flask equipped with a stirring rod was added protected alkyne, potassium carbonate (5 equivalents to 1 equivalent of protected alkyne), methanol, and methylene chloride. The reaction was heated and upon completion of the reaction the reaction mixture was diluted with methylene chloride and washed with brine (3 ×). The organic layer was dried over MgSO ₄ and the solvent was removed in vacuo.

General HOF Oxidation Procedure. H ₂ O (2 mL) and CH ₃ CN (60 mL) were put into a 125 mL polyethylene bottle and cooled to -20 ° C. F ₂ (20% in He) was then bubbled through the solution at a rate of 50 sccm for 2 hours. The resulting HOF / CH ₃ CN solution was washed with He for 15 minutes. The material to be oxidized was added in acetone or ethyl acetate (10 mL) and mixed for 5 min at -20 ° C before neutralization by injection into saturated NaHCO ₃ solution. The organic phase was then separated, dried over MgSO 4 and the solvent removed in vacuo.

General procedure for diazotizing aniline using nitrosonium tetrafluoroborate in an acetonitrile-sulfola system. A nitrogen-filled dry box was weighed NOBF4 and placed in a round bottom flask equipped with a magnetic stir bar and sealed with septum. Acetonitrile and sulfolane were injected at a volume ratio of 5: 1 and the resulting suspension was cooled to -40 ° C in a dry ice / acetone bath. A solution of aniline was prepared by adding warm sulfolane (45-50 ° C.) to the amine under a nitrogen blanket and sonicating for 1 minute followed by the addition of acetonitrile (10-20% by volume). The aniline solution was then added to the nitrosonium salt suspension over 10 minutes. The reaction mixture was kept at -40 [deg.] C. for 30 minutes then left to come to room temperature. At this point, the diazonium salt was precipitated by addition of ether or dichloromethane, filtered to recover solids, washed with ether or dichloromethane and dried. Further purification was done by reprecipitating the salts from DMSO using dichloromethane and / or ether.

4-ethynylphenyl-2,4-dinitrobromobenzene (5). 2-bromo-4-nitro-5-ethylphenylaniline (490 mg, 1.48 mmol) in ethyl acetate (10 mL) was oxidized according to a general HOF oxidation reaction procedure to give 320 mg (60%) of a yellow solid.

IR (KBr) 3442.7, 3101.4, 2216.8, 1610.6, 1540.9, 1461.3, 1384.8, 1358.7, 1337.1, 1264.4, 906.2, 849.6, 824.4, 760.2, 689.8 cm ^-1 . ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.41 (s, 1H), 8.09 (s, 1H), 7.60-7.58 (m, 2H), 7.41-7.39 (m, 3H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 152.1, 150.4, 132.7, 131.7, 131.0, 130.7, 129.1, 121.5, 119.8, 113.9, 102.0. HRMS calculated: 345.9589. Found: 345.9585.

2 ', 5'-dinitro-4,4'-diethynylphenyl-1-thioacetylbenzene (1) . Compound 4 (300 mg, 0.86 mmol), 4-ethynyl (thioacetyl) benzene (183 mg, 1.04 mmol), bis (dibenzylideneacetone) palladium (12 mg, 0.02 mmol), copper iodide (I) (4 mg, 0.02 mmol), triphenylphosphine (13 mg, 0.05 mmol), Huenig base (0.60 mL), and THF (20 mL) were reacted according to the general coupling procedure. The reaction mixture was heated to 60 ° C. overnight and proceeded according to the procedure above. The crude compound was purified by flash chromatography (silica, 3: 1 dichloromethane: hexane) to give 90 mg (24%) of a light yellow solid.

IR (KBr) 2220.2, 1705.2, 1545.5, 1499.81, 1396.8, 1337.5, 1286.1, 1252.1, 1108.6, 1087.2, 953.2, 926.0, 868.3, 827.2, 756.7, 684.1, 618.3 cm ^-1 . ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.34 (d, J = 0.4, 1H), 8.35 (d, J = 0.4, 1H), 7.63-7.59 (m, 4H), 7.46-7.40 (m, 5H), 2.49 (s, 3 H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 193.2, 151.1, 134.7, 133.1, 132.7, 131.0, 130.7, 129.1, 122.8, 121.7, 119.4, 118.6, 102.4, 100.9, 84.8, 83.5, 30.8. HRMS calcd: 442.0623. Found: 442.0634.

2-bromo-4-nitro-5-phenylacetanilide (7). Compound 6 (676 mg, 2 mmol), triphenylphosphine (52 mg, 0.2 mmol), phenylboronic acid (293 mg, 2.4 mmol), bis (triphenylphosphine) palladium dichloride (70 mg, 0.1 mmol) , And cesium carbonate (977 mg, 3 mmol) were placed in a 100 mL round bottom flask and air was replaced by nitrogen. Toluene (30 mL) was added and the reaction heated to 60 ° C. for 2 days. The reaction was diluted with ether and washed with aqueous ammonium chloride solution (2 ×), dried over MgSO ₄ and the solvent removed in vacuo. The crude product was purified by flash chromatography (CH ₂ C1 ₂ ) to give 430 mg (64%) of a white solid.

IR (KBr) 3373.6, 3322.4, 3086.5, 1774.0, 1681.7, 1568.9, 1528.8, 1445.8, 1389.4, 1358.6, 1245.8, 1179.1, 1112.5, 1056.1, 1030.4, 999.6, 872.0, 850.9, 768.9, 697.1 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 8.54 (s, 1H), 8.15 (s, 1H), 7.80 (br s, 1H), 7.40-7.38 (m, 3H), 7.29-7.27 (m, 2H), 2.26 (s, 3 H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 168.44, 143.77, 139.34, 137.74, 136.81, 128.67, 128.51, 128.47, 127.85, 123.31, 110.59, 25.05. HRMS calcd for C ₁₄ H ₁₁ BrN ₂ O ₃ : 333.9953. Found: 333.9952.

2-bromo-4-nitro-5-phenylaniline (8) . Compound 7 (500 mg, 1.49 mmol), potassium carbonate (1.031 g, 7.46 mmol), methanol (30 mL), and methylenechlorite (30 mL) were placed in a 100 mL round bottom flask for 2 hours at room temperature under a nitrogen blanket. Stirred. K ₂ CO ₃ was filtered off from the reaction and washed with CH ₂ CI ₂ to give 437 mg (100%) of the title compound.

IR (KBr) 3463.7, 3349.2, 3221.3, 1623.9, 1584.6, 1555.4, 1495.5, 1443.6, 1406.9, 1305.6, 1259.4, 1123.9, 1051.7, 896.7, 846.5, 760.1, 701.3, 632.1, 563.8 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 8.21 (s, 1H), 7.39-7.36 (m, 3H), 7.23-7.21 (m (nested), 2H), 6.61 (s, 1H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 148.5, 139.4, 138.5, 130.7, 128.8, 128.4, 128.2, 128.1, 117.2, 106.3. HRMS calculated: 291.9848. Found: 291.9846.

2,5-dinitro-4-phenylbromobenzene (9). According to the general HOF oxidation reaction procedure Compound 8 (373 mg, 1.28 mmol) in ethyl acetate (10 mL) was oxidized to give 407 mg (99%) of an orange solid.

IR (KBr) 3446.7, 3090.4, 1542.8, 1461.1, 1443.1, 1347.3, 1257.7, 1114.6, 1076.2, 1051.8, 1021.0, 904.5, 842.5, 768.8, 743.7, 699.9, 551.0, 485.16 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 8.16 (s, 1H), 7.89 (s, 1H), 7.47-7.45 (m, 3H), 7.31-7.29 (m, 2H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 151.5, 150.6, 137.2, 134.4, 130.8, 130.1, 129.7, 128.9, 128.1, 114.1. HRMS calcd: 321.9589. Found: 321.9592.

2,4'-dinitro-5'-phenyl-4-ethynylphenyl-1-thioacetylbenzene (2) . Compound 9 (147 mg, 0.46 mmol), 4-ethynyl (thioacetyl) benzene (106 mg, 0.60 mmol), bis (dibenzylideneacetone) palladium (26 mg, 0.05 mmol), copper iodide (I) (9 mg, 0.05 mmol), triphenylphosphine (12 mg, 0.05 mmol), Huenig base (0.16 mL) and THF (20 mL) were coupled according to the general coupling procedure. The reaction mixture was stirred and heated to 45 ° C. overnight. The crude product was purified via column chromatography (silica, 3: 1 dichloromethane: hexanes) to give 75 mg (39%) of an orange solid.

IR (KBr) 2922.7, 2214.3, 1702.7, 1542.8, 1488.1, 1357.1, 1271.1, 1115.1, 1088.6, 956.0, 908.6, 829.9, 770.5, 707.0, 623.4 cm ^-1 . ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.16 (s, 1H), 8.10 (s, 1H), 7.63 (d, J = 8.4, 2H), 7.48-7.44 (m, 5H), 7.36-7.33 (m, 2H), 2.44 (s, 3H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 193.3, 151.2, 150.6, 136.8, 134.8, 134.7, 133.1, 130.8, 130.2, 130.1, 129.6, 128.6, 128.1, 122.9, 119.0, 99.8, 84.5, 30.8. HRMS calcd: 418.0623. Found: 418.0619.

2,5-dibromo-1,4-dimethoxybenzene (11). 1,4-dimethoxybenzene (10.0 g, 72.4 mmol) was dissolved in glacial acetic acid (20 mL) in a 100 mL round bottom flask. Bromine solution (7.42 mL, 145.0 mmol) in glacial acetic acid (7.5 mL) was added dropwise to the initial solution at room temperature over 40 minutes. The resulting mixture was stirred for 2 hours. The crude product was washed with ice water and ice cold methanol to give fine white crystals. The mother liquor was concentrated and cooled to give more white crystals (15.9 g, 74% yield).

Mp 136-138 ° C. (lit ²¹ mp 144-145 ° C.). IR (KBr) 3091.9, 3022.1, 2968.8, 2944.4, 2842.8, 1694.9, 1494.2, 1475.6, 1436.5, 1358.2, 1275.0, 1211.8, 1185.0, 1065.4, 1021.9, 860.5, 760.4, 441.8 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) 7.13 (s, 2H), 3.87 (s, 6H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 150.93, 117.53, 110.90, 57.43.

2,5-di (ethynylphenyl) -1,4-dimethoxybenzene (12) . Compound 11 (8.745 g, 29.55 mmol), bis (triphenylphosphine) palladium dichloride (0.415 g, 0.591 mmol), copper iodide (I) (0.225 g, 1.182 mmol), triphenylphosphine (0.310 g, 1.182) mmol), THF (35 mL), Huenig base (20.5 mL, 118 mmo]), and phenylacetylene (7.8 mL, 70.92 mmol) were used according to the general coupling procedure. The solution was heated in a 65 ° C. oil bath for 3 days. Recrystallization from benzene gave the desired product (9.22 g, 92%) which was mp 175-177 ° C. (lit. ¹⁶ 176-177 ° C.).

¹ H NMR (400 MHz, CDC1 ₃ ) δ 7.57 (m, 4H), 7.34 (m, 6H), 7.03 (s, 2H), 3.89 (s, 6H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 154.10, 131.89, 128.60, 128.50, 123.39, 115.86, 113.57, 95.23, 85.86, 56.66.

2,5-di (ethynylphenyl) benzoquinone (13). Compound 12 (0.300 g, 0.886 mmol) and THF (6 mL) were placed in a 25 mL round bottom flask with stir bar. A solution of ceric ammonium nitrate (1.46 g, 2.658 mmol) dissolved in water (3 mL) was slowly added to the flask and stirred for 15 minutes. Water was added and the organics extracted with dichloromethane. Flash column chromatography (silica gel, using 1: 1 hexanes / dichloromethane as eluent) afforded the desired product (0.129 g, 47%).

IR (KBr) 3047.5, 2203.0, 1716.2, 1655.3, 1568.3, 1215.4, 1100.6, 902.1, 757.6, 686.4 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) 7.58 (dd, J = 7.9, 1.5 Hz, 4H), 7.38 (m, 6H), 6.99 (s, 2H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 182.87, 136.55, 133.34, 132.83, 130.57,128.97, 121.83, 105.26, 82.90. HRMS calcd for C ₂₂ , H ₁₂ , 0 ₂ : 308.0837 found: 308.0834.

2-bromo-5-ethynylphenyl-1,4-dimethoxybenzene (14). Compound 11 (2.96 g, 10.0 mmol), bis (dibenzylideneacetone) palladium (0.115 g, 0.20 mmol), copper iodide (I) (0.038 g, 0.20 mmol), triphenylphosphine (0.131 g, 0.50 mmol) , THF (15 mL), Huenig base (6.97 mL, 40.0 mmol) and phenylacetylene (1.21 mL, 11.0 mmol) were used according to the general coupling procedure. The tube was heated in a 50 ° C. oil bath for 18 hours. Column column chromatography (silica gel, using 19: 1 hexanes / diethyl ether as eluent) gives the desired product with a slight impurity (about 15% impurity by NMR analysis) in normal yield (1.02 g, 32% yield). ) This was used for the next step in the impurity state.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.54 (m, 2H), 7.33 (m, 3H), 7.09 (s, 1H), 7.02 (s, 1H), 3.86 (s, 6H).

l, 4-dimethoxy-2-ethynylphenyl-5-(trimethylsilylethynyl) benzene. Compound 14 (1.0 g, 3.15 mmol), bis (dibenzylideneacetone) palladium (0.036 g, 0.063 mmol), copper iodide (I) (0.012 g, 0.063 mmol), triphenylphosphine (0.042 g, 0.16 mmol) , THF (20 mL), Huenig base (2.2 mL, 12.6 mmol), and trimethylsilylacetylene (0.89 mL, 6.3 mmol) were used according to the general coupling procedure. The tube was capped and heated in a 60 ° C. oil bath for 1 day. Flash column chromatography (silica gel, using 24: 1 hexanes / ethyl acetate as eluent) afforded the desired product with slight impurities (0.83 g, 79% yield).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.55 (m, 2 H), 7.32 (m, 3H), 6.98 (s, 1H), 6.95 (s, 1H), 3.84 (s, 3H), 3.83 (s, 3H), 0.27 (s, 9H).

1,4-dimethoxy-2-ethynyl-5- (ethynylphenyl) benzene (15) . 1,4-dimethoxy-2-ethynylphenyl-5- (trimethylsilylethynyl) benzene (0.830 g, 2.48 mmol), potassium carbonate (1.71 g, 12.4 mmol), methanol (50 mL), and dichloromethane ( 50 mL) was used following the general procedure for deprotection to afford the desired product (0.513 g, 79% yield).

¹ H NMR (400 MHz, CDC1 ₃ ) δ 7.55 (m, 2H), 7.33 (m, 3H), 7.00 (s, 1H), 6.98 (s, 1H), 3.87 (s, 3H ), 3.86 (s, 3H ), 3.39 (s, 1 H).

4,4'-di (ethynylphenyl) -2 ', 5'-dimethoxy-1-benzenethioacetate (16). Compound 15 (0.513 g, 1.96 mmol), bis (dibenzylideneacetone) palladium (0) (0.058 g, 0.10 mmol), copper iodide (I) (0.019 g, 0.10 mmol), triphenylphosphine (0.066 g, 0.25 mmol), THF (20 mL), Huenig base (1.37 mL, 7.84 mmol), and 4- (thioacetyl) iodobenzene (0.608 g, 2.16 mmol) were used following the general procedure for coupling. The tube was capped and heated in a 55 ° C. oil bath for 3 days. Flash column chromatography (silica gel, using dichloromethane as eluent) afforded the desired product with slightly impurities (0.621 g, 76% yield).

¹ H NMR (400 MHz, CDC1 ₃ ) δ 7.57 (in, 4H), 7.38 (d, J = 8.1 Hz, 2H), 7.33 (m, 3H), 7.03 (s, 1H), 7.02 (s, 1H), 3.874 (s, 3H), 3.870 (s, 3H), 2.40 (s, 3H).

2-ethynylphenyl-5-((4'-thioacetyl) ethynylphenyl) benzoquinone (17). Compound 16 ( 0.050 g, 0.12 mmol), acetonitrile (5 mL), and THF (5 mL) were charged to a 25 mL round bottom flask containing a stir bar. Ceric ammonium nitrate solution (0.13 g, 0.24 mmol) dissolved in water (1 mL) was added in one portion. After stirring for 30 minutes at room temperature, the same amount of ceric ammonium nitrate (0.13 g, 0.24 mmol) was added again. After another 20 minutes, the reaction was cooled by adding water (30 mL) to precipitate an orange solid. Flash column chromatography (silica gel, using dichloromethane as eluent) afforded the desired product (0.034 g, 74% yield).

IR (KBr) 3053.0, 2924.3, 2852.6, 2205.4, 1703.4, 1652.7, 1568.8, 1483.7, 1442.2, 1354.8, 1221.3, 1105.4, 1089.4, 949.6, 920.1, 830.9, 758.2, 688.2, 620.6 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 7.58 (m, 4H), 7.42 (m, 2H), 7.38 (m, 3H), 6.98 (s, 1H), 6.97 (s, 1H), 2.42 (s, 3H ). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 193.22, 182.74, 182.67, 136.88, 136.51, 134.63, 133.34, 133.24, 132.99, 132.84, 130.94, 130.63, 128.99, 122.81, 121.80, 105.38, 103.99, 84.17, 82.92, 92.92 HRMS calcd for C ₂₄ , H ₁₄ , 0 ₃ , S: 382.0664. Found: 382.0663.

l, 4-dimethoxy-2,5-bis (trimethylsilylethynyl) benzene. Compound 11 (1.75 g, 5.91 mmol), bis (triphenylphosphine) palladium dichloride (0.207 g, 0.296 mmol), copper iodide (I) (0.113 g, 0.591 mmol), triphenylphosphine (0.155 g, 0.591 mmol), THF (20 mL), Huenig base (4.1 mL, 23.64 mmol), and trimethylsilylacetylene (2.51 mL, 17.73 mmol) were used following the general procedure for coupling. The tube was capped and heated in a 55 ° C. oil bath for 2 days. Flash column chromatography (silica gel, using 1: 1 hexanes / dichloromethane as eluent) afforded the desired product (1.54 g, 79% yield).

IR (KBr) 2957.0, 2898.2, 2851.2, 2829.0, 2149.1, 1496.8, 1464.1, 1449.1, 1388.2, 1283.7, 1249.0, 1223.6, 1203.1, 1172.4, 1039.6, 883.2, 841.3, 757.4, 714.9,696.2, 626.4 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ.89 (s, 2H), 3.81 (s, 6H), 0.25 (s, 18H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 154.56, 116.59, 113.81, 101.22, 100.84, 56.83, 0.40. HRMS calcd for C ₁₈ , H ₂₆ , 0 ₂ , Si ₂ : 330.1471, found: 330.1468.

1,4-dimethoxy-2,5-diethynylbenzene (18). 1,4-dimethoxy-2,5-bis (trimethylsilylethynyl) benzene (1.50 g, 4.54 mmol), potassium carbonate (6.27 g, 45.4 mmol), methanol (50 mL), and dichloromethane (50 mL) Was used following the general procedure for deprotection to give the desired product (0.829 g, 98%).

¹ H NMR (400 MHz, CDC1 ₃ ) δ 6.96 (s, 2H), 3.84 (s, 6H), 3.37 (s, 2H).

2,5-bis (4 '-(thioacetyl) ethynylphenyl) -1,4-dimethoxybenzene (19). Compound 18 (0.810 g, 4.35 mmol), bis (dibenzylideneacetone) palladium (0.253 g, 0.44 mmol), copper iodide (I) (0.084 g, 0.44 mmol), triphenylphosphine (0.115 g, 0.44 mmol) , THF (30 mL), Hnig's base (4.5 mL, 26.1 mmol), and 4- (thioacetyl) iodobenzene ²² (2.54 g, 9.14 mmol) was used according to the general procedure for coupling. The solution was stirred for 16 h in a 60 ° C. oil bath. Crystallization from dichloromethane / hexanes afforded the desired product (1.81 g, 85%).

IR (KBr) 3129.1, 3057.4, 3006.2, 2975.5, 2940.0, 2847.4, 2207.2, 1697.7, 1506.8, 1483.1, 1463.1, 1396.2, 1279.2, 1223.5, 1122.2, 1034.2, 949.5, 898.8, 825.5, 765.6, 616.8 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 7.57 (dt, J = 8.5, 1.9 Hz, 4H), 7.39 (dt, J = 8.5, 2.0 Hz, 4H), 7.01 (s, 2H), 3.89 (s, 6H ), 2.42 (s, 6 H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 193.85, 154.43, 134.58, 132.65, 128.64, 124.84, 116.08, 113.75, 94.76, 87.73, 56.91, 30.70. HRMS calcd for C ₂₈ , H ₂₂ , 0 ₄ , S ₂ : 486.0960 Found: 486.0956.

2,5-bis (4 '-(thioacetyl) ethynylphenyl) benzoquinone (20). Compound 19 ( 0.050 g, 0.103 mmol), acetonitrile (5 mL), and THF (3 mL) were added to a 25 mL round bottom flask containing a stir bar. A solution of ceric ammonium nitrate (0.339 g, 0.618 mmol) in water (2 mL) was added in two portions at 30 minute intervals. After stirring for 3 hours at room temperature, water was added to the reaction to precipitate an orange solid. Flash column chromatography (silica gel, using dichloromethane as eluent) afforded the desired product (0.023 g, 49% yield).

IR (KBr) 2922.2, 2847.4, 2203.4, 1694.9, 1660.1, 1569.9, 1351.8, 1212.3, 1119.7, 1084.6, 1013.2, 960.3, 826.8, 620.6 cm ^-1 . ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.60 (dt, J = 8.3, 1.6 Hz, 4H), 7.42 (dt, J = 8.3, 1.6 Hz, 4H), 7.00 (s, 2H), 2.43 (s, 6H ). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 193.23, 182.61, 136.86, 134.64, 133.25, 133.07, 130.97, 122.78, 104.14, 84.08, 30.79. HRMS calcd for C ²⁶ , H ¹⁵ , 0 ⁴ , S ² : 456.0500, found: 456.0490.

2,5-bis (4'-ethynylpyridyl) -l-nitrobenzene (22) . 2,5-dibromonitrobenzene (0.28 g, 0.997 mmol), bis (triphenylphosphine) palladium dichloride (0.07 g, 0.098 mmol) in THF (4 mL), copper iodide (I) (0.019 g, 0.098 mmol), triphenylphosphine (0.106 g, 0.40 mmol) and Compound 21 (0.377 g, 2.15 mmol) in THF (4 mL) and MeOH (2 mL) in a solution of K ₂ CO ₃ (1.1 g, 7.96 mmol). ) Was added via cannula. The mixture was heated at 64 ° C. for 20 hours. Solvent was removed with a rotary evaporator and the black residue K ₂ C0 ₃ Washed with aqueous solution and extracted with Et ₂ 0. The combined organic layers were dried over Na ₂ SO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, hexanes / AcOEt 70/30, 50/50, 20/80, 0/100) afforded 60 mg (24% yield) of the title compound as a yellow solid.

Mp: 178-180 ° C. IR (KBr) 3414.0, 3036.7, 1616.0, 1589.4, 1538.1, 1519.9, 1407.9, 1345.7, 1271.1, 1214.1, 828.3 cm ^-1 . ¹ H NMR (400 MHz, DMSO-d) δ 8.69 (br s, 4H), 8.44 (d, J = 1.4 Hz, 1H), 8.04 (1/2 ABqd, J = 8.0, 1.4 Hz, 1H), 7.99 ( 1/2 ABq, J = 8.0 Hz, 1H), 7.60 (d, J = 5.8 Hz, 2H), 7.57 (d, J = 5.8 Hz, 2H). ¹³ C NMR (100 MHz, DMSO-d) δ 150.21, 150.13, 149.42, 136.27, 135.36, 129.16, 129.11, 127.96, 125.50, 125.39, 123.25, 116.55, 94.98, 90.63, 90.59, 88.13. HRMS calcd for C ²⁰ H ¹¹ N ³ 0 ² : 325.0851. Found: 325.0847.

1-bromo-4- (4'-ethynylpyridyl) -3-nitrobenzene (23). 2,5-dibromonitrobenzene (0.43 g, 1.53 mmol), bis (triphenylphosphine) palladium (Il) dichloride (0.052 g, 0.074 mmol) in THF (2 mL), copper iodide (I) ( 0.015 g, 0.078 mmol), compound 21 (0.342 g) in THF (4 mL) and MeOH (1.5 mL) in a solution of triphenylphosphine (0.079 g, 0.30 rnrnol) and K ₂ CO ₃ (0.83 g, 6.0 mmol) , 1.95 mmol) was added via cannula. The mixture was heated at 23 ° C. for 2 days. The solvent was removed on a rotary evaporator and the residue was diluted with water and extracted with Et ₂ 0. The combined organic layers were dried over Na ² SO ⁴ , filtered and the solvent was evaporated in vacuo. Flash chromatography (silica gel, hexanes / AcOEt 90/10, 70/30, 50/50) afforded 330 mg (71% yield) of the title compound as off white solid.

Mp: 166-171 ° C .. IR (KBr) 3424.4, 3093.3, 1592.3, 1521.4, 1409.3, 1341.4, 1272.6 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 8.68 (br s, 2H), 8.29 (d, J = 1.9 Hz, 1H), 7.79 (dd, J = 8.3, 2.0 Hz, 1H), 7.62 (d, J = 8.3 Hz, 1H), 7.44 (d, J = 4.7 Hz, 2H). 13 C NMR (100 MHz, CDCl ₃ ) δ 149.96, 136.22, 135.69, 130.14, 128.08, 126.67, 125.65, 123.19, 116.48, 94.80, 87.81. HRMS calcd for C ₁₃ H ₇ BrN ₂ O ₂ : 303.9672, found: 303.9682.

5-Ethynylphenyl-2- (4'-ethynylpyridyl) -l-nitrobenzene (24) . Compound 23 (88.8 mg, 0.293 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.011 g, 0.016 mmol) in THF (4 mL), copper iodide (I) (0.004 g, 0.021 mmol) and To a solution of triphenylphosphine (0.008 g, 0.029 mmol) was added Et ₃ N (0.25 mL, 1.76 mmol) and phenylacetylene (0.1 mL, 9.1 mmol). The mixture was stirred at 56 ° C for 36 h. The solvent was evaporated in vacuo. The residue was diluted with water and extracted with Et ₂ 0. The combined organic layers were dried over MgSO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, AcOEt / hexane 20/80) gave 65 mg (69% yield) of the title compound as a yellow solid.

Mp: 130-132 ° C. IR (KBr) 3445.3, 3046.3, 2203.5, 1548.5, 1529.1, 1399.9, 1341.6 cm ^-1 . 1 H NMR (400 MHz, CDCl ₃ ) δ 8.67 (br d, J = 4.9 Hz, 2H), 8.27 (d, J = 1.5 Hz, 1H), 7.76 (1/2 ABqd, J = 8.0, 1.6 Hz, 1H) 7.72 (1/2 ABqd, J = 8.0, 0.5 Hz, 1H), 7.56 (m, 2H), 7.45 (dd, J = 5.9, 1.7 Hz, 2H), 7.40 (m, 3H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 149.58, 135.39, 134.65, 131.81, 129.34, 128.54, 127.67, 125.32, 121.85, 116.66, 95.30, 94.30, 88.52, 86.63. HRMS calcd for C ₂₁ H ₁₂ N ₂ 0 ₂ : 324.0899. Found: 324.0895.

1-bromo-4-ethynylphenyl-3-nitrobenzene (25). In THF (4 mL) 2,5-dibromonitrobenzene (0.937 g, 3.34 mmol), bis (dibenzylideneacetone) palladium (0.095 g, 0.166 mmol), copper iodide (I) (0.032 g, 0.168 mmol) and triphenylphosphine To a solution of (0.173 g, 0.66 mmol) was added Et ₃ N (1 mL, 7.2 mmol) and phenylacetylene (0.5 mL, 4.56 mmol). The mixture was stirred at 23 ° C for 48 h. The mixture was washed with saturated solution of NH ₄ Cl and then extracted with Et ₂ O. The combined organic layers were dried over Na ₂ SO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, CH ₂ C1 ₂ / hexanes 1/8) afforded 0.48 g (47% yield) of the title compound as a yellow solid.

Mp: 58-74 ° C. IR (KBr) 3421.9, 3085.5, 2213.4, 1595.7, 1545.9, 1521.3, 1336.5, 1269.2 cm ^-1 . ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.23 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.3 Hz, 2.0, 1H), 7.59 (m, 3 H), 7.40 (m, 3 H). ¹³ C NMR (100 MHz, CDCl ³ ) δ 149.71, 135.91, 135.45, 131.99, 129.44, 128.46, 127.78, 122.03, 121.75, 117.69, 98.43, 84.00. HRMS calcd for C ₁₄ H ₈ NO ₂ Br: 302.9720, found: 302.9725.

2-ethynylphenyl-5- (4'-ethynylpyridyl) -l-nitrobenzene (26). Compound 25 (0.306 g, 1.01 mmol), K ₂ CO ₃ (0.713 g, 5.16 mmol) in THF (2 mL), bis (triphenylphosphine) palladium dichloride (0.035 g, 0.05 mmol), copper iodide ( I) (0.009 g, 0.047 mmol) and triphenylphosphine (0.052 g, 0.198 mmol) were added via cannula compound 21 (0.217 g, 1.24 mmol) in THF (2 mL) and MeOH (1 mL). . The mixture was heated at 60 ° C. for 18 h. The solvent was removed by rotary evaporator and the brown residue was diluted with water and extracted with Et ₂ 0. The combined organic layers were dried over Na ₂ SO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, AcOEt / hexane 20/80, 40/60) gave 260 mg (79% yield) of the title compound as a yellow solid.

Mp: 144-146 ° C. IR (KBr) 3442.3, 3053.0, 2209.4, 1631.3, 1584.8, 1524.7, 1404.3, 1344.7, 1269.0, 826.4, 755.2, 686.6 cm ^-1 . ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.67 (dd, J = 4.4, 1.6 Hz, 2H), 8.27 (br s, 1H), 7.74 (m, 2H), 7.63 (d, J = 1.8 Hz, 1H) , 7.60 (m, 1 H), 7.42 (m, 5 H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 149.99, 135.41, 134.65, 132.14, 130.19, 129.61, 128.54, 127.95, 125.50, 122.68, 122.06, 119.15, 99.67, 90.83, 90.27, 84.62. HRMS calcd for C ₂₁ H ₁₂ N ₂ 0 ₂ : 324.0899. Found: 324.0897.

2,5-bis (trimethylsilylethynyl) -4-nitroacetanilide (27). Compound 6 (0.78 g, 2.3 mmol), bis (dibenzylideneacetone) palladium (0.068 g, 0.118 mmol) in THF (8 mL), copper iodide (I) (0.023 g, 0.012 minol), triphenylphosphine ( To a solution of 0.123 g, 0.47 mmol) was added Et ₃ N (1 mL, 7.2 mmol) and trimethylsilylacetylene (1 mL, 7.0 mmol). The mixture was heated at 67 ° C. for 48 h. The solvent was removed by rotary evaporator and the brown residue was diluted with water and extracted with Et ₂ 0. The combined organic layers were dried over Na ₂ SO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, CH ₂ Cl ₂ / hexanes 35/65) gave 410 mg (47% yield) of the title compound as an off white solid.

Mp: 162-164 ° C. IR (KBr) 3372.9, 2962.9, 2146.0, 1727.2, 1611.2, 1544.9, 1501.5, 1457.1, 1404.3, 1338.2, 1250.6, 1222.3, 881.9 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 8.75 (s, 1H), 8.15 (s, 1H), 8.10 (br s, 1H), 2.27 (s, 3H), 0.33 (s, 9H), 0.28 (s, 9H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 168.21, 144.19, 142.41, 128.11, 123.82, 120.18, 111.52, 106.66, 106.16, 99.50, 97.44, 24.90, -0.31, -0.46. HRMS calcd for C ₁₈ H ₂₄ N ₂ 0 ₃ Si ₂ : 372.1326, found: 372.1326.

2,5-bis (4'-ethynylpyridyl) -4-nitroaniline (28) . Compound 27 (0.056 g, 0.15 mmol), 4-iodopyridine (0.08 g, 0.39 mmol), K ₂ CO ₃ (0.17 g, 1.2 mmol), bis (triphenylphosphine) palladium in THF (4 mL) II) To a solution of dichloride (0.01 g, 0.015 mmol), copper iodide (l) (0.004 g, 0.021 mmol) and triphenylphosphine (0.016 g, 0.061 mmol) MeOH (1 mL) was added. The mixture was heated at 60 ° C. for 50 h. The solvent was removed by a rotary evaporator and the brown residue was diluted with water and extracted with AcOEt. The combined organic layers were dried over Na ₂ SO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, AcOEt) gave 8 mg (16% yield) of the title compound as a yellow solid.

Mp: 154-160 ° C .. IR (KBr) 3730.2, 3438.6, 2204.8, 1592.4, 1541.1, 1409.8, 1308.5, 1249.9, 818.8 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 8.67 (dd, J = 4.4, 1.7 Hz, 2H), 8.65 (dd, J = 4.5, 1.7 Hz, 2H), 8.34 (s, 1H), 7.44 (dd, J = 4.5, 1.7 Hz, 2H), 7.40 (dd, J4, 4, 1.6 Hz, 2H), 6.99 (s, IH), 5.03 (br s, 2H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 151.26, 150.03, 149.90, 139.56, 130.71, 130.52, 130.00, 125.65, 125.33, 120.33, 118.52, 106.57, 94.67, 94.19, 89.55, 87.27. HRMS calcd for C ₂₀ H ₁₂ N ₄ 0 ₂ : 340.0960, found 340.0958.

2-Amino-4- (4′-ethynylpyridyl) -5-nitrobromobenzene (29) . Compound 6 (0.877 g, 8.84 mmol), K ₂ CO ₃ (1.08 g, 7.81 mmol) in THF (4 mL), bis (triphenylphosphine) palladium dichloride (0.054 g, 0.077 mmol), copper iodide (1 ) (0.025 g, 0.13 mmol) and triphenylphosphine (0.068 g, 0.26 mmol) were added via cannula compound 21 (0.404 g, 2.30 mmol) in THF (8 mL) and MeOH (3 mL). did. The mixture was heated at 23 ° C. for 1 day. The solvent was removed in vacuo and the residue was diluted with water and extracted with AcOEt. The combined organic phases were dried over MgSO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, AcOEt / hexane 40/60 50/50) afforded 290 mg (39% yield) of the title compound as a yellow solid.

Mp: 226-228 ° C. IR (KBr) 3385.4, 3297.7, 3171.3, 1646.8, 1591.7, 1556.9, 1471.3, 1297.8 cm ^-1 . ¹ H NMR (400 MHz, DMSO-d) δ 8.66 (br d, J = 3.8 Hz, 2H), 8.32 (d, J = 1.3 Hz, 1H), 7.53 (br d, J = 4.5 Hz, 211), 7.06 (d, J = 1.3 Hz, 1 H), 6.94 (br s, 2 H). ¹³ C NMR (100 MHz, DMSO-d) δ 151.33, 150.12, 136.44, 130.70, 129.64, 125.32, 118.13, 117.73, 106.02, 91.85, 89.72. HRMS calcd for C ₁₃ H ₈ BrN ₃ O ₂ : 316.9800, found: 316.9801.

4-amino-2- (4'-ethynylpyridyl) -1-nitro-5- (trimethylsilylethynyl) benzene. Compound 29 (0.310 g, 0.975 mmol), bis (triphenylphosphine) palladium dichloride (0.035 g, 0.05 mmol) in THF (10 mL), copper iodide (I) (0.011 g, 0.05 mmol) and triphenylforce To a solution of pin (0.026 g, 0.10 mmol) was added Et ₃ N (0.9 mL, 6.5 mmol) and trimethylsilylacetylene (0.2 mL, 1.4 mmol). The mixture was heated at 60 ° C. for 2 days. The solvent was removed in vacuo and the residue was diluted with water and extracted with AcOEt. The combined organic phases were dried over MgSO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, Et 2 O) afforded 160 mg (49% yield) of the title compound as a yellow solid.

Mp: 145-150 ° C. IR (KBr) 3451.9, 3379.1, 2960.5, 2149.5, 1620.4, 1597.9, 1545.5, 1512.2, 1317.0 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 8.65 (dd, J = 4.6, 1.5 Hz, 2H), 8.25 (s, 1H), 7.44 (dd, J = 4.3, 1.5 Hz, 211), 6.93 (s, 1H ), 4.90 (s, 2H), 0.30 (s, 9H). ¹³ C NMR (100 MHz, CDC1 ₃ ) δ 151.44, 149.90, 139.35, 130.65, 130.43, 125.65, 119.56, 118.06, 107.93, 104.28, 98.37, 93.70, 89.79, -0.15. HRMS calcd for C ₁₈ H ₁₇ N ₃ 0 ₂ Si: 335.1090, found 335.1089.

4-amino-5-ethynyl-2- (4-ethynylpyridyl) -1-nitrobenzene. (30). 4-amino-2- (4'-ethynylpyridyl) -1-nitro-5- (trimethylsilylethynyl) benzene (160 mg, 0.477 mmol) in MeOH (15 mL) and CH ₂ Cl ₂ (15 mL) To the solution was added K ₂ CO ₃ (0.66 g, 4.77 mmol).

The solution was heated at 23 ° C. for 2 hours. The reaction mixture was diluted with water and extracted with AcOEt. The combined organic layers were dried over MgSO ₄ , filtered and the solvent was evaporated in vacuo. The reaction resulted in 0.11 g (88% yield) of the title compound as a yellow solid. The product was so unstable that complete character data could not be obtained.

¹ H NMR (400 MHz, DMSO-d) δ 8.67 (dd, J = 4.5, 1.6 Hz, 2H), 8.12 (s, 1H), 7.53 (dd, J = 4.5, 1.6 Hz, 2H), 7.03 (s, 1H), 6.97 (br s, 2H), 4.70 (s, 1H).

4-amino-2- (4'-ethynylpyridyl) -5- (4'-thioacetylphenylethynyl) -1-nitrobenzene (31). Compound 30 (0.110 g, 0.418 mmol), 4-thioacetyliodobenzene (0.124 g, 0.446 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.015 g, 0.021 mmol) in THF (13 mL) ), Et ₃ N (0.4 mL, 2.9 mmol) was added to a solution of copper iodide (I) (0.004 g, 0.021 mmol) and triphenylphosphine (0.014 g, 0.053 mmol). The mixture was stirred at 50 ° C. for 2 days. The reaction was checked by TLC (AcOEt / hex 75/25). Additional bis (triphenylphosphine) palladium dichloride (0.014 g, 0.020 mmol), copper iodide (I) (0.035 g, 0.0 18 mmol) and triphenylphosphine (0.085 g, 0.324 mmol) were added and the reaction was carried out. It stirred at 60 degreeC for 1 day. The solvent was evaporated in vacuo. The residue was diluted with water and extracted with AcOEt. The combined organic layers were dried over MgSO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, AcOEt / hex 66/33) gave 130 mg (75% yield) of the title compound as a yellow solid.

Mp: 185-188 ° C. IR (KBr) 3438.2, 3195.9, 2922.4, 1695.4, 1627.7, 1596.5, 1545.1, 1514.8, 1477.2, 1402.8, 1316.4, 1249.9 cm ^-1 . ¹ H NMR (400 MHz, DMSO-d) δ 8.68 (br d, J = 4.0 Hz, 2H), 8.23 (s, 1H), 7.79 (d, J = 8.1 Hz, 2H), 7.54 (d, J = 5.0 Hz, 2H), 7.49 (d, J = 8.0 Hz, 2H), 7.13 (br s, 2H), 7.06 (s, 1H), 2.46 (s, 3H). ¹³ C NMR (100 MHz, DMSO-d) δ 192.98, 153.79, 150.13, 136.28, 134.31, 132.32, 130.69, 129.67, 128.66, 125.34, 123.05, 118.70, 118.26, 105.43, 95.72, 92.51, 90.12, 85.54, 30.32. HRMS calcd for C ₂₃ H ₁₅ N ₃ 0 ₃ S: 413.0834, found: 413.0940.

2- (4'-ethynylpyridyl) -4-nitro-5-phenylaniline (32) . Compound 7 (80.5 mg, 0.241 mmol), K ₂ CO ₃ (0.151 g, 1.09 mmol) in THF (2 mL), bis (triphenylphosphine) palladium (II) dichloride (0.009 g, 0.014 mmol), iodide To a solution of copper (I) (0.003 g, 0.014 mmol) and triphenylphosphine (0.0 14 g, 0.053 mmol), dilute compound 1 (0.053 g, 0.3 mmol) in THF (2 mL) and MeOH (1 mL). Added via cannula. The mixture was heated at 70 ° C. for 3 days. The solvent was removed on a rotary evaporator and the brown residue was diluted with water and extracted with Et ₂ O. The combined organic layers were dried over Na ₂ SO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, AcOEt / hex 30/70) gave 60 mg (79% yield) of the title compound as a yellow solid.

Mp: 187-190 ° C. IR (KBr) 3410.2, 3323.4, 3212.1, 2215.1, 1627.6, 1592.4, 1548.4, 1511.7, 1410.5, 1331.9 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) δ 8.64 (br d, J = 4.8, 2H), 8.16 (s, 1H), 7.39 (m, 5H), 7.27 (m, 2H), 6.62 (s, 1H), 5.03 (br s, 2 H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 151.23, 149.82, 140.65, 138.82, 138.19, 130.49, 128.36, 128.06, 127.52, 125.34, 116.41, 104.85, 93.24, 87.89. C, ⁹ H, ³ N ³ HRMS calculated values for 0 ^2: 315.1008, measured value: 315.1011.

1-bromo-4- (4'-ethynyl) pyridine-3-nitrobenzene (34) .

Compound 33 ¹ (0.84 g, 2.34 mmol), bis (triphenylphosphine) palladium dichloride (0.083 g, 0.117 mmol) in THF (4 mL), copper iodide (I) (0.022 g, 0.117 mmol), and K To a solution of ₂ CO ₃ (1.94 g, 14.04 mmol) was added via cannula compound 21 (0.451 g, 2.57 mmol) in THF (12 mL) and MeOH (4 mL). The mixture was heated at 55 ° C. for 14 h. The solvent was removed on a rotary evaporator and the residue was diluted with water and extracted with AcOEt. The combined organic phases were dried over MgSO ₄ , filtered and the solvent was evaporated in vacuo. Purification by flash chromatography (silica gel, AcOEt) gave 271 mg (34% yield) of the title compound as a yellow solid.

Mp: 224-229 ° C. IR (KBr) 3451.7, 3351.1, 3202.6, 2206.4, 1622.9, 1588.4, 1539.0, 1474.4, 1306.7, 1249.8 cm ^-1 . ¹ H NMR (400 MHz, DMSO-d) δ 8.64 (d, J = 5.7 Hz, 2H), 8.25 (s, 1 11), 7.67 (dd, J = 4.5, 1.5 Hz, 2H), 7.59 (m, 2H ), 7.47 (m, 3 H), 7.15 (br s, 1 H), 7.03 (s, 1 H). ¹³ C NMR (100 MHz, DMSO-d) δ 153.97, 149.83, 136.31, 131.67, 131.17, 130.01, 129.69, 128.99, 125.45, 121.78, 120.40, 118.06, 103.92, 96.13, 93.41, 88.37, 86.25. HRMS calcd for C ₂₁ H ₁₃ N ₃ 0 ₂ : 339.1008, found 339.1004.

1-bromo-3-nitro-4- (4-aminophenylethynyl) benzene (36). 1,4-dibromo-2-nitrobenzene (5.62 g, 20.0 mmol), bis (triphenylphosphine) palladium dichloride (0.140 g, 0.20 mmol), copper iodide (I) (0.038 g, 0.20 mmol) , Triethylamine (10.0 mL), THF (10 mL) and Compound 35 (1.170 g, 10.0 mmol) were used following the general procedure for coupling. The reaction mixture was stirred at rt for 4 h. After removing the solvent in vacuo, the residue was chromatographed on a silica column to give a mixture of the desired product and its regioisomer as a red solid. By recrystallization twice from dichloromethane / hexane, the desired product was separated from the mixture into fine bright needles (1.561 g, 49% yield).

Mp 147-149 ° C. IR (KBr) 3457, 3367, 2194, 1623, 1593, 1513, 1550, 1334, 1273, 1136, 834, 817, 528 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) 8.21 (d, J = 2.0 Hz), 7.67 (dd, J = 8.4, 2.0 Hz), 7.51 (d, J = 8.4 Hz), 7.96 (m, AA'XX 'pattern AA 'part of,

J = 8.2, 2.7, 1.9, 0.4 Hz, 2H), 7.93 (m, XX 'portion of the AAXX' pattern, J = 8.2, 2.7, 1.9, 0.4 Hz, 2H), 3.39 (s, 2H). ¹³ C NMR (100 MHz, CDCl ₃ ) 149.27, 147.85, 135.82, 135.12, 133.71, 127.73, 120.62, 118.59, 114.63, 111.09, 100.24, 82.86. HRMS calcd for C ₁₄ H ₉ N ₂ BrO ₂ : 315.9848, found: 315.9845.

4- (2-nitro-4-phenylethynylphenylethynyl) aniline (37). Compound 36 (0.697 g, 2.20 mmol), bis (triphenylphosphine) palladium dichloride (0.062 g, 0.088 mmol), copper iodide (I) (0.0084 g, 0.044 mmol), triethylamine (10.0 mL) and Tynylbenzene (0.306 g, 3.00 mmol) was used according to the general procedure for coupling. The reaction mixture was stirred at 80 ° C. for 2 hours. After removing the solvent in vacuo, the residue was chromatographed on a silica and dichloromethane column to give the desired product as a red needle (0.72 g, 97% yield).

Mp 166-168 ° C. IR (KBr) 3454, 3381, 3360, 2177, 2197, 1594, 1623, 1539, 1520, 1299, 1342, 1133, 829, 758, 690, 527 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ ) 8.20 (dd, J = 1.6, 0.3 Hz), 7.66 (dd, J = 8.2, 1.6, Hz), 7.61 (d, J = 8.1 Hz), 7.52-7.57 (m, 2H), 7.36-7.43 (m, 5H), 3.94 (s, 2H). ¹³ C NMR (100 MHz, CDC1 ₃ ) 148.93, 147.81, 135.12, 134.04, 133.76, 131.74, 129.04, 128.49, 127.59, 122.97, 122.18, 118.95, 114.64, 111.29, 100.75, 93.03, 87.05, 83.71. HRMS calcd for C ₂₂ H ₁₄ N ₂ 0 ₂ : 338.1055, found: 338.1058.

4- (2-nitro-4-phenylethynylphenylethynyl) benzenediazonium tetrafluoroborate (38). Compound 37 (0.0845 g, 0.250 mmol) was treated with NOBF ₄ (0.0322 g, 0.275 mmol) in acetonitrile (2 mL) / sulfolan (2 mL) according to the general diazotization procedure. The product was precipitated on dark orange scale using ether (12 mL). The salt was washed with ether and reprecipitated from DMSO (0.5 mL) and CH ₂ C1 ₂ (20 mL) into a glossy dark orange plate (0.0885 g, 81% yield).

IR (KBr) 3103, 2279, 2209, 1576, 1345, 1540, 1084, 841, 764 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ / DMSO-d ₆ , linewidth of approximately 1.9 Hz observed) 8.78 (d, J = 8.9 Hz, 2H), 8.30 (s, 1H), 8.03 (d, J = 8.9 Hz , 2H), 7.85-7.92 (m, 2H), 7.57-7.60 (m, 2H), 7.42-7.44 (m, 3H). ¹³ C NMR (100 MHz, CDC1 ₃ / DMSO-d ₆ ) 149.00, 135.46, 134.85, 134.15, 133.31, 132.84, 1.34, 129.13, 128.21, 127.15, 125.66, 121.06, 114.81, 114.25, 94.57, 94.42, 94.11, 86.29.

4- (3-nitro-4-phenylethynylphenylethynyl) aniline (39). Compound 25 (1.208 g, 4.0 mmol), bis (triphenylphosphine) palladium dichloride (0.070 g, 0.10 mmol), copper iodide (I) (0.019 g, 0.10 mniol), triethylamine (6.0 ml), THF (6.0 mL) and Compound 35 (0.479 g, 4.10 mmol) were used following the general procedure for coupling. The reaction mixture was stirred at rt for 15 h. After removing solvent in vacuo, the residue was chromatographed on a short column of silica gel and dichloromethane / hexanes (1: 1) to afford the desired product as an orange solid (0.560 g, 44% yield):

mp 175-177 ° C. IR (KBr) 3303, 2985, 1696, 1587, 1522, 1406, 1314, 1243, 1153, 1060, 839, 757, 692 cm ⁻¹ . ¹ H NMR (400 MHz, CDC1 ₃ ) 8.16 (t, J = 1.0 Hz, 1H), 7.64 (d, J = 1.0 Hz, 2H), 7.58-7.61 (m, 2H), 7.34-7.40 (m, 3H) , 7.35 (m, AA 'portion of the AA'XX' pattern, J = 8.0, 2.5, 2.0, 0.4 Hz, 2H), 6.65 (m 'XX' portion of the m, AA'XX 'pattern, J = 8.0, 2.5, 2.0 , 0.4 Hz, 2H), 3.91 (s, 2H). ¹³ C NMR (100 MHz, CDC1 ₃ ) 149.4, 147.5, 134.9, 134.3, 133.3, 132.0, 129.3, 128.5, 127.1, 124.9, 122.3, 117.1, 114.7, 11.1, 98.4, 94.9, 85.3, 85.0. HRMS calcd for C ²² H, ⁴ N ² 0 ² : 338.1055, found: 338.1059.

4- (3-nitro-4-phenylethynylphenylethynyl) benzenediazonium tetrafluoroborate (40). Compound 39 (0.0676 g, 0.200 mmol) was treated with NOBF ₄ (0.025 g, 0.210 mmol) in acetonitrile (2 mL) / sulfolan (2 ml) according to the general diazotization procedure. The product was precipitated into fine orange-red crystals using ether (20 mL). The salt was washed with ether and reprecipitated from DMSO (0.6 mL) and CH ₂ C1 ₂ (10 mL) into a very shiny red plate (0.0676 g, 77% yield).

IR (KBr) 3101, 2279, 2209, 1576, 1540, 1346, 1083, 1034, 840, 764 cm ^-1 . ¹ H NMR (400 MHz, CDC1 ₃ / DMSO-d ₆ ) 7.94 (m, AA 'portion of AA'XX' pattern, J = 8.7, 2.4, 1.7, 0.4 Hz, 2H), 7.82 (dd, J = 1.7, 0.4 Hz, 1H), 7.49 (m, XX 'portion of AA'XX' pattern, J = 8.7, 2.4, 1.7, 0.4 Hz, 2H), 7.62 (dd, J = 8.1, 1.7 Hz, 1H), 7.56 ( dd, J = 8.1, 0.4 Hz, 1H), 7.07 (m, AA 'portion of AA'XX'Y pattern, J = 7.8, 7.6, 1.8, 1.3, 1.3, 0.6 Hz, 2H), 6.94 (tt, J = 7.6, 1.3 Hz, 1H), 6.91 (m, YY 'portion of the AA'XX'Y pattern, J = 7.8, 7.6, 1.8, 1.3, 1.3, 0.6 Hz, 2H). ¹³ C NMR (100 MHz, CDC1 ₃ / DMSO-d ₆ ) 137.24, 136.97, 136.23, 135.40, 133.72, 133.00, 131.08, 129.96, 129.48, 122.81, 122.75, 120.68, 114.12, 100.47, 98.81, 91.04, 85.57.

4- (2,5-dinitro-4- (4-aminophenylethynyl) phenylethynyl) aniline (42). 1,4-dibromo-2,5-dinitrobenzene ¹² (0.977 g, 3.0 mmol), bis (triphenylphosphine) palladium dichloride (0.042 g, 0.06 mmol), copper iodide (I) (0.011 g , 0.06 mmol), triethylamine (5.0 mL), THF (5.0 mL) and 4-ethynylaniline (0.468 g, 4.00 mmol) were used according to the general procedure for coupling. The reaction mixture was stirred at rt for 12 h. After removing solvent in vacuo, the residue was sonicated with dichloromethane (10 mL) and filtered. The filtered cake was washed 5 times with dichloromethane (10 ml) and dried in vacuo to give dark purple crystals of diamine 42 (0.432 g, 36% yield).

Mp> 270 ° C. IR (KBr) 3494, 3387, 2184, 1600, 1400, 1523, 1537, 1308, 1337, 1251, 1136 cm ⁻¹ . ¹ H NMR (400 MHz, DMSO-d ₆ ) 8.37 (s, 2H), 7.27-7.29 (m, 2H), 6.59-6.61 (m, 2H), 5.93 (br s, 4H). ¹³ C NMR (100 MHz, DMSO-d ₆ ) 151.18, 149.89, 133.67, 129.43, 116.95, 113.66, 106.10, 103.45, 82.23. HRMS calcd for C ₂₂ H ₁₄ N ₄ 0 ₄ : 398.1015, found: 398.1018.

4- (2,5-dinitro-4- (4-diazoniophenylethynyl) phenylethynyl) benzenediazonium tetrafluoroborate (43). Compound 42 (0.199 g, 0.500 mmol) was treated with NOBF ₄ (0.128 g, 1.10 mmol) in acetonitrile (5.0 mL) / sulfolan (5.0 mL) according to the general diazotization procedure. The product was precipitated with ether (20 mL). The salt was washed with ether and reprecipitated from DMSO and CH ₂ C1 ₂ to give light-sensitive yellow crystals (0.215 g, 72% yield).

IR (KBr) 3107, 2291, 1579, 1546, 1342, 1078, 830 cm ⁻¹ . ¹ H NMR (400 MHz, CDC1 ₃ / DMSO-d ₆ ) 8.85 (s, 2H), 8.79 (d, J = 9 Hz, 2H), 8.20 (d, J = 9 Hz, 2H). ¹³ C NMR (100 MHz, CDC1 ₃ / DMSO-d ₆ ) 150.60, 133.93, 133.83, 133.14, 132.40, 131.75, 117.62, 116.32, 96.91, 91.51.

Many oligo (phenyleneethynylene) compounds with reversible reducible functionality based on quinone and nitro cores have been synthesized. For these molecules, a method is provided for attaching to metal surfaces ranging from standard protective thiol groups to novel diazonium and pyridyl bonds.

Example 2 Molecular Electronic Device Containing Pyridine Unit

6 shows two groups of potential molecular devices synthesized. The first group has nitro functionality on the inner phenyl ring, designed to retain electrons so that the molecule can act as a memory device. The second group has a nitro group and an amino group, and it appears to operate in the same way even at a relatively low temperature.

Potential molecular devices 2 and 4 are designed to have two pyridyl end groups to act as crosslinkers for the gold junction.

Scheme 2. (a) K ₂ CO ₃ , MeOH, Pd (PPh ₃ ) ₂ Cl ₂ , PPh ₃ , CuI, THF, 64 ° C., 20 h, 24%.

Scheme 2 gives an overview of the synthesis of compound 2 from 2,5-dibromonitrobenzene. Compound 1 is readily prepared (99%) via Sonogashira ⁶ coupling of 4-iodopyridine ⁷ with trimethylsilylacetylene. Potassium carbonate is used as a base to remove the TMS protecting group in situ and to couple while free alkyne is degraded after several hours. Attempts to run the reaction at room temperature resulted in bis (ethynylpyridine) as main product and coupling to one side of aryl dibromide.

Scheme 2. (a) Et ₃ N, Pd (dba) ₂ , PPh ₃ , CuI, THF, 60 ° C., 48 h, 47%. (b) K ₂ CO ₃ , Pd (PPh ₃ ) ₂ Cl ₂ , PPh ₃ , CuI, THF, 60 ° C., 50 h, 16%.

Compound 4 is similar to compound 2 but has a nitroaniline core instead of a nitro core. Unlike the latent molecular device (2), the synthesis of compound 4 (scheme 2) begins with the coupling of 2,5-dibromo-4-nitroacetanilide 9 with trimenylsilylacetylene to give compound 3 This was coupled with 4-iodopyridine to obtain a low yield. The low yield of the coupling reaction can be due to the cyclization reaction between the nitro unit and the alkyne unit.

Scheme 3. (a) K ₂ CO ₃ , MeOH, Pd (PPh ₃ ) ₂ Cl ₂ , PPh ₃ , CuI, THF, room temperature, 24 h, 39%. (b) Et ₃ N, Pd (PPh ₃ ) ₂ Cl ₂ , PPh ₃ , CuI, THF, 60 ° C. (c) K ₂ CO ₃ , MeOH, CH ₂ Cl ₂ , room temperature, 2 hours, 88%.

The synthesis process of compound 8 is shown in scheme 3. Compound 8 has a protected benzenethiol end group capable of binding to the gold surface. The other end of the molecule has a pyridyl group, which may serve as a better top linker than the phenyl group. Synthesis of Compound 8 was carried out by first coupling 2,5-dibromo-4-nitroacetanilide with Compound 1 to obtain Compound 5 in normal yield. Compound 5 was then coupled with trimethylsilylacetylene to give compound 6 in a yield of 49%, which was deprotected with potassium carbonate to give compound 7 . The final step in this synthesis was coupling with 4-thioacetyliodobenzene, where a potential device (8) was obtained with good yield (75%).

Scheme 4. (a) K ₂ CO ₃ , MeOH, Pd (PPh ₃ ) ₂ Cl ₂ , PPh ₃ , CuI, THF, room temperature, 2 days, 71%. (b) Et ₃ N, Pd (PPh ₃ ) ₂ Cl ₂ , PPh ₃ , CuI, THF, 56 ° C., 36 h, 69%.

Compounds 10 and 12 were synthesized to correlate the importance of the position of nitro groups relative to “alligator clips” during the self-assembly process. Synthesis of compound 10 with nitro group (scheme 4) oriented in the pyridyl group direction first compounded compound 1 with 2,5-dibromonitrobenzene and removes TMS group in situ to obtain compound 9 in good yield , 9 was made by coupling compound 9 with phenylacetylene to obtain compound 10 .

Scheme 5. (a) Et ₃ N, Pd (dba) ₂ , PPh ₃ , CuI, THF, room temperature, 48 hours, 47%. (b) K ₂ CO ₃ , MeOH, Pd (PPh ₃ ) ₂ Cl ₂ , PPh ₃ , CuI, THF, 64 ° C., 18 h, 79%.

Synthesis of Compound 12 (Scheme 5) with nitro groups pointing in the opposite direction to the pyridyl group is similar to the approach used for Compound 10 except that the reaction steps are reversed. In this case, first, phenylacetylene was coupled to 2,5-dibromonitrobenzene to give compound 11 in an ordinary yield. Compound 1 was then coupled to compound 11 to obtain compound 12 in good yield.

These organic oligomers all have phenyl rings in the same plane to conduct electrons with minimal disturbance. If the terminal phenylethynyl group is replaced by a phenyl group, the molecule is slightly distorted. Compound 14 was synthesized to study the effect of this rotational barrier. To synthesize compound 13 , 2,5-dibromo-4-nitroacetanilide was Suzuki coupled with phenylboronic acid (scheme 6), followed by coupling compound 13 to 4- (trimethylsilylethynyl) pyridine ( 1 ). Ring 14 was obtained.

The structures of compounds 2, 4, 8, 10, 12 and 14 were confirmed by IR, ¹ H NMR, ¹³ C NMR and MS.

Scheme 6. (a) Pd (dba) ₂ , PPh ₃ , Cs ₂ CO ₃ , toluene, 67 ° C., 3 days, 51%. (b) K ₂ CO ₃ , MeOH, Pd (PPh ₃ ) ₂ Cl ₂ , PPh ₃ , CuI, THF, 70 ° C., 3 days, 79%.

In conclusion, the synthesis of conjugated aromatic molecules containing pyridine units for molecular electronic devices has been achieved using coupling reactions based on palladium.                 

Example 3. Negative Differential Resistance

Referring again to FIG. 3, an exemplary molecular type diode 30, in particular a mono-nitro substituted oligophenylene 32 molecule, in particular 4,4′-diphenyleneethynylene-2′-nitro-1- Negative differential resistance was observed in benzenethiol and dinitro substituted oligophenylenes (34), especially 2 ', 5'-dinitro-4,4'-diphenyleneethynylene-1-benzenethiol.

Referring now to FIGS. 4A and 4B, the I (V) response curves of the molecules shown in FIG. 2 are shown where I is the current and V is the voltage. These curves were obtained by measuring the response of the self-assembled monolayers of molecules 32 and 34. In each monolayer, the molecules were oriented with the thiol substituted end in contact with the gold lead and the unsubstituted opposite end in contact with the second gold lead.

Referring to FIG. 4A, the I (V) response is initially in the “0” state (open circle) for molecule 32. When a 1.75V pulse is applied, the molecule is set to a new state representing negative differential resistance (NDR), or "1" (black circle), with the current rising and then falling with increasing voltage.

Referring to FIG. 4B, initially for the molecule 34, the I (V) response is in the “1” state (closed circle), representing the NDR. When a 1.5V pulse is applied, the molecule is set to the new state of the molecule, ie "0" (open circle). The initial state is recovered by applying a negative bias. This is the inverse of the initial / final switching observed for molecule 32 as shown in FIG. 3A. However, each operation is an example of the duality of the switch state. The advantage of molecule 34 is that it is a molecule that exhibits negative differential resistance at room temperature. In addition, the duration of the switched state was observed for 24 hours. It is believed that longer packaging times are possible by improving the packaging of the system. In order to improve the stability of the switched state for a longer time, it is preferable that the nanocell 12 be completely sealed.

The NDR curves shown in FIG. 4B were used for the dynamic nanocell simulation and SPICE simulation described below.

Example 4

The inventors have discovered that mock nanocells based on nano-networks with arranged molecular switches connected by nanoparticles can be trained to act as exemplary known logic elements. The molecular switch is a molecule that exhibits an I (V) response characterized by a negative differential resistance.

Simulated nanocells are believed to represent actual physical nanocells. Therefore, it is believed that the actual nanocell programming technology was first discovered. The inventors do not know another example of demonstrating the learning of logic by a network comprising "dendrite" (using concepts similar to the structure of the brain) with these I (V) properties. In particular, neural network models and other simulation systems of the conventional brain are based on the presentation of a system with a “dendritic crystal” I (V) curve, typically selected from step functions, hyperbolic tangents, etc., none of which has negative differential resistance. Do not.

Genetic algorithms were used to train mock nanocells almighty. That is, the algorithm knows the state of the remote molecular switch. The algorithm trained nanocells by universal switching, ie by directly controlling the state of the switch. However, these results are believed to represent the results achievable by self-adaptive algorithms that mortally configure remote molecular switches by regulating the voltage at the input and output leads.

General programming

The goal in programming or training nanocells is to take a random fixed nanocell and switch the nanocell's switch "on" or "off" until the nanocell functions as the target logic device. First, the physical position of each molecular switch is fixed; In other words, the internal shape of the nanocell is static. The nanocells are then trained post-fabrication. Only the "on" or "off" state of the molecular switch can be changed.

Here we introduce the terms omniscience, omnipotence and mortal switching in connection with the programming algorithm used. Omniscience means that the location and state of each switch and connections within the nanocells are known. Omnipotence means that the search algorithm has a precise and selective approach to knowing the position of each molecular switch and reversing its "on" or "off" state. Naturally, the definition of omnipotence includes omniscience. Finally, in the term of hair switching, the algorithm does not know the location of the connections or switches inside the nanocell, and switching is limited to voltage pulses applied to the input / output pins. The actual physical nanocells are preferably programmed in a mortal manner, and switching occurs only through voltage pulses between the contact pads along the periphery.                 

In the simulations presented here, we demonstrate that there is a switch state that allows a given nanocell to function as a target logic device. Given the particular density of nanoparticles and molecular switches, it is desirable to determine whether any random nanocells can be trained as some target logic element, under the assumption of absolute control over the switch state. Some preliminary tactics for extending the method of hair switching include the use of capacitors of gold particles for better access to individual switches. If there is exactly one switch and several capacitors between two gold particles, the line of molecular switch between the two I / O pins can be used in any pattern of "on" and "off" using these capacitors. It is believed that it can be set. Molecular switches and networks of gold particles inside the nanocells are much more complex than simple switch lines between I / O pins, but simulations show that the solution space for some logic gates is quite dense. This means that there is no need to access every individual molecule specifically. In fact, if there are several switches between two gold particles, all switches oriented in one direction will be switched at the same time. However, this is not a problem since the toggling group of molecules will be nearly enough.

The problem of training nanocells with omnipotence is a combinatorial optimization problem where the search space is a set of all possible switch states for some fixed nanocells. If a nanocell contains 250 nanoparticles and about 750 molecular switches in a suitable orientation for switching, the size of this search space is 2 ⁷⁵⁰ (as a comparison of sizes, the number of elemental particles in the universe is 2 ³⁰⁰⁾ . Estimated). Genetic algorithms are used to search this space. First, random nanocells are generated and target logic devices are defined (eg NAND). The states of the switches of the nanocells are stored as "chromosomes" of a plurality of "1s" and a plurality of "0" s. The first generation of random chromosomes is made. Each of the chromosomes corresponds to a different set of switch states for nanocells with fixed positions of nanoparticles and molecular switches. A fitness functio is created that causes the nanocells to run as target logic devices with low scores and switch states that do not perform target logic functions. When the chromosome in the switched state receives zero, the search stops, thus allowing the desired logic to be executed. After the first generation, each generation of new chromosomes is produced by the manipulations performed for the previous generation. Highly adaptive, ie low score chromosomes are combined in pairs to form new and much better performing chromosomes. In this way, a spatial search is made until a chromosome of adaptive zero is obtained.

Here we present two methods for simulating this omnipotent training process. To calculate the adaptability of each configuration or combination of switch states inside the nanocell, a series of circuits must be analyzed. Each of these circuits includes a complex network of nonlinear resistors. The pattern of input voltage over time is applied to some of the input / output pins and the resulting output current over time must be calculated. This involves solving a series of nonlinear equations, usually differential equations. It is difficult to solve this system, but the simulation presented here deals with this in two ways. In the second model we present, SPICE, a circuit engineering software, is used to analyze each configuration of the nanocells. The software is very accurate but time consuming because it is not designed to iterate over circuits assembled in a random manner. Accuracy is sacrificed for speed in our first dynamic nanocell model. In other words, the approximation of the electrical behavior of the nanocells does not solve the complex system of equations, but a useful approximation is obtained.

The genetic algorithm used is recorded in the file name vzNanocell.cpp in the appendix.

Dynamic Nanocell Model

Cellular automata (CA) is a dynamic system with individual values for space and time. The state of the cells in the regular lattice is updated in a synchronous manner according to deterministic rules that depend only on the state of the local or neighboring cells [c]. The state of each cell is often limited to a small set of individual values, but it is not uncommon to extend the concept of CA to allow state variables that actually evaluate [d]. The dynamic nanocell model is a cellular automata in which the hexagonal lattice represents nanocells and the cells in the lattice represent individual gold nanoparticles. The actual evaluated state variable for the cell is the potential difference of the nanoparticles and the transition rule for changing the state variable at each time step is to adjust the potential difference of the nanoparticles to conform to Kirchhoff as the adjacent cell. Computer scientists use cellular automata when physicists use field theories governed by "field equations," and the use of CA is said to provide an alternative computerized approach that can be done tens of thousands of times over conventional methods. come. The inventors believe that a dynamic nanocell model allows us to run our search algorithm in a timely manner while at the same time accurately modeling the electrical properties of the physical device.

The conversion rules for the dynamic nanocell model accounted for the nonlinearity of the I (V) curve in the NDR device and allowed the model to simulate the flow of fluid as well as the current flowing through the nanocell. This makes it possible to model more interesting logic devices such as those with negating logic.

The dynamic model was evaluated in an incremental manner as follows. All metallic nanoparticles were initialized with a potential difference of zero, and then a nonzero potential difference was applied to some of the nanoparticles designated as input / output points. The potential difference applied to the input point gradually increased until reaching a level indicating Boolean evaluated input to the nanocell, and then remained constant throughout the simulation. The obtained nanoparticles signaled adjacent particles in which the change occurred. Next, the nanoparticle reevaluated its potential difference by comparing its potential difference with the potential difference of each immediately adjacent nanoparticle. The amount of current passing through each of the adjacent particles was determined by the potential difference of each of the adjacent particles along the I (V) characteristics of the interposed molecular switch. The sum of the currents coming from some neighboring particles was not equal to the sum of the currents flowing out of the remaining neighboring particles, so the potential difference of the nanoparticles was controlled. Once regulation was made, adjacent nanoparticles were signaled to reevaluate their potential. This process continues until the nanoparticles satisfy their inrush currents with the same currents, resulting in the system being Kirchhoff compliant. Finally, the current was calculated at each input / output.

Genetic algorithms were used to determine the combination of switch settings that caused the nanocell to act as the desired logic gate. Since the switch is in one of the "on" and "off" states, the chromosome model is a set of bits that indicate the state of all switches in the cell, either "off" or "on", respectively, at values of 0 or 1. It was. Hexagonal arrays were used. That is, the nanoparticles were placed at the vertices of the triangle and the switch was placed along the sides of the triangle. Genetic algorithms could find a combination of switch settings to allow small 4x4 nanocells to act as XOR devices. In addition, in a "circular" nanocell with a radius of 1 (i.e. surrounded by the perimeter of 6 nanoparticles in which one central nanoparticle is approximately circular), the nanocell is any of 8 2x1 truth tables (2 inputs, 1 output). It has been proven that it can be trained to function as one. In addition, in "circular" nanocells with a radius of 2 (where the radius 1 nanocell is surrounded by the perimeter of approximately 12 nanoparticles with a circular shape), it has been demonstrated for any of 64 2x2 truth tables (2 inputs, 2 outputs). . This dynamic nanocell model runs simple and relatively fast, making it an excellent tool for studying nanocell retrieval techniques and logical properties.

Each of the following materials is incorporated herein by reference:

[a] T. Toffoli, N.H. Margolus; "Invertible Cellular Automata: A Review," Cellular Automata: Theory and Experiment, H. Gutowitz, editor; 1991, A Bradford Book, The MIT Press, Cambridge, Massachusetts, London England.                 

[b] T. Toffoli; "Cellular Automata as an Alternative to (Rather than An Approximation of) Differential Equations in Modeling Physics.PHYSICA D, Nonlinear Phenomena, Vol 10D (1984) Nos. 1 & 2, January 1984

[c] H. Gutowitz; "Intriduction", Cellular Automata: Theory and Experiment, H. Gutowitz, as above [a]

[d] Chopard, Droz; Cellular Automata Modeling of Physical Systems; 1998, Cambridge University Press

SPICE model

Spice Model

The SPICE model simulates the composite cell circuit characteristics of nanocells. We configured SPICE to interfere with the genetic algorithm described above. The nanocell simulator was developed using Microsoft's COM platform to interfere with Intusoft's ICAPS / 4 Windows SPICE variant from OLE. The calculation is also available from HSPICE v. Available from Avant. It was done in 1999.2. The nanocell simulator randomly generates nanocells and configures them to function as simple logic gates. Given the density and dimensions of the nanoparticles and the average density of the molecular switches, random nanocells are created as hexagonal grids of metal particles with specific select densities. Molecular switches connecting adjacent nanoparticles are distributed according to a poason distribution based around a given mean density (FIG. 7). After the nanocells are created, the setpoints for 20 peripheral input / output pins (five pins on each side) are defined. Each input / output pin can be configured to input, output, or float to behave like a nanoparticle. Inside the SPICE engine, individual molecules are modeled using monolinear resistor circuit elements. Achieving convergence in SPICE was addressed by including the parasitic capacitance expected between nanoparticles. The added capacity prevents abrupt changes in current during the simulation, which helps to more realistic model and converge the nanocells.

In the tasks described herein, logic gates are voltage-input and current-output circuits. When setting the input / output pins to "high" or "low", we set V _IL and V _IH to low and high voltages for the input pins, respectively. When the truth table value of the input is 1, the V _IH volt is applied to this pin. A truth table value of zero means that the V _IL volt is applied. Likewise, we set I _OL and I _OH as output current thresholds, respectively. The pin is considered "off" if the current through the output pin is below I _OL , and the pin is "on" if the current is above I _OH .

Given a number of two-state inputs and outputs, the truth table describes the desired logic. It is not enough to test each individual truth. Each conversion between truths should also be tested. The input graph for the inverter and the corresponding truth table, the inverses of the NAND gate and the half adder are displayed in later sections.

By interpreting the output from SPICE, we measured the output of the nanocells at each clock step. These readings were then compared to I _OH and I _OL to determine whether the output pin was “on” or “off” or not (between individual threshold settings). In this way, we determined the logic of any given nanocell. By comparing this logic with the desired truth table, we can determine whether the nanocell performs the desired logic function.

It is desirable to search for all possible combinations of switch states when the position of each switch is fixed relative to the fixed nanocell. In other words, new switches cannot be added between nanoparticles and existing switches cannot be removed. Only the wrong switch status can be changed. In the SPICE model, the pin setpoints and the "on" and "off" current thresholds (I _OH and I _OH ) were constant. The goal was to fix these parameters so that any random nanocells of a particular nanoparticle and molecular switch density could be trained as part of the target logic gate. Exemplary setpoints have been determined for the inverter, the NAND gate and the inverse half adder.

A list of representative SPICEs of exemplary nanocells in their unprogrammed state is recorded in the Trained Nanocell.doc file in the attached appendix. The "on"-"off" states for the molecular switches of the unprogrammed nanocells are shown in FIG. 7.

A representative SPICE list of the same nanocell reprogrammed to function as an inverter is recorded in the Trained Nanocell.doc file in the attached appendix. The "on"-"off" states of the nanocells functioning as programmed inverters are shown in FIG. 8.                 

A representative SPICE listing of the same nanocell programmed to function as a NAND gate is recorded in the Trained Nanocell.doc file in the attached appendix. The "on"-"off" state of the nanocells functioning as programmed NAND is shown in FIG. 9.

A representative list of SPICEs of the same nanocell programmed to function as a reverse half adder is recorded in the Trained Nanocell.doc file in the attached appendix. The "on"-"off" states of the nanocells functioning as programmed reverse half adders are shown in FIG. 10.

The results described above demonstrate the possibility of programming and reprogramming the exemplary nanocells presented in FIG. 7.

While the preferred embodiments of the present invention have been shown and described, those skilled in the art can make modifications thereto without departing from the spirit or teaching of the present invention. Embodiments disclosed herein are illustrative only and not restrictive. Many modifications and variations of the device, computer, and method are possible and are included in the invention. Thus, the scope of protection is not limited to the embodiments described herein but only by the claims that follow, and the scope includes all equivalents to the subject matter of the claims.

Addendum pages 60-224.                 

Claims (56)

At least one input lead; At least one output lead; And A nano-network connecting the input lead and the output lead Including, The nano-network includes a plurality of molecular circuit components Programmable Molecular Device. The method of claim 1, And the nano-network is self-assembled. The method of claim 1, A programmable molecular device in which the nano-network is random. The method of claim 1, A programmable molecular device, wherein the device can be programmed by a self-adaptive algorithm for constructing the molecular circuit components. The method of claim 4, wherein The self-adaptive algorithm may be a genetic algorithm, a simulated annealing algorithm, a go with the winner algorithm, a temporal difference learning algorithm, a reinforcement learning algorithm, and Programmable molecular device selected from the group consisting of a combination of these. The method of claim 4, wherein And the molecular circuit component can be configured by applying a voltage across the input lead and the output lead. The method of claim 1, Programmable molecular device, wherein the device can be programmed to function as a logical unit. The method of claim 7, wherein And the logic unit is selected from the group consisting of a truth table supported by the at least one input lead and the at least one output lead. The method of claim 8, The logic unit is selected from the group consisting of AND, OR, XOR, NAND, NOT, adder, half-adder, inverse half-adder, multiplexer, decoder, and combinations thereof A programmable molecular device that can be programmed to function as. The method of claim 1, Programmable molecular device, wherein the programmable molecular device can be programmed to function as a memory unit. The method of claim 1, A programmable molecular device, wherein said device can be reprogrammed. The method of claim 1, And wherein said molecular circuit components are selected from the group consisting of molecular switches, molecular diodes, molecular wires, molecular rectifiers, resistors, transistors, molecular memories, and combinations thereof. The method of claim 12, And the molecular circuit component comprises a molecular switch. The method of claim 13, Programmable molecular device, wherein the device can be programmed by an algorithm for setting the molecular switch. The method of claim 14, And the switch can be set by applying a voltage across the input lead and the output lead. The method of claim 1, And the nano-network further comprises nanoscale components. The method of claim 16, And the nanoscale component is selected from the group consisting of nanotubes, nanoparticles, nanorods, and combinations thereof. The method of claim 17, Wherein said nanoscale circuit component comprises nanoparticles, said molecular circuit component comprises a molecular switch, said molecular switch interconnecting said nanoparticles. The method of claim 18, And a programmable molecular device in which the nanoparticles are arranged in a random manner. The method of claim 18, And the molecular switch interconnects the nanoparticles in a random manner. (a) providing a self-assembled nanocell; And (b) programming the nanocell to function as an electronic component Method of manufacturing an electronic component comprising a. The method of claim 21, The nano cell At least one input lead; At least one output lead; And Nano-network connecting the input lead and the output lead Including, The nano-network includes a plurality of molecular circuit components Method of manufacturing electronic components. The method of claim 22, Wherein said molecular circuit components are selected from the group consisting of molecular switches, molecular diodes, molecular wires, molecular rectifiers, molecular resistors, molecular transistors, molecular memories, and combinations thereof. The method of claim 23, wherein And the molecular circuit component comprises a molecular resonant tunneling diode. The method of claim 24, And the molecular circuit component exhibits negative differential resistance. The method of claim 22, The nano-network further comprises a nanoscale component selected from the group consisting of nanotubes, nanoparticles, nanorods, and combinations thereof. The method of claim 22, And wherein said nano-network is random. The method of claim 21, Step (b) (b1) constructing the molecular circuit components Method of manufacturing an electronic component comprising a. The method of claim 28, Step (b1) (b1.i) adjusting characteristics affecting the conductivity of at least one of the molecular circuit components by applying a voltage across the input lead and the output lead. Method of manufacturing an electronic component comprising a. The method of claim 29, And wherein said property affecting conductivity is selected from the group consisting of charge, conformalal state, electronic state, and combinations thereof. The method of claim 28, Step (b) (b2) testing the performance of the nanocells Method of manufacturing an electronic component further comprising. The method of claim 31, wherein Step (b) (b3) applying a self-adaptive algorithm to reconstruct the molecular circuit components Method of manufacturing an electronic component further comprising. 33. The method of claim 32, And the self-adaptive algorithm is selected from the group consisting of genetic algorithms, simulated annealing algorithms, high with the winner algorithms, time difference learning algorithms, reinforcement learning algorithms, and combinations thereof. 33. The method of claim 32, (b4) repeating steps (b2) and (b3) until the nanocells function as electronic components Method of manufacturing an electronic component further comprising. The method of claim 22, The electronic component manufacturing method of the electronic component is composed of a logical unit. 36. The method of claim 35 wherein And the logic unit is selected from the group consisting of truth tables supported by the input leads and output leads. The method of claim 36, And said logic unit is selected from the group consisting of AND, OR, XOR, NOR, NAND, NOT, adder, half adder, inverse half adder, multiplexer, decoder, and combinations thereof. The method of claim 22, And the electronic component comprises a memory unit. The method of claim 22, Step (a) (a1) allowing a plurality of nanoscale components to self-assemble into a random array; (a2) allowing the plurality of molecular circuit components to self-assemble into a random molecular interconnect between the nanoscale components; And (a3) coupling the molecular circuit component to the nanoscale component with a molecular alligator clip Method of manufacturing an electronic component comprising a. The method of claim 39, Wherein said molecular alligator clip is selected from the group consisting of sulfur, oxygen, selenium, phosphorus, isonitrile, pyridine, carboxylate, and thiol moiety. The method of claim 39, And said nanoscale component is selected from the group consisting of nanotubes, nanoparticles, nanorods, and combinations thereof. The method of claim 39, Wherein said molecular circuit component is selected from the group consisting of molecular switches, molecular diodes, molecular wires, molecular rectifiers, molecular resistors, molecular transistors, and combinations thereof. A plurality of programmable nanocells; And Plural metal wires As a molecular computer comprising a, The nanocells each include a plurality of nanoparticles and a plurality of molecular diodes, The molecular diode interconnects the nanoparticles, The metal wires interconnect the nanocells. Molecular Computer. The method of claim 43, A molecular computer in which the nanocells are self-assembled. The method of claim 43, A molecular computer in which the nanoparticles are arranged in a random color. The method of claim 43, And the molecular diode interconnects the nanoparticles in a random manner. The method of claim 43, A molecular computer, each of said nanocells having a linear dimension of no greater than 2 μm. The method of claim 43, A molecular computer that can be programmed to function as at least one of the nanocells as a logical unit. The method of claim 48, And said logic unit is selected from the group consisting of truth tables supported by said wire interconnections. The method of claim 49, At least one of the nanocells may be programmed to function as an element selected from the group consisting of AND, OR, XOR, NOR, NAND, NOT, adder, semiadder, inverse half adder, multiplexer, decoder, and combinations thereof. computer. The method of claim 43, A molecular computer that can be programmed to function as at least one of the nanocells as a memory unit. The method of claim 43, A molecular computer in which the nanocells can be programmed by algorithms for constructing their molecular diodes. The method of claim 43, The nanocell further comprises first and second leads, The diode may be configured by applying a voltage to the first and second leads. Molecular Computer. The method of claim 43, At least one of the molecular diodes exhibits a negative differential resistance. (a) providing a plurality of trained self-assembled nanocells; (b) interconnecting the trained nanocells to a plurality of untrained nanocells; And (c) causing the trained nanocell to train the untrained nanocell Computer manufacturing method comprising a. The method of claim 55, (d) repeating steps (b) and (c) hierarchically Computer manufacturing method further comprising.

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