論文の公開元へConstruction of Charge-Separation-Type Ionic Crystals Based on Monocationic AuI4MIICoIII (M = Ni, Cu) Hexanuclear Complexes
概要
Title
Author(s)
Construction of Charge-Separation-Type Ionic
Crystals Based on Monocationic AuI4MIICoIII (M
= Ni, Cu) Hexanuclear Complexes
Pratikha, Rycce Sylviana
Citation
Issue Date
oaire:version
URL
https://hdl.handle.net/11094/77592
rights
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Osaka University Knowledge Archive : OUKA
https://ir.library.osaka-u.ac.jp/
Osaka University
A b s t ra c t o f T h e s i s
Name
RYCCE SYLVIANA PRATIKHA
Title
The ionic crystal based on supramolecular compounds has received a great attention owing to their potential physical and
chemical properties by the attempt to design and control of intermolecular interactions. The metalloligand approach is one of the
sophisticated strategies to build a supramolecular architecture. Due to the modular nature of metalloligand, it is feasible to create
a series of analogous metal complexes by the replacement of organic ligands or metal ions in the metalloligand. Recently, our
group designed a digold(I) metalloligand, [Au2(dppe)(D-Hpen)2] (dppe = 1,2-bis(diphenylphosphino)ethane,
D-penicillamine).
D-H2pen
=
The reaction of [Au2(dppe)(D-Hpen)2] with CoII ion in air produced dicationic [Au 4Co2(dppe)2(D-pen)4]X2
hexanuclear complexes (X 2 = (NO3 )2, (Cl )2, (Br )2, (ClO4 )2, SiF62 or SO42 )). The unique charge-separation (CS)-type
structure was observed in [Au4Co2(dppe)2(D-pen)4]X2, in which the complex cations and inorganic anions were separately
aggregated. This is a very rare example of ionic crystals that show the separate assembling of cations and anions.
This thesis focused on the effect of molecular charge on the creation of the CS-type ionic crystals by using monocationic
complexes, [Au4NiIICoIII]+ and [Au4CuIICoIII]+.
In chapter II, the formation of the CS-type structure and the crystallization behavior of the monocationic
[Au4NiCo(dppe)2(D-pen)4]+ were investigated through the reaction of a metalloligand, [Au 2(dppe)(D-Hpen)2], with a mixture of
NiII and CoII ions. From the spectroscopic analysis, it was found that this reaction gives the CS-type structure in
(H3O)2/3[Au4Ni2/3Co4/3(dppe)2(D-pen)4](NO3)2 ([1Na](NO3)2). Single-crystal X-ray diffraction analysis revealed that a solid
solution of [1Na](NO3)2 contains a hexameric aggregation of four [Au 4NiCo(dppe)2(D-pen)4]+ and two [Au 4Co2(dppe)2(D-pen)4]2+
complex cations together with four H 3O+ ions to form {(H3O)4[Au4NiCo(dppe)2(D-pen)4]4[Au4Co2(dppe)2(D-pen)4]2}12+, together
with the adamantane-like (NO3 )10 in (H3O)2/3[Au4Ni2/3Co4/3(dppe)2(D-pen)4](NO3)2. The crystallization using alkali metal nitrates
(ANO3; A+ = K, Rb, Cs) produced similar CS-type structures in A2/3[Au4Ni2/3Co4/3(dppe)2(D-pen)4](NO3)2. However, [1A](NO3)2
was
found
to
accommodate
of
four
A+
ions
{A4[Au4NiCo(dppe)2(D-pen)4]4[Au4Co2(dppe)2(D-pen)4]2}
12+
in
place
of
. In [1B](NO3)2 (B
2+
H 3O+
ions
in
[1Na](NO3)2
to
give
= Ca, Sr, Ba), the same hexameric aggregation
with H3O+ ions, {(H3O)4[Au4NiCo(dppe)2(D-pen)4]4[Au4Co2(dppe)2(D-pen)4]2}12+, was found, but the NO 3 anions formed the
rhombic
dodecahedron
accommodating
two
B 2+
ions,
2B@(NO3 )14,
to
afford
(H3O)2/3[Au4Ni2/3Co4/3(dppe)2(D-pen)4](NO3)2·1/3B(NO3)2. This site-selective incorporation of cationic species is explained by
the difference in not only ionic sizes but also charge balance.
In Chapter III, the reaction of [Au 2(dppe)(D-Hpen)2] with a 1:1 mixture of Cu II and CoII ions was examined. It was found that
the resulting crystals of [3Na](NO3)2 have the CS-type ionic structure with (H3O)2/3[Au4Cu2/3Co4/3(dppe)2(D-pen)4](NO3)2. The
heterogeneous catalytic decomposition of hydrogen peroxide was investigated. [3Na](NO3)2 showed a higher O2 gas production
than [1Na](NO3)2 and [Au4Co2(dppe)2(D-pen)4](NO3)2, indicating the order of the catalytic activity Cu II > CoII > NiII. The high
catalytic activity is caused by the low activation energy of the O-O bond cleavage as the rate determined step at the Cu 2+ center.
In Chapter IV, the creation of the CS-type structure, [4]NO3, from the reaction of [Au 2Cl2(dppe)] with a 1:1 mixture of
II
[Ni (D-H2ebp)] and [CoIII(D-ebp)] with NaNO3 was described. Single-crystal X-ray analysis revealed that six complex cations of
[Au4NiCo(dppe)2(D-ebp)2]+
are
self-assembled
into
an
octahedron-shaped
supramolecular
structure,
6+
{[Au4NiCo(dppe)2(D-ebp)2]6} . On the other hand, a tetrahedral aggregate of four NO 3 , (NO3 )4, is packed in each hydrophilic
tetrahedral interstice, which balances the charge in [Au 4NiCo(dppe)2(D-ebp)2]NO3. The decreased number of anions is caused by
the presence of an ethylene moiety in [M( D-ebp)]n , which is exposed directly to each hydrophilic tetrahedral interstice.
Finally, in this study, the CS-type structures containing monocationic Au I4MIICoIII (MII = Ni, Cu) hexanuclear complex with
D-pen
and D-ebp were systematically synthesized. It was found that the different charges of the mixing metal ions affect not only
the aggregation behavior of cations and anions in the CS-type ionic crystals, but also the catalytic activity. These results will
contribute significantly to the development of ionic crystals based on ionic metallosupramolecular coordination compounds.
様式 7
論文審査の結果の要旨及び担当者
氏
名
（
RYCCE
SYLVIANA
（職）
論文審査担当者
主 査
教授
副 査
教授
副 査
教授
PRATIKHA
）
氏
名
今野
石川
吉村
巧
直人
崇
論文審査の結果の要旨
本論文は、配位可能な部位として含硫アミノ酸を、錯体配位子の機能を調節する部位としてジホス
フィン類を導入した金(I)錯体配位子を用い、それらの混合金属イオンへの配位挙動、ならびに形成
される多核金属錯体の構造と性質についてまとめたものである。Co III に Ni II を混合させた系におい
ては、Au I 4Co III 2 錯体、Au I 4Co III Ni II 錯体、および Au I4 Ni II 2 錯体の３種類の六核錯体が形成され、その
うち Au I4 Co IIINi II 錯体と Au I 4Ni II2 錯体が共結晶化して、電荷分離型のイオン結晶を形成することを見
出している。その際、用いるアルカリ金属イオンおよびアルカリ土類金属イオンの違いにより、錯体
カチオン集積体およびアニオン集積体の構造が変化することを明らかにしている。同様の挙動は、
Co III に Cu II を混合させた系においても確認しており、さらには、用いる錯体配位子の化学修飾によ
り、結晶中のアニオン集積状況を調整できることも見出している。これにより、電荷分離型イオン結
晶の形成における錯イオンの電荷および共存するイオン種の重要性を明らかにするとともに、錯体
配位子の化学修飾が分子集積化挙動の制御に重要であることを示した。よって、本論文は博士（理
学）の学位論文として十分価値あるものと認める。
