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Jieying Jiao, Gary J. Long, Fernande Grandjean, Alicia M. Beatty and Thomas P. Fehlner- Building Blocks for the Molecular Expression of Quantum Cellular Automata. Isolation and Characterization of a Covalently Bonded Square Array of Two Ferrocenium and Two Ferrocene Complexes

Jieying Jiao, Gary J. Long, Fernande Grandjean, Alicia M. Beatty and Thomas P. Fehlner- Building Blocks for the Molecular Expression of Quantum Cellular Automata. Isolation and Characterization of a Covalently Bonded Square Array of Two Ferrocenium and Two Ferrocene Complexes

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Building Blocks for the Molecular Expression of Quantum Cellular Automata.Isolation and Characterization of a Covalently Bonded Square Array of TwoFerrocenium and Two Ferrocene Complexes
Jieying Jiao,
Gary J. Long,*
,‡
Fernande Grandjean,
§
Alicia M. Beatty,
and Thomas P. Fehlner*
,†
 Department of Chemistry & Biochemistry, Uni
V
ersity of Notre Dame, Notre Dame, Indiana 46556-5670, Department of Chemistry, Uni
V
ersity of Missouri
s
 Rolla, Rolla, Missouri 65409-0010, and Department of Physics, B5, Uni
V
ersity of Lie
`
ge, B-4000 Sart-Tilman, Belgium
Received March 10, 2003; E-mail: fehlner.1@nd.edu
The utilization of molecules as components of electronic circuitshas caught the imagination of many.
1
The temptation to look formolecular mimics of existing electronic components is strong;however, molecules are exceedingly poor charge conductors andresistive heating rules out high device densities
s
the primary justification of the approach. On the other hand, molecules areexcellent charge containers and a novel paradigm, quantum cellularautomata (QCA), which is based on field-coupled charge containers,has been proven theoretically as well as operationally at lowtemperature using 50 nm quantum dots.
2
-
4
Systems based on 2nm dots are expected to operate at room temperature, hence, ourinterest in developing molecular expressions of the QCA paradigm.
5
The smallest building block of QCA wires consists of two dotscontaining a single mobile electron. At the molecular level thisbuilding block is a mixed-valence complex about which much isknown.
6
-
8
A more versatile building block for constructing QCAcircuits is a square of four electronically coupled dots containingtwo mobile electrons. Although molecular squares containing redoxactive metal centers have been described
9
-
14
and mixed-valencecomplexes up to nuclearity three have been thoroughly analyzed,
8,15
there is no example of an isolated four-metal, mixed-valencecomplex containing two mobile electrons in a square geometry.The independent existence and compatible electronic properties of such a species are of fundamental importance to the realization of the QCA paradigm. Here we report the full characterization of asymmetrical square containing two ferrocene and two ferroceniummoieties possessing measured properties that make it suitable foruse as a component for charge-coupled QCA circuits.The basic requirements to be met by a molecular QCA cell aredots consisting of metal complexes possessing two stable redoxstates, a planar array of four such complexes with 4-fold symmetry,sufficient through-bond or through-space interaction so that the2-electron, 2-hole mixed-valence state is stable with respect tocomproportionation to lower and higher oxidation states, type IIor type III mixed-valence behavior appropriate for switching,
16
andcapability of isolation as a pure compound in useable yields fromreadily available starting materials. These design restrictions ledto several failures and caused us to focus efforts on a square of four ferrocene complexes already described in the literature, i.e.,
{
(
η
5
-C
5
H
5
)Fe(
η
5
-C
5
H
4
)
}
4
(
η
4
-C
4
)Co(
η
5
-C
5
H
5
),
1
.
17,18
Although thereported electrochemistry was discouraging (a wave at 0.29 V withthe “remaining 3 redox waves blend(ed) into a broad wave centeredat ... 0.4 V”),
18
visible and near-IR band positions were publishedfor the 1
+
, 2
+
, and 3
+
ions generated by bulk electrolysis. Noneof these ions were isolated. On the other hand, these spectroscopicdata provided sufficient impetus to revisit the system.The synthesis of 
1
was carried out as described previously, andanalytically pure material was isolated.
17,18
Single crystals permitteda solid-state structure, which provides the dimensions of the squarearray of ferrocene moieties. The structure is similar to that of [
1
]-[PF
6
] shown in Figure 1. Other spectroscopic properties are shownin Figures 3 and 4 and in the Supporting Information. Cyclic andsquare wave voltametry (Figure 2) reveals four waves sufficientlyseparated to suggest isolation of the 1
+
and 2
+
cations is feasible.Note that choice of solvent is critical to prevent precipitation of the cations on the electrode, thereby leading to complex behavior.
19
The analytically pure 1
+
ion, [
1
][PF
6
], was prepared by oxidationof 
1
with [(
η
5
-C
5
H
5
)
2
Fe][PF
6
]. It too was characterized in the solidstate by X-ray diffraction (Figure 1). In contrast to
1
, [
1
][PF
6
]exhibits a near-IR band (Figure 3) which is solvent dependent (TypeII), an axial EPR spectrum at 4 K similar to that of ferrocenium
University of Notre Dame.
University of Missouri
s
Rolla.
§
University of Lie`ge.
Figure 1.
Molecular structure of [
1
][PF
6
]. Fe
-
Fe edge distance 5.980 Å.The
η
5
-C
5
H
5
ring bound to the Co atom (green) is not shown for clarity.
Figure 2.
Cyclic and square wave voltametry of 
1
at 100 mv/s on a Ptelectrode in CH
2
Cl
2
 /CH
3
CN mixed solvent, TBA[PF
6
] electrolyte, and Ptwire reference electrode (
 E 
1/2
(FcH
+
 /FcH)
)
0.344 V). The solid and opendots in the diagrams represent Fe(II) and Fe(III), respectively.
Published on Web 06/03/2003
7522
9
J. AM. CHEM. SOC. 2003
,
125 
, 7522
-
7523
10.1021/ja035077c CCC: $25.00 © 2003 American Chemical Society

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