molecules

Review
Functionalization of Endohedral Metallofullerenes
with Reactive Silicon and Germanium Compounds †
Masahiro Kako 1, *, Shigeru Nagase 2, * and Takeshi Akasaka 3,4,5,6, *
1 Department of Engineering Science, The University of Electro-Communications, Chofu 182-8585, Japan
2 Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
3 Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Ibaraki 305-8577, Japan
4 Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan
5 Foundation for Advancement of International Science, Ibaraki 305-0821, Japan
6 School of Materials Science and Engineering, Huazhong University of Science and Technology,
Wuhan 430074, China
* Correspondence: kako@e-one.uec.ac.jp (M.K.); nagase@ims.ac.jp (S.N.); akasaka@tara.tsukuba.ac.jp (T.A.);
Tel.: +81-42-443-5570 (M.K.)
† Dedicated to Professor Marian Mikołajczyk on the occasion of his 80th birthday.

Academic Editor: Kyriakos Porfyrakis

Received: 20 May 2017; Accepted: 10 July 2017; Published: 14 July 2017

Abstract: Exohedral derivatization of endohedral metallofullerenes (EMFs) has been exploited

as a useful method for characterizing the structural and chemical properties of EMFs, and for
functionalizing them for potential applications. The introduction of heteroatoms, such as
electropositive silicon atoms, to fullerene cages is a novel functionalization method that remarkably
affects the electronic characteristics of fullerenes. This review comprehensively describes the results
of the reactions of monometallofullerene, dimetallofullerene, and trimetallic nitride template EMFs
with disilirane, silirane, silylene, and digermirane, which afforded the corresponding silylated and
germylated fullerenes. Several examples emphasize that exohedral functionalization regulates the
dynamic behaviors of the encapsulated metal atoms and clusters in the fullerene cages. The electronic
effects of silyl and germyl groups are represented by comparing the redox properties of silylated and
germylated EMFs with those of other EMFs derivatized with carbon-atom-based functional groups.

Keywords: endohedral metallofullerene; silylation; germylation; disilirane; silirane; silylene;

digermirane

1. Introduction
Endohedral metallofullerenes (EMFs) are attracting great interest because of their unique
structures and properties [1–15]. Encapsulation of metal atoms and metal clusters inside EMFs results
in electron transfer from the inner species to the carbon cages. Results of earlier studies show that
EMFs have remarkable electronic properties such as oxidation and reduction potentials. The difference
in redox potentials between EMFs and hollow fullerenes is a key factor characterizing the properties
and reactivities of EMFs.
Exohedral derivatization of EMFs and empty fullerenes has been explored extensively as
an effective method to modify and enhance the characteristics of fullerenes for various nanomaterials
science and biomedicine applications [1–15]. To date, many reactions have been applied for the
exohedral derivatization of EMFs with respect to their use for functional materials. However,
the derivatization reactions of EMFs remain sparse compared to those of empty fullerenes. In many
cases, the derivatizing organic groups are bonded covalently to the carbon cages of EMFs through C–C

Molecules 2017, 22, 1179; doi:10.3390/molecules22071179 www.mdpi.com/journal/molecules

Molecules 2017, 22, 1179 2 of 17
Molecules 2017, 22, 1179 2 of 17

C–C bonds. Therefore, derivatization that exploits the heteroatom properties is expected to
bonds. Therefore, derivatization that exploits the heteroatom properties is expected to contribute to
contribute to the development of EMFs as functional materials.
the development of EMFs as functional materials.
In this context, derivatization of fullerenes using silicon and germanium atoms is an attractive
In this context, derivatization of fullerenes using silicon and germanium atoms is an attractive
method for modifying the electronic properties of fullerenes because of the electron-donating effects
method for modifying the electronic properties of fullerenes because of the electron-donating effects
of silyl and germyl groups [16–19]. We found that the reactions of empty fullerenes with reactive
of silyl and germyl groups [16–19]. We found that the reactions of empty fullerenes with reactive
silicon and germanium compounds afforded the corresponding fullerene derivatives [20–32]. These
silicon and germanium compounds afforded the corresponding fullerene derivatives [20–32]. These
results prompted us to investigate properties of EMFs by examining their reactivities toward silicon
results prompted us to investigate properties of EMFs by examining their reactivities toward silicon
and germanium compounds. The combination of fullerenes and silicon and germanium compounds
and germanium compounds. The combination of fullerenes and silicon and germanium compounds
provide a basis for the production of novel functional materials for electronic device, as mentioned
provide a basis for the production of novel functional materials for electronic device, as mentioned
in the section on potential applications. This review presents a summary of our results of silylation
in the section on potential applications. This review presents a summary of our results of silylation
and germylation reactions as part of our continuing investigation of the chemical functionalization
and germylation reactions as part of our continuing investigation of the chemical functionalization
of EMFs [1,4–8,11,12,15]. We demonstrate that the introduction of silicon and germanium atoms
of EMFs [1,4–8,11,12,15]. We demonstrate that the introduction of silicon and germanium atoms
markedly perturbs the electronic properties of fullerenes because of the electron-donating effects of
markedly perturbs the electronic properties of fullerenes because of the electron-donating effects of
these atoms. More specifically, derivatization of EMFs using reactive compounds containing heavier
these atoms. More specifically, derivatization of EMFs using reactive compounds containing heavier
group 14 elements, such as silylene (silicon analog of carbene), disilirane (disilacyclopropane),
group 14 elements, such as silylene (silicon analog of carbene), disilirane (disilacyclopropane), silirane
silirane (silacyclopropane), and digermirane (digermacyclopropane) will be outlined. For several
(silacyclopropane), and digermirane (digermacyclopropane) will be outlined. For several silylated and
silylated and germylated derivatives of EMFs, the electronic properties are discussed in comparison
germylated derivatives of EMFs, the electronic properties are discussed in comparison with reference
with reference compounds that possess the same addition patterns because the redox behaviors of
compounds that possess the same addition patterns because the redox behaviors of derivatized EMFs
derivatized EMFs depend on the regiochemistry of the addends on the carbon cages. We also
depend on the regiochemistry of the addends on the carbon cages. We also describe how derivatization
describe how derivatization with organosilicon compounds influences the behaviors of
with organosilicon compounds influences the behaviors of encapsulated metal atoms. In this review,
encapsulated metal atoms. In this review, we will focus on the functionalization of the following
we will focus on the functionalization of the following EMFs: La@C2v -C82 , La2 @Ih -C80 , Ce2 @Ih -C80 ,
EMFs: La@C2v-C82, La2@Ih-C80, Ce2@Ih-C80, Ce2@D3h-C78, Sc3N@Ih-C80, and Lu3N@Ih-C80 (Figure 1).
Ce2 @D3h -C78 , Sc3 N@Ih -C80 , and Lu3 N@Ih -C80 (Figure 1).

Figure Structures
1. 1.
Figure of of
Structures (a)(a)
La@C 2v -C
La@C 2v-C ; ;(b)
8282 (b)La
La2 @I
2@Ihh-C 80;; (c)
-C80 (c) Ce
Ce22@D
@D3h3h-C
-C7878 ; and(d)
; and (d)ScSc3 N@I
3N@I h -C
h-C 80. 80 .

2.
2. Comparative
Comparative Studies
Studies of
of Reactions
Reactions of
of EMFs
EMFs with
with Disilirane
Disilirane
In 1995, the first
In first chemical
chemical derivatization
derivatizationofofEMFs EMFswaswasachieved
achievedbybythe thephotochemical
photochemical reaction
reactionof
of
La@CLa@C -C
2v
2v 82 -C and
82 and disilirane
disilirane 1 1
[33]. [33].
It is It is particularly
particularly interesting
interesting that La@C that -C
2v 82La@C -C
reacted
2v 82 reacted
both both
thermally
thermally and photochemically
and photochemically withthe1 corresponding
with 1 to afford to afford the adduct,
corresponding
althoughadduct,
the emptyalthough the Cempty
fullerenes 60 and
fullerenes
C70 did notCreact
60 andwith
C70 did not react
1 under withreactions
thermal 1 under in thermal reactions
the absence in the absence of[21,23].
of photoirradiation photoirradiation
This result
[21,23]. This result explained
can be reasonably can be reasonably explained
by the higher by the higher ability
electron-accepting electron-accepting
of La@C2v -C82 ability
than of La@C
that 2v-C82
of empty
than that ofSince
fullerenes. emptythisfullerenes.
discovery,Since this discovery,
the reactivities the reactivities
of various EMFs have of been
various EMFs have
investigated been1
using
investigated
as a chemical using 1 as
probe a chemical
(Scheme probe (Scheme
1). Digermirane 1). Digermirane
3 reacted with La@C3 reacted
-C
2v 82 with La@C
showing -C
higher
2v 82 showing
thermal
higher thermal
reactivity than reactivity than 1,from
1, which results which results
the from electron-donating
enhanced the enhanced electron-donating property of 3 [34].
property of 3 [34].
Molecules 2017, 22, 1179 3 of 17
Molecules 2017, 22, 1179 3 of 17

Scheme
Scheme 1.
1. Synthesis
Synthesis of
of disilirane
disilirane and
and digermirane
digermirane adducts
adducts of
of EMFs.
EMFs.

Redox potentials
Redox potentials
potentialsof of selected
ofselected
selectedEMFs EMFs
EMFsand and empty
andempty
empty fullerenes
fullerenes are shown in
in Figure 2.
2. Values of the
Redox fullerenes areare shown
shown Figure
in Figure 2. ValuesValues
of the offirst
the
first reduction
first reduction (denoted
(denoted as E red1) potentials are regarded as an important index for the reactivities
as Eredas E 1) potentials are regarded as an important
index forindex for the reactivities
red
reduction (denoted 1 ) potentials are regarded as an important the reactivities toward 1
toward
toward 11 because
because fullerenes
fullerenes are
are believed
believed to
to function
function as
as electron
electron acceptors
acceptors toward
toward 1,
1, which
which is
is aa good
good
because fullerenes are believed to function as electron acceptors toward 1, which is a good electron
electron
electron donor
donor [15].
[15]. All
All the
the fullerenes
fullerenes shown
shown in
in Figure
Figure 2
2 reacted
reacted with
with 11 by
by photoirradiation
photoirradiation to
to afford
afford
donor [15]. All the fullerenes shown in Figure 2 reacted with 1 by photoirradiation to afford the
the
the corresponding
corresponding adducts.
adducts. However,
However, the
the EMFs
EMFs and
and empty
empty fullerenes
fullerenes with
with lower
lower
red
EE
red1 potentials did
red1 potentials did
corresponding adducts. However, the EMFs and empty fullerenes with lower E 1 potentials did not
not
not undergo
undergo addition
addition reactions
reactions under thermal conditions at 80
80 °C [15]. For
For example, La22@I
@Ihh-C
-C80
undergo addition reactions underunder
thermal thermal conditions
conditions at 80 ◦ Cat[15]. °C
For[15].
example, example,
La2 @Ih -CLa 80 reacted
80
reacted
reacted with
with 1
1 both
both photochemically
photochemically and
and thermally
thermally [35],
[35], although
although Sc
Sc 3N@Ih-C80 was found to be
3N@Ih-C80 was found to be
with 1 both photochemically and thermally [35], although Sc3 N@Ih -C80 was found to be reactive only
reactive
reactive only
only under
under photolytic
photolytic conditions
conditions [36,37], although the first
first oxidation (denoted as E°x11))
E° x
under photolytic conditions [36,37], although[36,37],
the firstalthough
oxidationthe (denoted oxidation (denoted of
as E◦ x 1 ) potentials as these
potentials
potentials of
of these EMFs
EMFs are
theseTherefore, arethesimilar.
similar. Therefore,
Therefore, the
the higher
higher thermal reactivity of
of La
La22@I
@Ihh-C
-C80 toward 1
EMFs are similar. higher thermal reactivity ofthermal
La2 @Ih -Creactivity 80 toward 1
80 toward 1 might be attributed
might
might be attributed
be attributed to its good
to its good electron acceptor properties.
electron acceptor properties.
to its good electron acceptor properties.

1.32
1.50 1.21 1.32
1.50 1.21
0.88 0.88
0.88 0.88
1.00 0.65 0.73
1.00 0.56 0.57 0.53 0.62 0.61 0.65 0.73
0.56 0.57 0.53 0.62 0.61
0.50 0.20 0.25
0.20 0.25
(V)

0.50 0.07 0.08 0.07 0.09 0.10 E

Potential(V)

ox
0.07 0.08 0.07 0.09 0.10 Eox11
Potential

-0.39 -0.39 -0.37 -0.31

0.00
0.00 -0.42 -0.41
-0.42 -0.41 -0.39 -0.39 -0.37
-0.31 -0.39
-0.39 -0.40
-0.40 -0.52 E red
Ered1
-0.52 1
-0.74
-0.50
-0.50 -0.74 -0.89 -0.76
-0.76
-0.97 -0.89 -1.00
-0.97 -1.00 -1.10 -1.13
-1.22 -1.10 -1.13
-1.00
-1.00 -1.22 -1.39
-1.39
[35,36]
[35]
[33,39]

8080[35,36]

-1.50
[35,40]

-C8282[35]
-C8282[33,39]

-1.50
8080[35,40]

[62]

[42]

[51]
[91]
[89]

-C8080[62]

-C7878[42]

8080[51]
[90]

[41]
-C8282[91]

[39]
-C8282[89]

-C8282[90]

8080[41]

[27,28]
-C8282[39]

[27,28]

-2.00
-C7878[27,28]

7878[27,28]

-2.00
-C

h-C
h-C

[30]

[30]
3v3v
-C

-C

h-C
h-C

8484[30]

7676[30]
h-C
Gd@C2v2v-C

h-C

2@C
Ce@C2v2v-C
La@C2v2v-C

5h5h

3h3h
Pr@C2v2v-C

h-C
h-C
Y@C2v2v-C

2@C

3N@I
3N@I

[31]

[31]
2@D

2@D

Lu3N@I
Sc3N@I

CC7070[31]

CC6060[31]
2@I
2@I

Ce2@D

Ce2@D
Gd@C
Ce@C

Ce2@I
La@C

La2@I

2-C

3-C

2-C
Pr@C

2C
Y@C

CC2v2v-C
DD2-C

DD3-C

DD2-C
Sc2C
Ce

Ce

Ce

Lu
La

Sc

Sc

Figure 2. Redox potentials of EMFs and empty fullerenes. Values are in V relative to the ferrocene/
Figure
Figure 2.
2. Redox
ferrocenium couplepotentials
Redox (Fc/Fc+ ). of
potentials of EMFs
EMFs andand empty
empty fullerenes.
fullerenes. Values
Values are
are in
in V
V relative
relative to
to the
the
ferrocene/ferrocenium couple (Fc/Fc
ferrocene/ferrocenium couple (Fc/Fc ).
+
+ ).

It is noteworthy that the reactivities of EMFs were tunable by chemical oxidation or

It
It is
is noteworthy
noteworthy that
thatofthe
the reactivities
reactivities of
of EMFs
EMFs were were tunable
tunable
+ −by
by chemical
chemical oxidation
oxidation oror reduction
reduction
reduction [38]. Oxidation La@C 2v -C82 by (p-BrC6 H4 )3 N SbCl6 produced the corresponding cation,
[38].
[38]. Oxidation
Oxidation + of
of − La@C
La@C 2v-C82 by (p-BrC6H4)3N++SbCl6−− produced the corresponding cation,
-C by (p-BrC H ) N SbCl produced the corresponding cation,
[La@C2v -C82+] SbCl 6 , which reacted with 1 even at room temperature. In contrast, the addition of
2v 82 6 4 3 6
[La@C
[La@C2v-C2v-C82] +SbCl6−−, which reacted with 1 even at room temperature. In contrast, the addition of
82] SbCl6 , which reacted with 1 even at room temperature. In contrast, the addition of
+ −
NaSCH 3 to La@C2v -C82 afforded the corresponding anionic species, Na [La@C2v -C82 ] , which was
NaSCH 3 to La@C2v-C82 afforded the corresponding anionic species, Na++[La@C2v-C82]−−, which was
found to be La@C
NaSCH 3 to 2v-C
inert to afforded
1.82These thedemonstrate
results corresponding anionic
that the species, Na
electrophilicity of[La@C -C82] an
EMFs2vplays , which was
important
found
found to
to be
be inert
inert to
to 1.
1. These
These results
results demonstrate
demonstrate that
that the
the electrophilicity
electrophilicity of
of EMFs
EMFs plays
plays an
an important
important
role in controlling their reactivities toward 1.
role
role in
in controlling
controlling their
their reactivities
reactivities toward
toward 1.
1.
Molecules 2017, 22, 1179 4 of 17
Molecules 2017, 22, 1179 4 of 17

Reactions of
3. Reactions of La@C
La@C2v2v-C
-C8282with
withDisilirane
Disilirane1 1
Figure 2 shows that that La@C
La@C2v -C8282isishighly
2v-C highlyreactive
reactivetoward
toward 11 because
because of of its
its good
good electron-accepting
electron-accepting
ability. The The molecular
molecularsymmetry
symmetryofofLa@C La@C -C-C
2v2v 82,82 , which
which possesses
possesses 24 24 non-equivalent
non-equivalent carbon
carbon atoms
atoms in
in the
the C2vC 2v82-Ccage,
-C 82 cage,
is is low.Therefore,
low. Therefore,additionadditionreactions
reactionsof of La@C
La@C2v2v-C-C8282might
might produce
produce multiple
structural isomers. In fact, thermal reactions of La@C La@C2v -C8282with
2v-C with11afforded
affordedat at least
least six
six isomers
isomers of of the
mono-adducts based basedon onanalysis
analysisofofthe theEPREPR spectrum
spectrum of ofthethereaction
reactionmixture
mixture [33].[33].
A similar
A similarresult was
result
was
obtainedobtained
for theforthermal
the thermal addition
addition of digermirane
of digermirane 3 [34],3 indicating
[34], indicating that
that the the addition
addition reactionsreactions of
of 1 and
13 and
to La@C3 to 2v
La@C -C82 were
-C822vwere not regioselective.
not regioselective.
The
The major isomer of the adducts adducts derived
derived from from thethe reaction
reaction of of La@C
La@C2v 2v-C8282 with
with 11 was isolated
using HPLC
using HPLC separation
separation [39]. The The EPR EPR spectrum
spectrum of of this
this isomer
isomer showed
showed only only one one set
set ofof an octet
hyperfine that was smaller smaller than
than that
that of of pristine
pristineLa@C La@C2v 2v-C8282.. The
The addition
addition of
of 11 also
also caused
caused a
a change
change in
the absorption spectrum, suggesting that the π-conjugation of the carbon cage was altered. Although Although
the structures
structuresofof thethe disilirane
disilirane adducts
adducts of La@C of 2vLa@C -C82 not
-C82 2vhave have beennotdetermined,
been determined,their redox their redox
properties
properties
were obtained were obtained
from from electrochemical
electrochemical measurements. measurements.
The results show Thethat
results ◦ x and
the Eshow that
E red
the E° x1 and
potentials
1 1
E 1 potentials
ofredthe disiliraneofadducts
the disilirane
of La@C adducts of La@C
2v -C82 were 2v-C82
shifted were shiftedrespectively,
cathodically, cathodically, byrespectively,
140 mV and by 80 140
mV.
mV
These and 80 mV.shifts
cathodic These cathodic
of the redox shifts of the
potentials of redox
silylatedpotentials
derivatives of silylated
of EMFs derivatives
are reasonably of EMFs
explainedare
reasonably explained by the electron-donating effects of the silyl group, including σ–π conjugation
by the electron-donating effects of the silyl group, including σ–π conjugation between the C–Si
between
σ-orbitalsthe andC–Si σ-orbitalsofand
the π-orbitals the π-orbitals
the fullerene of the fullerene
cages [16–19]. The reaction cages
of Y@C[16–19].
2v -C82The
withreaction
1 affordedof
Y@C -C82 withproducts
two 2visomeric 1 afforded as two
the isomeric
1:1 adducts, products
for whichas thethe 1:1 cathodic
adducts, shifts
for which the cathodic
of redox potentials shifts of
were
redox
observed potentials
compared were toobserved compared
those of pristine Y@C to2vthose of pristine Y@C2v-C82 [39].
-C82 [39].

4. Reactions
4. Reactions of
of La
La22@I
@Ihh-C
-C8080and
andRelated
RelatedEMFs
EMFswith
withDisiliranes
Disiliranes1 1and
and2 2
Due to
Due to the
the symmetrical structure of
symmetrical structure the IIhh-C
of the -C80 cage, the
80 cage, the number
number of of isomers
isomers is is limited
limited in in the
the
addition reactions
addition reactions of of La
La22@I
@Ih-C-C80
80. .Only
Onlytwotwonon-equivalent
non-equivalent carboncarbon atoms
atoms exist
exist in the IIhh-C
in the -C80 cage: one
80 cage: one is
is
shared by one five-membered ring and two six-membered rings
shared by one five-membered ring and two six-membered rings (denoted as the [5,6,6]-ring (denoted as the [5,6,6]-ring junction);
the other is
junction); theshared
other is byshared
three six-membered
by three six-membered rings (denoted as the [6,6,6]-ring
rings (denoted junction).
as the [6,6,6]-ring The Ih -C
junction). The80
Icage
h-C80 also
cagehasalsotwohasnon-equivalent
two non-equivalent C–C bonds:
C–C bonds: one isoneshared by one
is shared by five-membered
one five-membered ring ring
and and
one
six-membered
one six-membered ring ring
(denoted as the
(denoted as[5,6]-ring junction);
the [5,6]-ring the other
junction); is shared
the other by two
is shared bysix-membered
two six-membered rings
(denoted
rings as theas
(denoted [6,6]-ring junction).
the [6,6]-ring junction).
Heating aa toluene
toluene solution ◦ C afforded the corresponding 1:1
Heating solution of of La @Ihh-C
La22@I -C8080and
anddisilirane
disilirane22at at80
80°C afforded the corresponding 1:1
adduct 5 as the sole product [40] (Scheme 2). The NMR and
adduct 5 as the sole product [40] (Scheme 2). The NMR and X-ray crystallographic X-ray crystallographic analyses established
analyses
the structures
established theofstructures
5 as the 1,4-adduct,
of 5 as theindicating
1,4-adduct, thatindicating
the silyl groups
that the aresilyl
bonded
groupsto theare[5,6,6]-junctions
bonded to the
of the Ih -C80 cage.
[5,6,6]-junctions of In
thethe
Ih-Ccrystal
80 cage. structure, the two
In the crystal encapsulated
structure, the two metal atoms were
encapsulated located
metal atoms close to
were
the two six-membered rings on the equator of the cage.
located close to the two six-membered rings on the equator of the cage. The The reaction of La 2 @I -C
hreaction
80 and 1 produced
of La2@Ih-C80
a similar
and adduct a4.similar
1 produced The corresponding
adduct 4. Theadduct of Ce2 @Ihadduct
corresponding -C80 6 was
of Cealso
2@Ihobtained
-C80 6 wasbyalso a similar
obtainedthermal
by a
reaction with 1, showing the same 1,4-addition pattern [41] (Scheme
similar thermal reaction with 1, showing the same 1,4-addition pattern [41] (Scheme 2). 2).

Scheme 2. Synthesis of disilirane adducts of M2@Ih-C80 (M = La, Ce).

Scheme 2. Synthesis of disilirane adducts of M2 @Ih -C80 (M = La, Ce).

In this review, the parent EMFs are shown respectively in brackets.

Scheme 3 shows that Ce2@D3h-C78 also reacts readily with disilirane 1 to produce the
corresponding 1,4-adduct 7 [42]. Based on X-ray crystallographic studies, the Ce atoms were found
to be located at two positions facing the six-membered rings on the C3 axis of the D3h-C78 cage. In the
Molecules 2017, 22, 1179 5 of 17

In this review, the parent EMFs are shown respectively in brackets.

Scheme 3 shows that Ce2 @D3h -C78 also reacts readily with disilirane 1 to produce the corresponding
1,4-adduct
Molecules [42].
2017,722, 1179Based on X-ray crystallographic studies, the Ce atoms were found to be located at
5 of 17
two positions facing the six-membered rings on the C3 axis of the D3h -C78 cage. In the paramagnetic
13 C-NMR spectral analysis, the observedanalysis,
carbon signals
paramagnetic 13C-NMR spectral the were more temperature-dependent
observed carbon signals were than more
those
of pristine Ce2 @D3h -C78 . than
temperature-dependent Therefore,
those the two Ce atoms
of pristine Ce2@Din 7 likely
3h-C interact with
78. Therefore, the Ce
the two C78atoms
cage more
in 7 firmly
likely
than those in pristine Ce @D
interact with the C78 cage2 more -C [42].
3h firmly
78 than those in pristine Ce2@D3h-C78 [42].

Scheme 3. Synthesis of a disilirane adduct of Ce2@D3h-C78.

Scheme 3. Synthesis of a disilirane adduct of Ce2 @D3h -C78 .

5. Reactions of La2@Ih-C80 with Silirane 8

5. Reactions of La2 @Ih -C80 with Silirane 8
Scheme 4 shows that La2@Ih-C80 also reacts with silirane 8 under thermal conditions to afford the
Scheme 4 shows that La2 @Ih -C80 also reacts with silirane 8 under thermal conditions to afford
corresponding 1,2-carbosilylated derivatives 9a and 9b [43]. Structural analyses, including X-ray
the corresponding 1,2-carbosilylated derivatives 9a and 9b [43]. Structural analyses, including X-ray
crystallographic measurements, determined 9a and 9b to be a pair of diastereomers of the
crystallographic measurements, determined 9a and 9b to be a pair of diastereomers of the [5,6]-adducts.
[5,6]-adducts. Furthermore, electrochemical measurements revealed that carbosilylation slightly
Furthermore, electrochemical measurements revealed that carbosilylation slightly altered the electronic
altered the electronic properties of La2@Ih-C80. Results of X-ray crystallographic analysis showed that
properties of La2 @Ih -C80 . Results of X-ray crystallographic analysis showed that the crystal structure
the crystal structure of 9a has eight sites for the La atoms because of disorder [43]. Theoretical
of 9a has eight sites for the La atoms because of disorder [43]. Theoretical calculations of adducts
calculations of adducts of La2@Ih-C80 and 8 indicated that changing the La atom positions resulted in
of La2 @Ih -C80 and 8 indicated that changing the La atom positions resulted in the differences in
the differences in relative energies within the range of 0.85–5.89 kcal mol−1. These small energy
relative energies within the range of 0.85–5.89 kcal mol−1 . These small energy differences suggest
differences suggest the movability of the La atoms inside the cage [43]. The La atoms sites are
the movability of the La atoms inside the cage [43]. The La atoms sites are arranged along the ten
arranged along the ten contiguously fused six-membered rings that constitute part of the Ih-C80 cage.
contiguously fused six-membered rings that constitute part of the Ih -C80 cage.
Figure 3 presents the redox potentials of pristine and derivatized dimetallofullerenes.
Figure 3 presents the redox potentials of xpristine and derivatized dimetallofullerenes. Remarkable
Remarkable cathodic shifts ◦of x both the
red E° 1 and Ered1 potentials were observed for the silylated
cathodic shifts of both the E 1 and E 1 potentials were observed for the silylated derivatives 4, 5,
derivatives 4, 5, 9a and 9b relative to that of pristine La2@Ih-C80. Results also confirmed that the redox
9a and 9b relative to that of pristine La2 @Ih -C80 . Results also confirmed that the redox potentials
potentials shifted cathodically as the number of silicon atoms introduced into La2@Ih-C80 increased as
shifted cathodically as the number of silicon atoms introduced into La @I -C80 increased as shown
shown by those of 4, 5, 9a, 9b and 10 [40,43,44]. The electronic effects of 2thehaddends are represented
by those of 4, 5, 9a, 9b and 10 [40,43,44]. The electronic effects of the addends are represented more
more exactly by comparing the [5,6]-carbosilylated adducts 9a, 9b, the [5,6]-pyrrolidino adduct 10
exactly by comparing the [5,6]-carbosilylated adducts 9a, 9b, the [5,6]-pyrrolidino adduct 10 [44], and
[44], and the [5,6]-tetracyanoethylene oxide (TCNEO) adduct 11 [45], which have the same addition
the [5,6]-tetracyanoethylene oxide (TCNEO) adduct 11 [45], which have the same addition patterns.
patterns. As expected from the effects of the electron-donating silyl group and electron-withdrawing
As expected from the effects of the electron-donating silyl group and electron-withdrawing TCNEO
TCNEO moieties, the redox potentials of 9a/9b and 11 shifted, respectively, to more negative and
moieties, the redox potentials of 9a/9b and 11 shifted, respectively, to more negative and more positive
more positive potentials than those of reference compound 10. Similar cathodic shifts of the redox
potentials than those of reference compound 10. Similar cathodic shifts of the redox potentials were
potentials were observed for 6 and 7, although the shift of E°x1 potential of 7 was somewhat smaller
observed for 6 and 7, although the shift of E◦ x 1 potential of 7 was somewhat smaller than expected for
than expected for a disilirane adduct.
a disilirane adduct.
Molecules 2017, 22, 1179 6 of 17
Molecules 2017, 22, 1179 6 of 17
Molecules 2017, 22, 1179 6 of 17
0.80 0.64
0.56 0.57
0.80 0.64
0.60 0.56 0.57
0.60
0.40 0.23 0.25

Potential (V)
0.40 0.11 0.13 0.23 0.25
0.20 0.04

Potential (V)
0.13
0.20 -0.06 -0.03 0.11 -0.07 0.04
0.00 -0.06 -0.03 -0.07
-0.21
0.00
-0.31 -0.21
-0.20
-0.31 -0.39 Eox1
-0.20 -0.45 -0.39 Eox1
-0.50 -0.53 -0.45 -0.52
-0.40 -0.50 -0.53 Ered1
-0.40 -0.52
-0.70 Ered1
-0.60 -0.76 -0.70 -0.73
-0.60 -0.76 -0.73 -0.81
-0.81
-0.80

La @I -C [35,40]
-0.80

[42]
80 [35,40]

-C78 [42]
-1.00

[41]
-1.00

8080[41]

78
80

@D3h-C
h-C

3h
@Ih-C
La22@Ih-C

[43]
h

[43]

[44]
[45]

Ce2@D
9b[43]
9a[43]

10[44]
11[45]
4 [40]
[40]

[41]

[42]
Ce22@I
4 [40]
55[40]

66[41]

77[42]
2
Ce

Ce
9b
9a

10
11
3.3. Redox potentials (in VVVvs. + of pristine and derivatized dimetallofullerenes.
Figure
Figure
Figure Redox potentials
3. Redox potentials(in
(in vs.Fc/Fc
vs. Fc/Fc++)))of
Fc/Fc of pristine
pristine and derivatized
derivatizeddimetallofullerenes.
dimetallofullerenes.

Scheme 4. Synthesis of silirane adducts of La2@Ih-C80. Partial structures are shown for 9a, 9b, 10 and 11.
Scheme 4. Synthesis of silirane adducts of La2@Ih-C80. Partial structures are shown for 9a, 9b, 10 and 11.
Scheme 4. Synthesis of silirane adducts of La2 @Ih -C80 . Partial structures are shown for 9a, 9b, 10 and 11.
6. Reactions of Sc3N@Ih-C80 with Disilirane 1
6. Reactions of Sc3N@Ih-C80 with Disilirane 1
Details
6. Reactions ofofScthe structures
3 N@I h -C80 withand Disilirane
physical properties
1 of silylated derivatives of Sc3N@Ih-C80, the most
Details oftrimetallic
abundant the structures
nitrideand physical(TNT)
template properties of silylated
fullerene, derivatives
have been reported of Sc 3N@I
[37]. h-C80, the most
Irradiation of
Details of the structures and physical properties of silylated derivatives of Sc3 N@Ih -C80 , the
disiliranetrimetallic
abundant 1 and Sc3N@I h-C80 in
nitride a mixed (TNT)
template solvent fullerene,
of toluene/1,3,5-trichlorobenzene
have been reported (3/1) [37]. produced
Irradiation the of
most abundant trimetallic nitride template (TNT) fullerene, have been reported [37]. Irradiation of
corresponding
disilirane 1 and Scadducts,
3N@Ih-Cwhich
80 in a were
mixedsubsequently purified using HPLC to afford (3/1)
solvent of toluene/1,3,5-trichlorobenzene a mixture of twothe
produced
disilirane andand
112a Sc312b
N@Iinh -C 80 in of
a mixed solvent 3:2 of toluene/1,3,5-trichlorobenzene (3/1) produced
corresponding adducts, which were subsequently purified using HPLC to afford a mixturenot
adducts a ratio approximately (Scheme 5). Although 12a and 12b could of be
two
theisolated,
corresponding adducts, which were subsequently purified using HPLC to afford a mixture of
adducts 12athe andNMR12b inspectra
a ratioof of
the mixture suggested
approximately that 12a5).
3:2 (Scheme and 12b consisted,
Although 12a and respectively,
12b could not of abe
two1,2-adduct
adducts 12a and 12b
at thespectra in a
[5,6]-junction,ratio of approximately
and a 1,4-adduct 3:2 (Scheme 5). Although 12a and 12b could
isolated, the NMR of the mixture suggestedatthat the 12a
[5,6,6]-junctions
and 12b consisted, on the Irespectively,
h-C80 cage. It is
of a
notparticularly
be isolated,interesting
the NMRthat spectra
when ofa the mixture
mixture of 12asuggested
and 12b thatheated
was 12a and in 12b consisted, respectively,
o-dichlorobenzene (ODCB)
1,2-adduct at the [5,6]-junction, and a 1,4-adduct at the [5,6,6]-junctions on the Ih-C80 cage. It is
of aat1,2-adduct
353 K, facile atisomerization
the [5,6]-junction,of 12aandto 12ba 1,4-adduct
occurred, whichat the suggests
[5,6,6]-junctions
that 12b on the Ih -C80 cage. It is
is thermodynamically
particularly interesting that when a mixture of 12a and 12b was heated in o-dichlorobenzene (ODCB)
particularly
more stable interesting
than 12a.thatThewhen a mixture
structure of 12b ofwas and 12b was
12aconfirmed heated
by X-ray in o-dichlorobenzene
crystallographic analysis(ODCB)
to be
at 353 K, facile isomerization of 12a to 12b occurred, which suggests that 12b is thermodynamically
at 353
the K, facile isomerization
1,4-adduct. of 12a tothe
Results also indicate occurred,
12blocation which
of the suggests Sc
encapsulated that
3N 12b is thermodynamically
cluster, which is oriented
more stable than 12a. The structure of 12b was confirmed by X-ray crystallographic analysis to be
moreso stable
that the Y-shaped
than 12a. The Sc3structure
N cluster of straddles
12b wasthe addition by
confirmed site. Furthermore,
X-ray crystallographictheoreticalanalysis calculations
to be the
the 1,4-adduct. Results also indicate the location of the encapsulated Sc3N cluster, which is oriented
suggest that
1,4-adduct. the free
Results alsocircular
indicatemotion of the of
the location Sc3the
N cluster is restricted
encapsulated Sc3 Nincluster,
12b. Similar
whichaddition
is oriented patterns
so that
so that the Y-shaped Sc3N cluster straddles the addition site. Furthermore, theoretical calculations
were reported for the 1,4-adducts, Sc N@I -C (CF ) [46] and Sc N@I
the Y-shaped Sc3 N cluster straddles the addition site. Furthermore, theoretical calculations suggest
3 h 80 3 2 3 h-C 80 (CH 2 C 6H 5 ) 2 [47], which
suggest synthesized,
that the free circular motion of the Sc 3N cluster is restricted in 12b. Similar addition patterns
thatwere
the free circularrespectively,
motion of the by Sc
radical addition reactions of CF3 and CH2C6H5 radicals.
3 N cluster is restricted in 12b. Similar addition patterns were
were reported for the 1,4-adducts, Sc3N@Ih-C80(CF3)2 [46] and Sc3N@Ih-C80(CH2C6H5)2 [47], which
reported for the 1,4-adducts, Sc3 N@Ih -C80 (CF3 )2 [46] and Sc3 N@Ih -C80 (CH2 C6 H5 )2 [47], which were
were synthesized, respectively, by radical addition reactions of CF3 and CH2C6H5 radicals.
synthesized, respectively, by radical addition reactions of CF3 and CH2 C6 H5 radicals.
Molecules 2017, 22, 1179 7 of 17
Molecules 2017, 22, 1179 7 of 17
Molecules 2017, 22, 1179 7 of 17

Scheme 5. Synthesis of disilirane adducts of Sc3N@Ih-C80.

Scheme 5. Synthesis of disilirane adducts of Sc3 N@Ih -C80 .
Scheme 5. Synthesis of disilirane adducts of Sc3N@Ih-C80.
The E°x1 and Ered1 potentials of 12b shifted remarkably to negative values by 540 and 230 mV,
The
TheE◦E°x and Ered potentials of 12b shifted remarkably to negative values by 540 and 230 mV,
respectively,1 x1 compared to those of
and Ered11 potentials of pristine Sc3N@I
12b shifted h-C80, reflecting
remarkably to negativethe addition
values by of 540
twoand silyl230
groupsmV,
respectively,
(Figure 4). compared
These shiftsto those
of the of pristine
redox Sc
potentials
3 N@I -C
correspond
h 80 , reflecting
to the
changes
respectively, compared to those of pristine Sc3N@Ih-C80, reflecting the addition of two silyl groups addition
in the of
lowest two silyl groups
unoccupied
(Figure
(Figure4).4).These
molecular Theseshifts
orbital (LUMO)
shifts ofoftheandredox
the highest
redox potentials
occupied
potentials correspond
molecular to
correspond to changes
orbital
changes ininthe
(HOMO) thelevels
lowest
lowest unoccupied
according
unoccupied to
molecular
theoreticalorbital
molecular calculations (LUMO)
orbital (LUMO) and
[37]. and highest
The HOMO occupied
highest and LUMO
occupied molecular
levels of orbital
molecular orbital (HOMO)
12b are(HOMO)
higher than levels
those
levels according
of pristine
according to to
theoretical
Sc3N@Ih-C
theoreticalcalculations
80.calculations
In addition, [37].
the The
[37]. The HOMO
HOMO and
HOMO–LUMO LUMO
energy
LUMO gap levels
of 12b
levels ofis12b
of 12b arehigher
smaller
are higher
than that than
than those
ofthose
Sc3N@I ofhof
-C pristine
. For
pristine
80

Sc3comparison,
N@I
Sc 3N@I-C-C
h 80
h .
80 . Inthe
In E° x1 andthe
addition,
addition, E
the potentials
redHOMO–LUMO
HOMO–LUMO
1 of Sc N@I
energy
energy
3 h -C
gapgap
80 (CF
of of)
12b
3 2 were
12b
is is reported
smaller
smaller than as
than +0.47
that that
of V
Scof
3 and
Sc
N@I 3
h −1.16
N@I
-C 80 V 80 .
h -C
. For
versus
Forcomparison,the
comparison, E° E
thethe ◦ x
ferrocene/ferrocenium red
E 1Epotentials couple (Fc/Fc +), respectively, in agreement with the
1 and 1 and 1 potentials
of Sc3N@Iof Sch-C
3 N@I
80(CF h -C
3)2 80 (CF3reported
were )2 were reported
as +0.47 Vasand +0.47
−1.16 V and
V
x red

electron-withdrawing
−1.16
versus
V versus effects of the CF3couple
the ferrocene/ferrocenium
the ferrocene/ferrocenium groups [46].
(Fc/Fc(Fc/Fc
couple +), + ), respectively,
respectively, in agreement
in agreement withwith thethe
electron-withdrawing
electron-withdrawing effectsofofthe
effects theCFCF3 3groups
groups [46].
[46].
1.00
0.62
1.00
0.50 0.62 0.24 0.25
0.08
0.50 0.24 0.25
(V) (V)

0.00 0.08
Potential

0.00
Eox1
Potential

-0.50 ox
Ered11
-0.50
-1.00 -1.22 -1.18 -1.22 Ered1
-1.45 -1.18
-1.00 -1.22 -1.22
-1.50 -1.45
80 [21]

-1.50
[21]

-2.00
h-C80h-C

[23] [23]

[57] [57]
29a [57]

-2.00
Sc3N@I

29a [57]
12b 12b

29b 29b
Sc3N@I

Figure 4. Redox potentials (in V vs. Fc/Fc+) of pristine and derivatized Sc3N@Ih-C80.
Figure
Figure 4. Redox
4. Redox potentials
potentials (in(in
VV Fc/Fc++)) of
vs.vs.Fc/Fc of pristine
pristineand
andderivatized
derivatizedScSc
3N@I h-C80
3 N@I .
h -C80 .
7. Reactions of Lu3N@Ih-C80 with Silylene
7. Reactions
7. Reactions ofof
In recent Lu Lu3N@I
years, h-C80 with Silylene
3 N@Iamong the TNT
h -C80 with EMFs, Lu3N@Ih-C80 has emerged as a suitable acceptor for
Silylene
organic solar cells because the LUMO
In recent years, among the TNT EMFs, level of Lu33N@Ihh-C80
80 is
hashigher than as
emerged thata of C60 andacceptor
suitable other TNT for
In recent years, among the TNT EMFs, Lu3 N@Ih -C80 has emerged as a suitable acceptor for
EMFs,
organicMsolar
3N@Icells
h-C80 (M = Sc, Y,
because theetc.)
LUMO[48,49]. Indeed,
level methano-bridged
of Lu3N@I h-C80 is higherderivatives
than that ofofCLu 3N@I
60 and h-C80 have
other TNT
organic solar cells because the LUMO level of Lu3 N@Ih -C80 is higher than that of C60 and other TNT
been
EMFs,synthesized
M3N@Ih-C80for (M application
= Sc, Y, etc.)in organic
[48,49]. photovoltaic
Indeed, (OPV) devices,
methano-bridged whichofshow
derivatives Lu3N@I increases in
h-C80 have
EMFs, Mcircuit
3 N@Ihvoltage
-C80 (M and= Sc,higher
Y, etc.)efficiencies.
[48,49]. Indeed, methano-bridged derivatives of Lu3 N@Ithe -C
open
been synthesized for application For the
in organic photovoltaic application of EMFs
(OPV) devices, whichto OPV increasesh in 80
show devices,
have been
silylationsynthesized
reaction for application
is attractive to adjustin organic
the LUMO photovoltaic (OPV) devices, which show increases
to in
open circuit voltage and higher efficiencies. For levels of the EMFs.
the application ofThese
EMFsresults
to OPV prompted
devices,usthe
open circuit reaction
investigate
silylation voltage and
the synthesis higher efficiencies.
and properties
is attractive For the application
of organosilicon
to adjust the LUMO of theofEMFs.
EMFs
levelsderivatives to3N@I
OPV
of These
Lu devices, the silylation
h-C80. prompted us to
results
investigate the synthesis and properties of organosilicon derivatives of Lu3N@Ih-C80.
Molecules 2017, 22, 1179 8 of 17

Molecules 2017, 22, 1179 8 of 17

reaction is attractive to adjust the LUMO levels of the EMFs. These results prompted us to investigate
Previously,
the synthesis andthe addition
properties of of silylene to derivatives
organosilicon C60 was achieved
of Lu3 N@I byh -C
photochemical
80 . reactions using
trisilane compounds 13 [50] as precursors of silylenes (Scheme
Previously, the addition of silylene to C60 was achieved by photochemical reactions 6). However, this reaction requires
using
short-wavelength
trisilane compounds ultraviolet
13 [50] asirradiation
precursorsusing low-pressure
of silylenes (Scheme mercury lamps.this
6). However, When a solution
reaction requiresof
Lu3N@Ih-C80 and 13
short-wavelength was photolyzed
ultraviolet irradiation via using
ultraviolet irradiation,
low-pressure no silylene
mercury lamps.adduct Whenwas obtained,
a solution of
whereas
Lu Lu80
3 N@Ih -C 3N@I
and h-C was photolyzed
1380 was consumed. This result indicates
via ultraviolet that ultraviolet
irradiation, no silylene irradiation
adduct was is unsuitable
obtained,
for silylene
whereas Lu3 N@Iaddition
-C
h 80 reactions
was consumed.of EMFs.
This Therefore,
result indicates we synthesized
that ultraviolet bicyclic
irradiation silirane
is 14
unsuitable as for
an
alternative silylene precursor, which extrudes 15 under thermal reaction
silylene addition reactions of EMFs. Therefore, we synthesized bicyclic silirane 14 as an alternative conditions [51]. An ODCB
solutionprecursor,
silylene of 14 and which
Lu3N@I h-C80 was
extrudes 15heated
under in the dark
thermal to afford
reaction two silylene
conditions [51]. An mono-adducts
ODCB solution 16aofand
14
16b (Scheme
and Lu3 N@Ih -C6).80Based on NMR
was heated in analysis,
the dark to theafford
structures of 16a and
two silylene 16b were determined
mono-adducts 16a and 16brespectively
(Scheme 6).
to be [5,6]-
Based on NMRand analysis,
[6,6]-adducts. Furthermore,
the structures of 16atheandfulleroid
16b were structure
determinedof 16a was established
respectively via X-ray
to be [5,6]- and
crystallographic
[6,6]-adducts. analysis. Adducts
Furthermore, 16a and
the fulleroid 16b were
structure sensitive
of 16a to ambientvia
was established light.
X-ray They decomposed
crystallographic
gradually Adducts
analysis. to afford16a pristine
and 16b Lu3were
N@Ih-C 80. In addition,
sensitive to ambient the light.
isomerization of 16b to 16a
They decomposed was also
gradually to
observed upon exposure to ambient light. In contrast, in the addition of
afford pristine Lu3 N@Ih -C80 . In addition, the isomerization of 16b to 16a was also observed upon silylene to Sc 3N@I h-C 80 using
14 under to
exposure the same conditions,
ambient the reaction
light. In contrast, was notofefficient.
in the addition silylene toIt Sc
afforded
3 N@Ih -C a 80poor
using product
14 under yield,
the
preventing further structural elucidation. Based on the electrophilic
same conditions, the reaction was not efficient. It afforded a poor product yield, preventing further character of silylenes, the
HOMOs ofelucidation.
structural M3N@Ih-C80Based (M = onSc and Lu) might play
the electrophilic an important
character role in
of silylenes, thetheir
HOMOs different
of Mreactivities
3 N@Ih -C80
toward
(M = Sc 15.
and Lu) might play an important role in their different reactivities toward 15.

Scheme6.6.Synthesis
Scheme Synthesisof
ofsilylene
silyleneadducts
adductsof
ofLu
Lu33N@I
N@Ihh-C80
80..

Electrochemical measurements
Electrochemical measurements yieldedyielded the the voltammograms
voltammograms of of 16a
16a and
and 16b, which showed
16b, which showed
irreversible oxidation and reduction processes. The formation of pristine Lu 3N@Ih-C80 was observed
irreversible oxidation and reduction processes. The formation of pristine Lu3 N@Ih -C80 was observed
from electrochemical
from electrochemical measurements
measurements [51]. [51]. The
The E° E◦ x11 potentials
x
potentials of
of 16a
16a and
and 16b
16b shifted toward more
shifted toward more
negative values by 340 and 180 mV, respectively, compared with those of
negative values by 340 and 180 mV, respectively, compared with those of Lu3 N@Ih -C80 (Figure 5). Lu 3N@Ih-C80 (Figure 5).

However, the
However, thecathodic
cathodicshifts
shiftsofofthe
the Ered1potentials
Ered potentialsofof 16a
16a andand
16b16b were
were observed
observed to 40
to be beand 40 and 130
130 mV,
1
mV, respectively,
respectively, relative
relative to that
to that of Luof N@I
Lu3N@I h-C80. As observed for 16a and 16b, the redox behaviors of
3 h -C80 . As observed for 16a and 16b, the redox behaviors of
derivatized EMFs depend on the addition
derivatized EMFs depend on the addition pattern pattern on on the
the carbon
carbon cages.
cages. The redox potentials
The redox potentials of 16a
of 16a
and 16b
and 16b were
were also
also compared
compared with with those
those ofof the
the [6,6]-Bingel–Hirsch
[6,6]-Bingel–Hirsch derivatives
derivatives 1717 [52],
[52], 18
18 [52],
[52], 1919 [53],
[53],
the [6,6]-carbene adduct 20 [54], and the [5,6]-carbene adduct 21 [54] (Figure 6).
the [6,6]-carbene adduct 20 [54], and the [5,6]-carbene adduct 21 [54] (Figure 6). The E 1 values of The E° x1 values of the
◦ x
17–21
the were
17–21 shifted
were lessless
shifted cathodically
cathodically thanthan those
those ofof16a
16aand
and16b,
16b,indicating
indicating that
that the
the addition
addition of of
silylenes raises
silylenes raises the
the HOMO
HOMO levelslevels of
of the
theproducts.
products.In Inaddition,
addition,the
thecathodic
cathodicshifts
shiftsofofthe
theEEred
red 1 values of
1 values
of the [6,6]-adduct 16b and the [5,6]-adduct 16a are 130 and 40 mV, respectively, compared to
the [6,6]-adduct 16b and the [5,6]-adduct 16a are 130 and 40 mV, respectively, compared to that of
that of
Lu 3N@Ih-C80. It is noteworthy that those shifts of 17–19 ([6,6]-adducts) are 30–160 mV, while that of
Lu3 N@Ih -C80 . It is noteworthy that those shifts of 17–19 ([6,6]-adducts) are 30–160 mV, while that of 21
21 ([5,6]-adduct)
([5,6]-adduct) is mV
is 70 70 mV [52–54].
[52–54].
Molecules 2017, 22, 1179 9 of 17
Molecules
Molecules 2017,
2017, 22,
22, 1179
1179 99 of
of 17
17

1.00
1.00
0.61
0.61
0.43
0.43
0.50
0.50 0.27
0.27
0.06
0.06 0.08
0.08 0.00
0.00
0.00
0.00

(V)
Potential (V)
Potential
-0.50
-0.50
E
Eox
ox
11

E
Ered
red
11
-1.00
-1.00
-1.39
-1.39 -1.43
-1.43 -1.52
-1.52 -1.55
-1.55 -1.61 -1.51
-1.51
-1.61
-1.50
-1.50

80 [51]
-2.00
-2.00

Lu33N@Ihh-C80

16b [51]
16a [51]

23 [55]

26[55]

27[56]
+
Figure 5.Redox
Figure5.5.
Figure Redoxpotentials
Redox potentials(in
potentials (inVV
(in Vvs.
vs.Fc/Fc
vs. Fc/Fc
Fc/Fc++)) of
of pristine
pristine and
and derivatized
derivatized Lu N@Ihhh-C
Lu333N@I
N@I -C808080
-C .. .

Figure 6.
6. Structures
Figure 6.
Figure of
Structures of
Structures 17–21.
of 17–21.
17–21.

8.
8. Reactions
Reactions of of Lu
Lu33N@I
N@Ihh-C
-C8080 with
with Disilirane
Disilirane and and Digermirane
Digermirane
8. Reactions of Lu3 N@Ih -C80 with Disilirane and Digermirane
The
The electronic
electronic effects
effects of
of silylene
silylene onon the
the redox
redox properties
properties of of EMFs
EMFs were
were found
found to to be
be moderate,
moderate, as as
The electronic effects of silylene on the redox properties of EMFs were found to be moderate,
observed
observed forfor 16a
16a and
and 16b.
16b. Therefore,
Therefore, the the reactions
reactions between
between Lu Lu33N@I
N@Ihh-C
-C8080 and
and disiliranes
disiliranes 11 and
and 22 were
were
as observed for 16a and 16b. Therefore, the reactions between Lu3 N@Ih -C80 and disiliranes 1 and 2
investigated
investigated to to evaluate
evaluate the the electronic
electronic effects
effects ofof bis-silylation
bis-silylation on on pristine
pristine LuLu33N@I
N@Ihh-C-C8080 [55].
[55].
were investigated to evaluate the electronic effects of bis-silylation on pristine Lu3 N@Ih -C80 [55].
Photoreaction
Photoreaction of of Lu
Lu33N@I
N@Ihh-C-C8080 and
and disilirane
disilirane 11 (or (or 2)2) was
was conducted
conducted in in aa mixed
mixed solvent
solvent of of
Photoreaction of Lu3 N@Ih -C80 and disilirane 1 (or 2) was conducted in a mixed solvent of
ODCB/toluene
ODCB/toluene using using halogen–tungsten
halogen–tungsten lamps. lamps. As As shown
shown in in Scheme
Scheme 7, 7, the
the reaction
reaction of of 11 afforded
afforded 22 22
ODCB/toluene using halogen–tungsten lamps. As shown in Scheme 7, the reaction of 1 afforded 22
and
and 23,
23, whereas
whereas that
that ofof 22 afforded
afforded 24,24, 25,
25, and
and 26,26, respectively,
respectively, asas 1:1
1:1 adducts
adducts of of Lu
Lu33N@I
N@Ihh-C
-C8080 and
and
and 23, whereas that of 2 afforded 24, 25, and 26, respectively, as 1:1 adducts of Lu3 N@Ih -C80 and
disiliranes.
disiliranes. In
In addition,
addition, 22,
22, 24,
24, and
and 25
25 were
were found
found to to be
be unstable;
unstable; 2222 readily
readily isomerized
isomerized to to 23,
23, whereas
whereas
disiliranes. In addition, 22, 24, and 25 were found to be unstable; 22 readily isomerized to 23, whereas
24
24 and
and 25
25 isomerized
isomerized to to 26.
26. Therefore,
Therefore, elucidation
elucidation of of the
the structures
structures and
and physical
physical properties
properties of of 22,
22, 24,
24,
24 and 25 isomerized to 26. Therefore, elucidation of the structures and physical properties of 22,
and 25 has been hitherto unsuccessful. The stable adducts 23 and 26
and 25 has been hitherto unsuccessful. The stable adducts 23 and 26 were determined to be the were determined to be the
24, and 25 has been hitherto unsuccessful. The stable adducts 23 and 26 were determined to be the
1,4-adducts
1,4-adducts on on the
the [5,6,6]-junctions
[5,6,6]-junctions of of the
the IIhh-C
-C8080 cage
cage via
via single
single X-ray
X-ray crystallographic
crystallographic analysis
analysis [56].
[56].
1,4-adducts on the [5,6,6]-junctions of the Ih -C80 cage via single X-ray crystallographic analysis [56].
Molecules 2017, 22, 1179 10 of 17
Molecules 2017, 22, 1179 10 of 17

Scheme 7. 7. Synthesis of disilirane

Synthesis of disilirane and
and digermirane
digermirane adducts
adducts ofofLu
LuN@I
3N@Ih-C80, and isomerization
Scheme 3 h -C80 , and isomerization
reactions of 22, 24 and 25.
reactions of 22, 24 and 25.

Furthermore, the photoreaction of Lu3N@Ih-C80 with digermirane 3 was investigated to compare

Furthermore, the photoreaction of Lu3 N@Ih -C80 with digermirane 3 was investigated to compare
the electronic properties of the germylated and silylated derivatives [56]. Due to the higher orbital
the electronic properties of the germylated and silylated derivatives [56]. Due to the higher orbital
energy levels of C–Ge bonds compared to those of C–Si bonds, it is expected that germylation will
energy levels of C–Ge bonds compared to those of C–Si bonds, it is expected that germylation
perturb the electronic properties of fullerenes effectively. It is particularly interesting that the
will perturb the electronic properties of fullerenes effectively. It is particularly interesting that
photoreaction of Lu3N@Ih-C80 with 3 proceeded faster than with 2 to afford the corresponding
the photoreaction of Lu3 N@Ih -C80 with 3 proceeded faster than with 2 to afford the corresponding
1,4-adduct 27 under the same reaction conditions (Scheme 7). The structure of 27 was also confirmed
1,4-adduct 27 under the same reaction conditions (Scheme 7). The structure of 27 was also confirmed
using X-ray crystallographic analysis. Results of our earlier study demonstrate that C60 functions as
using X-ray crystallographic analysis. Results of our earlier study demonstrate that C60 functions as
an electron acceptor in the photoreactions with 1 [25]. Therefore, a similar electron donor–acceptor
an electron acceptor in the photoreactions with 1 [25]. Therefore, a similar electron donor–acceptor
interaction is presumed to occur in the case of Lu3N@Ih-C80. In fact, the high electron donating
interaction is presumed to occur in the case of Lu3 N@Ih -C80 . In fact, the high electron donating
property of 3 is explained respectively based on the oxidation peak potentials of 2 (+0.54 V) and 3
property of 3 is explained respectively based on the oxidation peak potentials of 2 (+0.54 V) and 3
(+0.45 V) relative to the Fc/Fc+ couple. This result was also supported by comparison of the HOMO
(+0.45 V) relative to the Fc/Fc+ couple. This result was also supported by comparison of the HOMO
levels of 2 and 3 obtained using theoretical calculations. Furthermore, the calculated structures of 2
levels of 2 and 3 obtained using theoretical calculations. Furthermore, the calculated structures of 2
and 3 indicate that the Ge–Ge and Ge–C bonds of 3 are slightly longer, respectively, than the Si–Si
and 3 indicate that the Ge–Ge and Ge–C bonds of 3 are slightly longer, respectively, than the Si–Si
and Si–C bonds of 2. As expected, the high reactivity of 3 can be attributed to its good electron donor
and Si–C bonds of 2. As expected, the high reactivity of 3 can be attributed to its good electron donor
properties and its low steric hindrance around the Ge–Ge bond [56].
properties and its low steric hindrance around the Ge–Ge bond [56].
From electrochemical measurements of 23, 26 and 27, both oxidation and reduction processes
From electrochemical measurements of 23, 26 and 27, both oxidation and reduction processes
were found to be irreversible. Figure 5 shows that the E°x1 values of 23, 26, and 27 shifted to more
were found to be irreversible. Figure 5 shows that the E◦ x 1 values of 23, 26, and 27 shifted to more
negative potentials by 530 to 610 mV, compared with that of pristine Lu3N@Ih-C80. Cathodic shifts of
negative potentials by 530 to 610 mV, compared with that of pristine Lu3 N@Ih -C80 . Cathodic shifts of
Ered
red1 values were also observed for 23, 26, and 27 within the range of 120 to 220 mV. The E°x1 and Ered1
E 1 values were also observed for 23, 26, and 27 within the range of 120 to 220 mV. The E◦ x 1 and Ered 1
values of 27 showed slight cathodic and anodic shifts, respectively, compared to the corresponding
values of 27 showed slight cathodic and anodic shifts, respectively, compared to the corresponding
redox potentials of 23 and 26. As a result, 27 was found to be oxidized and reduced more readily
redox potentials of 23 and 26. As a result, 27 was found to be oxidized and reduced more readily than
than 23 or 26. These cathodic shifts of E°x1 values of 23, 26 and 27 were confirmed to be remarkably
23 or 26. These cathodic shifts of E◦ x 1 values of 23, 26 and 27 were confirmed to be remarkably larger
larger than those of 16a and 16b, as expected from the number of silicon and germanium atoms
than those of 16a and 16b, as expected from the number of silicon and germanium atoms introduced
introduced into the fullerene cages.
into the fullerene cages.
9. Reactions
9. Reactions of
of Sc
Sc33N@I
N@Ihh-C
-C8080with
withSilirane
Silirane2828
As described
As described above,
above, the
the addition
addition reaction
reaction between
between Sc N@Ih-C
Sc3N@I -C80 and silylene produced the
3 h 80 and silylene produced the
corresponding adduct
corresponding adduct in
in poor
poor yield.
yield. This
This result
result prompted
prompted us to develop
us to develop an
an alternative
alternative silylation
silylation
reaction of Sc3N@Ih-C80 using silirane 28 [57]. Photoirradiation of a toluene solution of Sc3N@Ih-C80
reaction of Sc3 N@Ih -C80 using silirane 28 [57]. Photoirradiation of a toluene solution of Sc3 N@Ih -C80
and 28
and 28 afforded
afforded three
three compounds
compounds 29a,29a, 29b,
29b, and
and 29c
29c (Scheme
(Scheme 8).
8). Results
Results of MALDI-TOF mass
of MALDI-TOF mass
spectrometry, VIS-NIR and NMR spectroscopy suggest that 29a and 29b are a pair of diastereomers
spectrometry, VIS-NIR and NMR spectroscopy suggest that 29a and 29b are a pair of diastereomers
of [5,6]-adducts, whereas 29c might be a [6,6]-adduct. However, further characterization of 29c has
not yet been achieved because of its low yield. It is noteworthy that the carbosilylation of La2@Ih-C80
Molecules 2017, 22, 1179 11 of 17

of [5,6]-adducts,
Molecules whereas 29c might be a [6,6]-adduct. However, further characterization of 29c
2017, 22, 1179 has
11 of 17
Molecules
not 2017, 22,
yet been 1179
achieved because of its low yield. It is noteworthy that the carbosilylation of La2 @I11h -C of 17
80
using 8 was conducted
conducted under
under thermal
thermalconditions.
conditions.However,
However,the
thereaction
reactionofofLa
La2 @Ihh-C
2@I 80 using 8 did not
-C80
using 8 was
proceed conducted under
efficiently thermal conditions. However, the reaction of La2@Ih-C80 using 8 did not
efficiently under
under photolytic
photolytic conditions
conditions [43].
[43].
proceed efficiently under photolytic conditions [43].

Scheme 8. Synthesis of silirane adducts of Sc3N@Ih-C80.

Scheme8.8.Synthesis
Scheme Synthesisof
ofsilirane
siliraneadducts
adductsofofSc
Sc33N@I
N@Ihh-C 80..
-C80
The E°x1 values of 29a and 29b shifted toward more negative potentials by 380 and 370 mV,
The EE°
The ◦ x1 values
values toof 29a
ofthat and
and 29b shifted toward
toward more
more negative
negative potentials
potentials by by 380
380 and
and 370
370 mV,
respectively, 1relative 29a of Sc329bN@Ishifted
h-C80 (Figure 4). However, the Ered1 values of 29a and 29b were
mV,
respectively,relative
respectively, relativetotothat thatofofScSc N@I
3 N@I -C
h -C 80 (Figure
(Figure 4).
4). However,
However, the
the E
E red
red1 values of 29a and 29b were
were
nearly equal to that of Sc3N@Ih-C380. These h 80properties were verified based 1 on the HOMO and LUMO
nearly equal
nearly equal to to that
thatofofSc N@Ihh-C80
Sc33N@I 80 .. These
These properties
properties were
were verified
verified based on the HOMO and LUMO LUMO
energies of 29a and 29b obtained using theoretical calculations. To confirm the electronic effects of
energies of
energies of 29a
29a andand 29b
29b obtained
obtained usingusing theoretical
theoretical calculations.
calculations. To confirm
confirm the the electronic
electronic effects
effects of
of
carbosilylation, these values were evaluated by comparing with those of the [5,6]-pyrrolidino
carbosilylation, these
carbosilylation, thesevalues
values werewere evaluated
evaluated by by comparing
comparing with with of
those those
the of the [5,6]-pyrrolidino
[5,6]-pyrrolidino adducts
adducts 30a [58], 30b [58], and 31 [59,60], and the [5,6]-benzyne adduct 32 [61] (Figure 7). Results
adducts
[58], 30a [58], and 30b [58], and 31 [59,60],
x1 [59,60], and the [5,6]-benzyne
adduct 32 adduct 32 [61]
7). (Figure
Results 7). Results
30a
show 30b
that both the E°31 and Eredand the [5,6]-benzyne [61] (Figure
1 potentials of 29a and 29b were shifted slightly toward more
show that
showthe
both that
E ◦ x
both and the
E red
E° x 1 and E of
potentials red 1 potentials
29a and of were
29b 29a and 29bslightly
shifted were shifted
toward slightly
more towardvalues
negative more
1 1
negative values than those of 30a, 30b, 31 and 32. By coupling the redox properties of 9a and 9b, it
negative
than values
those of 30a, than those of 30a,
31 and 30b, 31 and 32.
By coupling Byredox
the coupling the redox
properties properties
of 9a of 9a and 9b, it
appears that 30b,
carbosilylation of32.EMFs produces slight cathodic shifts ofand it appears
the9b,redox that
potentials
appears that
carbosilylation carbosilylation
of EMFs of
produces EMFs produces
slight cathodic slight cathodic shifts of the redox potentials
compared to those produced by derivatization withshifts of the redox
carbon-based potentials compared to those
addends.
comparedby
produced to derivatization
those produced by derivatization
with carbon-based addends. with carbon-based addends.

Figure 7. Partial structures of 30a, 30b, 31 and 32.

Figure 7.
Figure 7. Partial
Partial structures
structures of
of 30a,
30a, 30b,
30b, 31
31 and
and 32.
32.
10. Dynamic Behaviors of the Encapsulated Atoms
10. Dynamic
10. Dynamic Behaviors
Behaviors ofof the
the Encapsulated
Encapsulated AtomsAtoms
The behavior of encapsulated metal atoms is an interesting issue affecting chemical and
The behavior
The behavior of encapsulated metal atoms anisinteresting
an interesting issue affecting chemical and
physical propertiesofofencapsulated metal
EMFs. The movements atoms is encapsulated
of issue affecting
metal atoms are chemical
affectedand physical
by both the
physical
propertiesproperties of
of metal–cage EMFs.
EMFs. The movements The movements of
of encapsulated encapsulated
metal atoms metal atoms are affected by both the
electrostatic and the metal–metal interactions. In theare affected
case by both the electrostatic
of monometallic EMF, metal
electrostatic
metal–cage metal–cage and the metal–metal interactions. In the case of monometallic EMF, metal
atoms tend andnot the metal–metal
to move aroundinteractions. In theIn
inside the cages. case of monometallic EMF,
dimetallofullerenes with metal atoms tend
highly-symmetric
atoms
not tend
to move not to move around inside the cages. In dimetallofullerenes with highly-symmetric
carbon cages,around
such asinside
M2@Ithe cages.
h-C80 , two In dimetallofullerenes
atoms can rotate in everywith highly-symmetric
direction along thecarbon cages,
endohedral
carbon
such as cages, such, two
M2 @Ih -C as Matoms
2@Ih-C80, two atoms can rotate in every direction along the endohedral
can rotate in every direction along the endohedral surface [62–65].
surface [62–65]. However,
80 the positions and behaviors of metal atoms, as well as their electronic
surface [62–65].
However, However, the positionsofand behaviors of well
metalasatoms, as well asproperties,
their electronic
properties,the
werepositions
found to andbe behaviors metal
altered by exohedral atoms, as
derivatization. their
For electronic
example, the encapsulated were
Ce
properties,
found were found to be altered by exohedral derivatization. For example, the encapsulated Ce
atoms to
in be altered
6 were by exohedral
observed to be fixedderivatization. For example,
at two positions close to thethesix-membered
encapsulated Ce ringatoms
on theinequator
6 were
atoms in 6 were observed to be fixed at two positions close to the13six-membered ring on the equator
of the Ih-C80 cage via X-ray crystallographic and paramagnetic C-NMR spectral analysis [41]. In
of the Ih-C80 cage via X-ray crystallographic and paramagnetic 13C-NMR spectral analysis [41]. In
addition, variable temperature (VT) 139La NMR and X-ray crystallographic analysis of 5 revealed that
addition, variable temperature (VT) 139La NMR and X-ray crystallographic analysis of 5 revealed that
the La atoms circulate two-dimensionally along the equator of the C80 cage [40]. These results were
the La atoms circulate two-dimensionally along the equator of the C80 cage [40]. These results were
consistent with earlier reported results of theoretical calculations [66].
consistent with earlier reported results of theoretical calculations [66].
Molecules 2017, 22, 1179 12 of 17

observed to be fixed at two positions close to the six-membered ring on the equator of the Ih -C80 cage
via X-ray crystallographic and paramagnetic 13 C-NMR spectral analysis [41]. In addition, variable
temperature (VT) 139 La NMR and X-ray crystallographic analysis of 5 revealed that the La atoms
circulate two-dimensionally along the equator of the C80 cage [40]. These results were consistent with
earlier reported results of theoretical calculations [66].
The dynamic behaviors of the encapsulated metal atoms in 9a and 9b were also studied using VT
139 La NMR spectroscopy and theoretical calculations [43]. The results showed that the line width of

the 139 La signal is broadened at temperatures higher than 280 K, suggesting that the two La atoms
move dynamically inside the carbon cage of 9a and 9b. Coupling of these results with the X-ray
crystallographic analysis of 9a suggests that the La atoms are moving inside an annular belt formed
from the six-membered rings [43].

11. Potential Applications

As shown in this review, various EMFs and empty fullerenes showed high reactivities toward
disiliranes, which have activated Si–Si bonds. Moreover, polysilanes, i.e., polymers comprising of
catenated Si–Si bonds as polymer backbones, have attracted considerable interest as novel functional
materials because of their unique chemical and physical properties [67,68]. Based on the delocalization
of σ–electrons along the backbones of polysilanes, they have been studied as future functional materials,
such as conductive polymers [69–78], photoresists [79], and organic light emitting diodes (LEDs) [80].
Polysilanes are well-known for their high hole mobility, however, their photoinduced charge carrier
generation is not efficient. Doping C60 as an acceptor into polysilanes resulted in photoinduced electron
transfer between them, which dramatically improved the charge carrier generation efficiency [70,71].
The electron transfer processes between photoexcited C60 and polysilanes [81,82] or polygermanes [83]
were confirmed by laser flash photolysis experiments.
Due to their photoconductive properties, polysilanes may be applied to novel organic semiconductor
devices. Some researchers investigated the photovoltaic properties of bulk heterojunction solar
cells using C60 and [6,6]-phenyl C61 -butyric acid methyl ester (PCBM) as electron acceptors and
polysilanes as electron donors [84–87]. Furthermore, composite materials composed of polysilanes and
EMFs may exhibit improved electronic properties as compared with those of empty fullerene-based
materials. The organic solar cells using Lu3 N@Ih -C80 as an acceptor material showed higher open
circuit voltages and higher photovoltaic efficiencies than those of C60 because of the higher LUMO
level of Lu3 N@Ih -C80 [48,49].
The MO levels of the silylated and germylated EMFs were remarkably altered by the electron
donating silyl and germyl groups as compared with those of pristine EMFs. Therefore, silylation
and germylation would be useful for adjusting the electronic properties of EMF derivatives in
electronic devices. In addition, covalent bonding between fullerenes and polysilanes can be used to
construct donor–acceptor conjugate structures. The first prototype polysilane that incorporated C60
into the polymer backbone was synthesized by the photoreaction of a polysilane with C60 [88–91].
Development of silylation and germylation reactions of fullerenes will provide useful methods for
affording fullerene-polysilane/polygermane conjugates.

12. Summary
This review provided an overview of our studies of the synthesis and characterization of silylated
and germylated derivatives of EMFs using active silicon compounds and germanium compounds.
Among these, disilirane 1 has been used as a versatile substrate that is both photochemically and
thermally reactive. A comparison of the redox potentials of EMFs revealed that the reactivities of
EMFs toward 1 depend on the electron-accepting abilities of the EMFs. Moreover, NMR and X-ray
crystallographic examinations revealed that silylation affects the dynamic behavior of the encapsulated
metal atoms and clusters in the EMFs. For example, results show that the movement of the La atoms
in La2 @Ih -C80 was restricted to two-dimensional rotation near the equatorial plane of the carbon
Molecules 2017, 22, 1179 13 of 17

cage upon addition of 1. The electronic effects of silylation and germylation on EMFs were clarified
by electrochemical examinations and theoretical calculations. In general, the redox potentials of
silylated and germylated derivatives shifted to more negative values relative to those of pristine
EMFs. In particular, the cathodic shifts of the oxidation potentials were found to be remarkably large,
reflecting the electron-donating effects of the silyl and germyl groups. These results demonstrate that
EMFs with novel physical properties and functionalities are obtainable through chemical modification
by exploiting the properties of various heteroatom-based functional groups.

Acknowledgments: This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas
(No. 20108001, “pi-Space”), a Grant-in-Aid for Scientific Research (A) (No. 202455006), (B) (No. 24350019), and (C)
(No. 17K05797), and Specially Promoted Research (No. 22000009) from the Ministry of Education, Culture, Sports,
Science, and Technology of Japan.
Conflicts of Interest: The authors declare no conflict of interest.

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