Substrates carrying polymers of linked sandwich coordination...

Details Substrates carrying polymers of linked sandwich coordination... Substrates carrying polymers of linked sandwich coordination...

2002-07-12

2004-08-17

Choi, Ling Siu (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S263000, C526S308000, C526S259000

Reexamination Certificate

active

06777516

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to the articles of manufacture comprising a substrate having electric storage molecules bound thereto, along with methods of use thereof.
BACKGROUND OF THE INVENTION
Basic functions of a computer include information processing and storage. In typical computer systems, these arithmetic, logic, and memory operations are performed by devices that are capable of reversibly switching between two states often referred to as “0” and “1”. In most cases, such switching devices are fabricated from semiconducting devices that perform these various functions and are capable of switching between two states at a very high speed using minimum amounts of electrical energy. Thus, for example, transistors and transistor variants perform the basic switching and storage functions in computers.
Because of the huge data storage requirements of modern computers, a new, compact, low-cost, very high capacity, high speed memory configuration is needed. To reach this objective, molecular electronic switches, wires, microsensors for chemical analysis, and opto-electronic components for use in optical computing have been pursued. The principal advantages of using molecules in these applications are high component density (upwards of 10
10
bits per square centimeter), increased response speeds, and high energy efficiency.
A variety of approaches have been proposed for molecular-based memory devices. While these approaches generally employ molecular architectures that can be switched between two different states, all of the approaches described to date have intrinsic limitations making their uses in computational devices difficult or impractical.
For example, such approaches to the production of molecular memories have involved photochromic dyes, electrochromic dyes, redox dyes, and molecular machines, all having fundamental limitations that have precluded their application as viable memory elements. These molecular architectures are typically limited by reading/writing constraints. Furthermore, even in cases where the effective molecular bistability is obtained, the requirement for photochemical reading restricts the device architecture to a 2-dimensional thin film. The achievable memory density of such a film is unlikely to exceed 10
10
bits/cm
2
. Such limitations greatly diminish the appeal of these devices as viable molecular memory elements.
SUMMARY OF THE INVENTION
The present invention provides a polymer comprising or consisting of a plurality of covalently joined monomeric units, the monomeric units comprising sandwich coordination compounds. The covalently joined monomeric units in the polymer may be the same sandwich coordination compounds (e.g., the polymer is a homopolymer) or different sandwich coordination compounds (e.g., the polymer is a copolymer). The polymers may be covalently bound (direct or through a linker) or noncovalently bound (via ionic linkage or non-ionic “bonding”, etc.) to a substrate (a carrier substrate) to produce an article of manufacture. The substrate may be any of a variety of materials, including conductors, semiconductors, insulators, and composites thereof. Particular materials include metals, metal oxides, organic polymers, etc. The polymers may be bonded singly or co-deposited with one or more other polymers and/or other information storage molecules.
Such articles of manufacture are useful for a variety of purposes. For example, these polymers and articles of manufacture afford promising electrochromic display materials, potentially offering high contrast and a wide variety of colors by tuning the applied electric potential. These materials also find potential applications as intrinsic molecular semiconductors. The rich electrochemical properties of these materials also make them useful as potential battery materials and for applications in molecular-based information storage devices.
Polymers of the present invention may be represented by Formula I:
X
1
&Parenopenst;X
m+1
)
m
  (I)
wherein:
m is at least 1 (e.g., 1, 2, or 3 to 10, 20, 50 or 100 or more); and
X
1
through X
m+1
are sandwich coordination compounds (each of which may be the same or different).
Specific examples of polymers of Formula I are polymers of Formula II:.
X
1
—Y
1
—X
2
—Y
2
—X
3
—Y
3
—X
4
—Y
4
—X
5
—Y
5
—X
6
—Y
6
—X
7
—Y
7
—X
8
—Y
8
—X
9
—Y
9
—X
10
  (II)
wherein:
X
1
through X
10
are each independently selected sandwich coordination compounds;
Y
1
through Y
9
are independently selected linking groups or linkers; and
X
3
through X
10
(and Y
3
through Y
9
) may each independently or consecutively be present or absent (e.g., to provide a polymer of anywhere from 2 to 10 sandwich coordination compounds)
Articles of manufacture of the present invention may be represented by Formula III:
A—X
1
&Parenopenst;(X
m+1
)
m
  (III)
wherein:
A is a substrate (e.g., a conductor, a semiconductor, an insulator, or a composite thereof);
m is at least 1 (e.g., 1, 2, or 3 to 10, 20, 50 or 100 or more); and
X
1
through X
m+1
are sandwich coordination compounds (each of which may be the same or different).
Specific examples of articles of manufacture of Formula III are articles of Formula IV:
A-X
1
—Y
1
—X
2
—Y
2
—X
3
—Y
3
—X
4
—Y
4
—X
5
—Y
5
—X
6
—Y
6
—X
7
—Y
7
—X
8
—Y
8
—X
9
—Y
9
—X
10
  (IV)
wherein:
A is a substrate (e.g., a conductor, a semiconductor, an insulator, or a composite thereof);
X
1
through X
10
are each independently selected sandwich coordination compounds;
Y
1
through Y
9
are independently selected linking groups or linkers; and
X
3
through X
10
(and Y
3
through Y
9
) may each independently or consecutively be present or absent (e.g., to provide a polymer of anywhere from 2 to 10 sandwich coordination compounds)
Particular examples of sandwich coordination compounds that may be used to carry out the present invention have the Formula XI (for double-decker sandwich compounds) or Formula XII (for triple-decker sandwich compounds):
wherein:
M
1
and M
2
(when present) are metals independently selected from the group consisting of metals of the lanthanide series (Ln=La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, as well as Y, Zr, Hf, and Bi, and in the actinide series Th and U (radioactive elements such as Pm are generally less preferred);
L
1
, L
2
and L
3
(when present) are independently selected ligands (e.g., porphyrinic macrocycles); and
Q
1
, Q
2
and Q
3
may be present or absent and when present are independently selected linkers (the linker preferably including a protected or unprotected reactive group such as thio, seleno or telluro group). Preferably, at least one of Q
1
, Q
2
, and Q
3
is present.
In one particular embodiment, this invention provides an apparatus for storing data (e.g., a “storage cell”). The storage cell includes a fixed electrode electrically coupled to a “storage medium” comprising a polymer as described above, the polymer having a plurality of different and distinguishable oxidation states where data is stored in the (preferably non-neutral) oxidation states by the addition or withdrawal of one or more electrons from said storage medium via the electrically coupled electrode.
In preferred storage cells, the storage medium stores data at a density of at least one bit, and preferably at a density of at least 2 bits. Thus, preferred storage media have at least 2, and preferably at least 4, 8 or 10 or more different and distinguishable oxidation states. In particularly preferred embodiments, the bits are all stored in non-neutral oxidation states. In a most preferred embodiment, the different and distinguishable oxidation states of the storage medium can be set by a voltage difference no greater than about 5 volts, more preferably no greater than about 2 volts, and most preferably no greater than about 1 volt.
The storage medium is electrically coupled to the electrode(s) by any of a number of convenient methods including, but not limited to, covalent linkage (direct or through a linker), ionic linkage, non-ionic “bond

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