光照射・電位変化等の連続した環境変化に対し，繰り返し応 …p3 photo and...

光照射・電位変化等の連続した環境変化に対し，繰り返し応答性を示す

金属錯体系の構築

2010 年度大学教育研究重点配分経費研究成果報告書

2011 年 3 月

研究代表者中島清彦

（愛知教育大学理科教育講座・化学）

研究成果

（１）学術論文

Synthesis of Metal-Hydrazone Complexes and Vapochromic Behavior of Their Hydrogen-Bonded

Proton-Transfer Assemblies

A. Kobayashi, M. Dosen, M. Chang, K. Nakajima, S. Noro, M. Kato,

J. Am. Chem. Soc., 132(43), 15286-15298 (2010).

Photoluminescence via Two Different Excited States in a Mononuclear Europium(III) Complex with

Tetradentate Schiff Base Ligands

S. Ebato, M. Watanabe, K. Nakajima, M. Tsuchimoto,

Chem. Lett., 39 (7), 706-707 (2010).

Acid-Base Bahavior of Substituted Hydrazone Complexes Controlled by the Coordination Geometry

M. Chang, H. Horiki, K. Nakajima, A. Kobayashi, H. Chang, M. Kato,

Bull. Chem. Soc. Jpn., 83 (8), 905-910 (2010).

（２）学会発表

PS1-021 Photoisomerization of Azo-conjugated Pd(II) and Pt(II) Complexes

K. Nakajima, T. Harada (Aichi University of Education)

24th International Conference on Organometallic Chemistry (ICOMC) in Taipei, Taiwan

7/18-23/2010.

1PA-05 多様な配位様式を有するヒドラゾン‐Pd(Ⅱ),Ru(Ⅱ)錯体における配位様式の制御

(愛教大化・北大院理) 森麻美・小林厚志・張浩徹・加藤昌子・中島清彦

第 60 回錯体化学討論会 9/27-30/2010（大阪）

1PA-06 酸化還元可能な部位を有するヒドラゾン錯体の構造と性質

(愛教大化・北大院理) 田口祐香理・小林厚志・張浩徹・加藤昌子・中島清彦

第 60 回錯体化学討論会 9/27-30/2010（大阪）

IBC27 Chromotropy of the Transition Metal Complexes in the Solid and in Solution

K. Nakajima

16th Malaysian Chemical Congress (MCC) in Kuala Lumpur, Malaysia 10/12-14/2010.

P3 Photo and Thermal Isomerization of the Azo Moiety of the Ligand in Pd(II) and Pt(II)

Complexes

K. Nakajima, T. Harada

6th Asian Photochemistry Conference (APC) in Wellington, New Zealand 11/14-18/2010

ID1014 Vapochromism of a Self-assembled Hydrogen-bonded Proton-transfer Complex

Kobayashi, M. Dosen, M. Chang, S. Noro, K. Nakajima, and M. Kato

The International Chemical Congress of Pacific Basin Societies (PACIFICHEM) in Honolulu,

Hawaii, USA 11/15-20/2010

ID1235 Photoluminescence Properties of Mononuclear Europium(III) Complexes with

Tetradentate Schiff base Ligands －Emission Intensity Differences which Depend on the Variation

of Ligands and Counter Anions

M. Tsuchimoto, S. Ebato, M. Watanabe, and K. Nakajima


Hawaii, USA 11/15-20/2010

ID1255 Photoreactions and Luminescence Properties of the Metal Complexes Related to

Protonation and Deprotonation Behavior of the Hydrazone Ligands

K. Nakajima, D. Yamada, Y. Taguchi, H. Horiki, A. Kobayashi, H. Chang, and M. Kato


Hawaii, USA 11/15-20/2010

1PB-125 イオウ原子を有するヒドラゾン化合物が配位した錯体の構造と、配位イオウ原子上

のアルキル基の解離反応

(愛教大化・北大院理) 田口祐香理・山下祐理香・小林厚志・張浩徹・加藤昌子・

中島清彦

日本化学会第 91 春季年会 2011（神奈川）（東北地方太平洋沖地震による学会中止のため，

予稿集への採択）

1PB-126 ヒドラゾン化合物が配位した Pd(II)錯体における多様な配位様式と配位子上の置

換基の立体効果

(愛教大化・北大院理) 北村双美・森麻美・藤澤佐知恵・小林厚志・張浩徹・

加藤昌子・中島清彦



1PB-169 四座のシッフ塩基を配位子とする Eu(III)単核錯体の PMMA 中の発光特性

(千葉工大・原子力機構・愛教大化) 外口良平・中塩屋貴寛・槌本昌信・寺本直純・

柴田充弘・渡邉雅之・中島清彦



3A5-16 配位可能な部位を複数有するヒドラゾン‐Ru(II)錯体の合成と配位様式の変換

(愛教大化・北大院理) 森麻美・小林厚志・張浩徹・加藤昌子・中島清彦



Synthesis of Metal-Hydrazone Complexes and Vapochromic Behavior of

Their Hydrogen-Bonded Proton-Transfer Assemblies

Atsushi Kobayashi,*,† Masa-aki Dosen,

† Mee Chang,

† Kiyohiko Nakajima,

‡ Shin-ichiro

Noro,§ and Masako Kato*,

†

Department of Chemistry, Faculty of Science, Hokkaido University, North-10 West-8, Kita-ku,

Sapporo 060-0810, Japan, Department of Chemistry, Aichi University of Education, Igaya, Kariya,

Aichi 448-8542, Japan, and Research Institute for Electronic Science, HokkaidoUniversity, North-20

West-10, Kita-ku, Sapporo 001-0020, Japan

Abstract: We synthesized and investigated a new series of metal-hydrazone complexes,

including deprotonated [MX(mtbhp)] and protonated forms [MX(Hmtbhp)](ClO4) (M) Pd2+

,

Pt2+

; X ) Cl―, Br―; Hmtbhp) 2-(2-(2-(methylthio) benzylidene)hydrazinyl)pyridine) and

hydrogen-bonded proton-transfer (HBPT) assemblies containing [PdBr(mtbhp)] and

bromanilic acid (H2BA). The mtbhp hydrazone ligand acts as a tridentate SNN ligand and

provides a high proton affinity. UV-vis spectroscopy revealed that these metal-hydrazone

complexes follow a reversible protonation-deprotonation reaction ([MX(mtbhp)] + H+ ⇔

[MX(Hmtbhp)]+), resulting in a remarkable color change from red to yellow. Reactions

between proton acceptor [PdBr(mtbhp)] (A) and proton donor H2BA (D) afforded four types

of HBPT assemblies with different D/A ratios: for D/A ) 1:1, {[PdBr(Hmtbhp)](HBA) ·

Acetone} and {[PdBr(Hmtbhp)](HBA) ·2(1,4-dioxane)}; for D/A ) 1:2, [PdBr(Hmtbhp)]2(BA);

and for D/A ) 3:2, {[PdBr(Hmtbhp)]2(HBA)2(H2BA) ·2Acetonitrile}. Theproton donor gave at

least one proton to the acceptor to form the hydrogen bonded A···D pair of[PdBr(Hmtbhp)]+

···HBA―. The strength of the hydrogen bond in the pair depends on the kind of molecule

bound to the free monoanionic bromanilate OH group. Low-temperature IR spectra (T <

150 K) showed that the hydrogen bond distance between [PdBr(Hmtbhp)]+ and bromanilate

was short enough (ca. 2.58 Å) to induce proton migration in the [PdBr(Hmtbhp)]2(BA)

assembly in the solid state. The hydrogen bonds formed not only between [PdBr(Hmtbhp)]+

and HBA- but also between HBA― and neutral H2BA molecules in the

{[PdBr(Hmtbhp)]2(HBA)2(H2BA) ·2Acetonitrile} assembly. The H2BA-based flexible hydrogen

bond network and strong acidic host structure result in an interesting vapor adsorption ability

and vapochromic behavior in this assembly because the vapor-induced rearrangement of

the hydrogen bond network, accompanied by changes in π-π stacking interactions, provides

a recognition ability of proton donating and accepting properties of the vapor molecule.

J. Am. Chem. Soc., 132(43), 15286-15298 (2010)

Photoluminescence via Two Different Excited States in a Mononuclear

Europium(III) Complex with Tetradentate Schiff Base Ligands

Shouta Ebato,1 Masayuki Watanabe,

2 Kiyohiko Nakajima,

3 and Masanobu Tsuchimoto*

4

1Department of Life and Environmental Sciences, Chiba Institute of Technology, 2-17-1 Tsudanuma,

Narashino, Chiba 275-0016, 2Nuclear Science and Engineering Directorate, Japan Atomic Energy

Agency, Tokai-mura, Ibaraki 319-1195, 3Department of Chemistry, Aichi University of Education,

Kariya, Aichi 448-8542, 4Department of Chemistry, Chiba Institute of Technology, 2-1-1 Shibazono,

Narashino, Chiba 275-0023

A europium(III) complex with tetradentate Schiff base ligands (C2H5)3NH[Eu(3,5Clsalen)2]

was prepared, and its structure was determined by X-ray crystal structure analysis. The

complex has an eight-coordinate mononuclear structure with two Schiff base ligands in a

meridional form. The complex displays emission bands resulting from f―f transitions by

excitation at 357 or 234 nm in acetonitrile.

Chem. Lett., 39 (7), 706-707 (2010)

Acid Base Behavior of Substituted Hydrazone Complexes

Controlled by the Coordination Geometry

Mee Chang,1 Hiroyuki Horiki,

1 Kiyohiko Nakajima,

2 Atsushi Kobayashi,

1

Ho-Chol Chang,1 and Masako Kato*

1

1Division of Chemistry, Faculty and Graduate School of Science, Hokkaido University, Sapporo

060-0810

2Department of Chemistry, Aichi University of Education, Kariya 448-8542

A new series of substituted hydrazone complexes, [Cu(Hpbph)I] (1), [Cu(Hpbph)PPh3]PF6

(2-PF6), [NiCl(Hpbph)]Cl (3-Cl), [PtCl(Hpbph)]ClO4 (4-ClO4), and [PtCl(pbph)] (4b) (Hpbph =

2-(diphenylphosphino) benzaldehyde 2-pyridylhydrazone) have been synthesized and

characterized. X-ray crystallography revealed that the copper(I) complexes adopt

pseudo-tetrahedral geometry, while the nickel(II) and platinum(II) complexes provide

square-planar forms. All the complexes exhibit distinct color changes on the basis of the

deprotonation/protonation on the ligand although their acid/base behaviors are largely

different. The acidity constants (pKa) in methanol were determined to be 11.4 (1), 12.5 (2),

7.7 (3), and 6.7 (4). The results indicate that the dissociation of the proton on the ligand

strongly depends on the ligand deformation controlled by the coordination geometry of the

complexes and ancillary ligands also somewhat affect the acidity.

Bull. Chem. Soc. Jpn., 83 (8), 905-910 (2010)

PHOTOISOMERIZATION OF AZO-CONJUGATED Pd(II) AND Pt(II) COMPLEXES

Kiyohiko Nakajima, and Takashi Harada

Department of Chemistry, Aichi University of Education, Kariya, Aichi 448-8542, Japan

Considerable interest has been paid to the photo- and thermal- isomerization of orgnic azobenzenes in relation to the development of photo-switching devices and photon-mode information storage.1 In azo-conjugated metal complexes, isomerization properties can be controlled by altering the electronic state distribution on the ligands and/or metal ions.2 We successfully prepared several Pd(II) and Pt(II) complexes containing an azobenzene-attached ligand (L; (E)-N-(2-(diphenylphosphino)benzylidene)-4-((E)-phenyldiazenyl)aniline), determined the structures, and studied the photo- and thermal- isomerization properties. Fig.1 shows the structure of [PdCl2(L)] (1). The Pd aton is coordinated with a bidentate ligand L and two Cl－ ions, and the azo group has a trans structure. Complexes [PdBr2(L)] (2), [PdI2(L)] (3), [PtCl2(L)] (4) also have similar structure with complex 1, however, M－P bond lengths become longer in the following order: 1 < 2 < 3. The M－P bond length of complex 4 is similar with that of complex 1. A distinct steric repulsin was observed between the azobenzene moiety and the adjacent coordinating I－ ion in complex 3. The complexes 1-4 have strong absorption bands around 340 nm in chloroform. The absorption intensity at 340 nm decreased by irradiation with UV lights (λex = 340 nm), and the intensity at 450 nm slightly increased in complexes 1, 2, and 4. The reactions were attributed to trans to cis photoisomerization of the azo group from the 1H-NMR spectra. Quantum yields (Φt → c) of the photoisomerization reaction in chloroform changed in the order: 4 > 1 > 2, and no significant photoisomerization behavior was observed in complex 3. We provide further details of the structures and photoisomerization properties. Reference 1 For example, Ichimura, K. Chem. rev. 2000, 100, 1847. 2 Kurihara, M; Nishihara, H. Coord. Chem. rev. 2002, 226, 125.

Fig. 1. An ORTEP drawing of complex 1

N

MP

XX

NN

N

MP

XX

N

N

hν

Δ

X = Cl , Br , I_ _ _

M = Pd(II), Pt(II)Azo-conjugated complexes and the trans-cis isomerization

多様な配位様式を有するヒドラゾン‐Pd(Ⅱ),Ru(Ⅱ)錯体における配位様式の制御 (愛教大化・北大院理)○森麻美・小林厚志・張浩徹・加藤昌子・中島清彦

Control of the coordination mode of hydrazone ligands in Pd(II) and Ru(II) complexes

(1Dept. Chem., Aichi Univ. of Educ.; 2Dept. Chem., Hokkaido Univ.) Asami MORI,1 Atsushi

KOBAYASHI,2 Ho-Chol CHANG,2 Masako KATO,2 Kiyohiko NAKAJIMA1

【緒言】我々は，ヒドラゾン化合物を配位子として導入し

た金属錯体の配位子上のプロトンが可逆的に付加･解離す

ることに着目し，金属イオンの電子状態とプロトンの脱着

との相関から発現する機能に興味を持って研究を行ってい

る。本研究では，多様な配位様式が期待される，ヒドラゾ

ン化合物 (図 1) を配位子としてRu(Ⅱ)および Pd(Ⅱ)錯体を

合成し，その構造を明らかにした。これらの錯体の合成過

程において，反応条件の調整により，

どのように配位様式を制御できる

か，また，可視･紫外光の照射や加

熱，プロトン濃度変化，電位変化等

の外部刺激に対する構造変換につ

いて検討した。【実験】配位子 HL1 と[RuCl2(PPh3)3]の反応について，溶媒

としてエタノールあるいはジクロロメタンを使用し，加熱

条件を変えて反応させると異なる配位様式を有する錯体

1-3 が得られた。また，配位子 HL1 と[PdCl2(cod)]をアセト

ニトリル中で反応させて錯体 4 を得た。【結果と考察】錯体 1-4 の構造を図 2 に示す。錯体 1 およ

び錯体 2におけるHL1の配位様式はどちらも同じであるが，

Ru(Ⅱ)に配位している2つのPPh3が錯体1では互いに trans，錯体 2 では cis である。錯体 1 および錯体 3 では HL1 の配位

様式が異なる。このように，合成条件を変えることで異性

体をそれぞれ合成することに成功した。一方，Pd(Ⅱ)を中心

金属とした錯体 4 では HL1 のヒドラゾンの N 原子上のプロ

トンが解離し，Ru(Ⅱ)錯体とは異なる三座の配位様式をと

っていることが明らかになった。

1PA-05

酸化還元可能な部位を有するヒドラゾン錯体の構造と性質 (愛教大化・北大院理) ○田口祐香理・小林厚志・張浩徹・加藤昌子・中島清彦

Structure and properties of redox active complexes containing hydrazone ligands

(1Aichi University of Education; 2Hokkaido University) Yukari TAGUCHI,1 Atsushi KOBAYASHI,2

Ho-Chol CHANG,2 Masako KATO,2 Kiyohiko NAKAJIMA 1

【緒言】ヒドラゾン化合物は，N 原子上のプロトンが可逆

的に付加・解離することが可能で，この挙動にともなう共

役系の電子状態の変化やフォトクロミズムが報告されてい

る。そこで本研究では，金属イオンの電子状態とプロトン

の付加・解離とが相関する機能の発現を期待して，フェロ

セン部位を有するヒドラゾン化合物，あるいは様々な配位

様式が可能なヒドラゾン化合物（図 1）を配位子に用いて金

属錯体を合成し，その構造と性質について検討した。【実験】配位子 HL1 を

[PtCl2(PhCN)2] ， NiCl2 ・

6H2O，[RuCl2(PPh3)3]とそ

れぞれエタノール中で反

応させ，錯体 1-3 を得た。

配位子 HL2 についても同

様の反応を行い，錯体を

単離した。一方，配位子 HL3 を

[PtCl2(PhCN)2]とエタノール中で反応させると錯体 4 が得ら

れ，この反応を Et3N 存在下で行うと錯体 5 が得られた。錯

体 4, 5 に Et3N を加えて加熱すると，錯体 6 が得られた。

【結果と考察】錯体 1-3 は，溶液中のプロトン濃度を変化

させると，N 原子上のプロトンが可逆に付加・解離する。

また，酸を加えて光を照射した場合，フェロセン部位が解

離したと思われる。錯体 1-3 は，いずれもフェロセン部位

が電気化学的に可逆な酸化・還元応答を示した。錯体 5 の配位子の N 原子上にプロトンを付加すると，S原子上の

tBu 基が連動して解離し，錯体 4 を生成すること

がわかった。

1PA-06

Chromotropy of the Transition Metal Complexes in the Solid and in Solution

Kiyohiko NAKAJIMA

Department of Chemistry, Aichi University of Education, Kariya, Aichi 448-8542, Japan

Much attention has been paid to intelligent molecules which change the structures

and properties in response to external physical and chemical stimuli. For example,

photochromic reactions are of interest and value in relation to the development of

photo-switching devices and photon-mode information storage.

We focused attention on chromotropy of the transition metal complexes in the solid

and in solution. We prepared i) Pd(II) and Pt(II) complexes which have azo-conjugated

ligands, ii) tridentate and tetradentate Schiff base-Ru(II) complexes, iii) triazine or

imidazol coordinated Pd(II) complexes, and iv) hydrazone coordinated Pd(II) and Pt(II)

complexes. In azo-conjugated metal complexes, photo isomerization properties of the

azo moiety can be controlled by altering the electronic state distribution on the ligands

and/or metal ions. The reversible photo and thermal substitution was observed in the

Schiff base-Ru(II) complexes, and the kinetics of the reactions were investigated. In

triazine coordinated Pd(II) complexes, on the other hand, reversible ring-opening and

-closing reactions of the triazine ligands were observed. Hydrazone coordinated Pt(II)

complexes were luminescent, and the luminescence wavelength was controlled by

changing the proton concentration in solution. We provide further details of the

structures and chromotropic properties of the metal complexes.

Photo and Thermal Isomerization of the Azo Moiety of the Ligand in Pd(II) and Pt(II) Complexes Kiyohiko Nakajima, Harada Takashi Department of Chemistry, Aichi University of Education, Kariya, Aichi 448-8542, Japan Considerable interest has been paid to the photo- and thermal- isomerization of orgnic azobenzenes in relation to the development of photo-switching devices and photon-mode information storage.1 In azo-conjugated metal complexes, isomerization properties can be controlled by altering the electronic state distribution on the ligands and/or metal ions.2

We successfully prepared several Pd(II) and Pt(II) complexes ([PdX2(L)], (X = Cl-,

Br-, I

-), [PtCl2(L)], and [PdCl(Me)(L)]) containing an azobenzene-attached ligand (L;

(E)-N-(2-(diphenylphosphino)benzylidene)-4-((E)-phenyldiazenyl)aniline), determined the structures, and studied the photo- and thermal- isomerization properties.

In [PdCl2(L)] (1), the Pd aton is coordinated with a bidentate ligand L and two Cl-

ions, and the azo group has a trans structure. Complexes [PdBr2(L)] (2), [PdI2(L)] (3), [PtCl2(L)] (4) also have similar structure with complex 1, however, M-P bond lengths become longer in the following order: 1 < 2 < 3. The M-P bond length of complex 4 is similar with that of complex 1. A distinct steric repulsin was observed between the

azobenzene moiety and the adjacent coordinating I- ion in complex 3. In

[PdCl(Me)(L)] (5), coordinated P atom of the ligand L and Cl- ion have mutually trans

configuration. The complexes 1-5 have strong absorption bands around 340 nm in chloroform.

The absorption intensity at 340 nm decreased by irradiation with UV lights (ex = 340 nm), and the intensity at 450 nm slightly increased in complexes 1, 2, 4, and 5. The reactions were attributed to trans to cis photoisomerization of the azo group from the 1H-NMR spectra. Quantum yields (→c) of the photoisomerization reaction in chloroform changed in the order: 4 > 1 > 2, and no significant photoisomerization behavior was observed in complex 3. It seems that complex 5 becomes mixtures of cis(P, Cl)-[PdCl(Me)(L)] and trans(P, Cl)-[PdCl(Me)(L)] isomers, which include cis and trans forms for each azo moiety. We provide further details of the structures and photoisomerization properties.

Reference 1 For example, Ichimura, K. Chem. rev. 2000, 100, 1847. 2 Kurihara, M; Nishihara, H. Coord. Chem. rev. 2002, 226, 125.

Pacifichem 2010

ID# 1014 Location: Kamehameha Halls II and III (Convention Center)

Time of Presentation: Dec 18 10:00 AM - 12:00 PM

A. Kobayashi1; M. Dosen1; M. Chang1; S. Noro3; K. Nakajima2; M. Kato1

1. Division of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan. 2. Department of Education, Aichi University of Education, Kariya, Japan. 3. Research Institute for Electronic Science, Hokkaido University, Sapporo, Japan.

The design and synthesis of stable and reversible chemical sensors have received considerable attention in the past decade. Vapochromic materials showing drastic colour change upon exposure to vapours of volatile organic compounds are some of the most promising materials for sensing applications. To develop new sensing materials, we have synthesized several vapochromic Pt(II)-diimine complexes and found that their sensing functionalities are essentially derived from the Pt-Pt interaction.[1] For creation of a new vapochromic system in which the electronic structure can be strongly coupled with the vapochromic behavior, we have newly designed a hydrogen-bonded proton-transfer (HBPT) assembly [PdBr(Hmtbhp)]2(HBA)2(H2BA) comprised of a metal-hydrazone complex [PdBr

(H2BA). In this paper, we demonstrate an interesting vapochromism of this HBPT assembly,

which is derived from the self-assembling rearrangement of the hydrogen bond network

induced by vapor adsorption. In the crystal structure, two proton donor-acceptor (D-A) pairs were bridged by neutral H2BA

molecules to form A-D-D-D-A type hydrogen bond network. Although each molecule formed

segregated columns, the π-π interaction is effective not only in the HBA-

column but also between

the columns of HBA-

and [PdBr(Hmtbhp)]+

. Upon exposure of this HBPT assembly to several organic vapors, vapochromic behavior was observed. The vapochromic shift strongly

depends on the donor and acceptor numbers of the vapor molecules, suggesting that the HBPT

assembly can transform the hydrogen bond network in the solid state in response to the shape

and proton accepting ability of the vapor molecules. Details will be discussed. [Reference]

[1] a) A. Kobayashi et al, Eur. J. Inorg. Chem., 2010, in press. b) A. Kobayashi et al, Dalton Trans., 2010, 39, 3400. b) A. Kobayashi et al, Chem. Lett. 2009, 38, 998.

(mtbhp)] (Hmtbhp = 2-(2-(2-(methylthio)benzylidene) hydrazinyl)pyridine) and bromanilic acid

Vapochromism of a self-assembled hydrogen-bonded proton-transfer complex

Hydrogen bond network of the HBPT assembly

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Pacifichem 2010


Time of Presentation: Dec 18 7:00 PM - 9:00 PM

Photoluminescence properties of mononuclear europium(III) complexes with tetradentate Schiff base ligands: Emission intensity differences which depend on the variation of ligands and counter anions

M. Tsuchimoto1; S. Ebato2; M. Watanabe3; K. Nakajima4

1. Department of Chemistry, Chiba Institute of Technology, Narashino, Chiba, Japan. 2. Department of Life and Environmental Sciences, Chiba Institute of Technology, Narashino, Chiba, Japan. 3. Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Tokai-mura, Ibaraki, Japan. 4. Department of Chemistry, Aichi University of Education, Kariya, Aichi, Japan.

Photoluminescence is one of the distinctive properties of europium(III) complexes, and a large number of europium(III) complexes have been prepared and investigated extensively in relation to the development of emissive materials. Recently, we found out highly photoluminescent mononuclear europium(III) complexes with tetradentate Schiff base ligands, (C2H5)3NH[Eu

(3,5Clsalen)2] (H23,5Clsalen: N,N’-bis-3,5-dichlorosalicylidene-1,2-ethanediamine). The complex

shows red luminescence based on f-f transitions by irradiation with UV light in solutions and in the

solid state. In this study, we report photoluminescence properties of mononuclear europium(III) complexes with various salen-type Schiff base ligands X[Eu(L)2] (X=

(C2H5)3NH+ or (C2H5)4N+, L = salen-type Schiff base ligand dianion). The pale yellow

to the oxygen atom of the complex anion in (C2H5)3NH[Eu(L)2]. On the other hand, no definite

interaction between the complex anion and the tetraethyl ammonium cation was observed in (C2H5)4N[Eu(L)2]. All the complexes display emission bands based on f-f transitions by

excitation at 360 or 235 nm in acetonitrile. However, the intensities of the emission bands are considerably different between the mononuclear europium(III) complexes. We discuss on the emission intensitiy difference which was caused by changing the framework of diamine moieties, substituents on the salicylaldehyde moieties, and the type of counter cations.

Structure of (C2

H5

)3

NH[Eu(3,5Clsalen)2

]

europium(III) complexes were prepared by the reaction of europium(III) acetate with each Schiff base ligand (H2L) in methanol. The structures of the complexes were determined by X-ray crystal

structure analysis. The complexes have an eight-coordinate mononuclear structure with two Schiff base ligands in a meridional form. The triethylammonium cation is hydrogen bonded



Pacifichem 2010


Time of Presentation: Dec 18 7:00 PM - 9:00 PM

Photoreactions and luminescence properties of the metal complexes related to protonation and deprotonation behavior of the hydrazone ligands

K. Nakajima1; D. Yamada1; Y. Taguchi1; H. Horiki2; A. Kobayashi2; H. Chang2; M. Kato2

1. Department of Chemistry, Aichi University of Education, Kariya, Aichi, Japan. 2. Division of Chemistry, Faculty and Graduate School of Science, Hokkaido University, Sapporo, Japan.

The Pt(II) complexes of yellow [PtX(HL)]+ and red [PtX(L)] (X = Cl-, Br-, I-, HL and L-; protonated and deprotonated tridentate hydrazone ligands) were photoluminescent in solutions, and their emission peaks were distinct to each other. Large red shifts of the absorption and emission bands of [PtX(HL)]+ were observed in acetonitrile at room temperature when a drop of triethylamine was added. Absorption spectral changes of [PtCl(L)] were observed in dichloromethane during an irradiation of lights. We could obtain the reaction product, and assigned the structure on the basis of the MS spectra and an X-ray structure determination. We also obtained the Ru(II) complexes with hydrazone ligands, [RuCl2(PPh3)(HL)], and the

structures were determined by an X-ray method. The reversible redox reactions (Ru(II) ↔ Ru (III)) were observed by CV measurements. The dichloromethane solution of [RuCl2(PPh3)(HL)]

underwent a change in color from orange to brown upon addition of triethylamine. It seems that

the generated complex anion of [RuCl2(PPh3)(L)]- is susceptible to oxidation.

Hydrazones are extensively used for the identification of carbonylic compounds, and also used as plasticizing agents, polymerization initiators, etc. On the other hand, a certain type of hydrazones can act as a ligand to form metal complexes, which are of interest in the field of homogeneous catalysis and bioinorganic chemistry, and so on. Therefore, a considerable interest has been paied to the metal complexes containing such functional hydrazone ligands. We successfully prepared several transition metal complexes containing tridentate hydrazone ligands. All the complexes exhibited distinct color changes by an addition of trifuluoromethanesulfonic acid or triethylamine. The color changes arise from different electronic state distributions on the ligands and/or metal ions caused by the reversible protonation and deprotonation of hydrazone ligands.



イオウ原子を有するヒドラゾン化合物が

配位した錯体の構造と配位イオウ原子上

のアルキル基の解離反応

（愛教大化・北大院理）田口祐香理・○山下祐理香・小林厚志・張浩徹・加藤昌子・中島清彦 Structures of Transition-metal Complexes with Hydrazone Ligands Containing Sulfur Donor

Atom, and the Dissociation Reactivity of the Alkyl Group Attached to the Coordinated Sulfur

Atom(Aichi University of Education, Hokkaido University) Yukari TAGUCHI; ○Yurika

YAMASHITA; Atsushi KOBAYASHI; Ho-Chol CHANG; Masako KATO; Kiyohiko

NAKAJIMA

Abstract：Transition-metal complexes with hydrazone ligands containing sulfur donor atoms

were prepared, and the dissociation reactivity of the alkyl group attached to the coordinated sulfur

atom was investigated. The reactivity depends on the type of metals. We also studied the structure

and reactivity of metal complexes with hydrazone ligands containing ferrocene moiety.

Keywords：Hydrazone; Protonation and Deprotonation; Redox; Metal Complex

【実験】図１に示す配位子 HL

1 を[PdCl2(PhCN)2]，CuCl2・H2O とエタノール中で反応させ，それぞれ錯体 1，2を合成した。また，同様の反応をトリエチルアミンを加えて行い，それぞれ錯体 3，4 を合成した。配位子 HL

2についても[PdCl2(PhCN)2]，CuCl2・H2O

とエタノール中で反応させ，それぞれ錯体 5，6 を合成した。錯体 1 および 3，4 の構造はＸ線結晶構造解析により決定した。【結果と考察】配位子 HL

1のパラジウム錯体の場合，プロトン付加体である錯体 1 はtBu 基が解離し，プロトン解離体である錯体 3は t

Bu 基が解離していなかった。それに対して，銅錯体では，プロトン付加体，解離体のどちらの場合でも，t

Bu 基の解離は見られなかった。錯体 5，6の構造については，当日報告する。

【序】配位可能なイオウ原子上に tBu 基を持つ化合物は，金属に配位

するとイオウ原子上の tBu 基が解離する例が報告されている。これは，

金属に配位すると，イオウ原子の電子状態が変化するために起こると考えられる。また，ヒドラゾン化合物は，酸や塩基を添加すると，窒素原子上のプロトンが可逆的に付加・解離する。以上のことから，配位イオウ原子上にアルキル基を有するヒドラゾン配位子を用いた金属錯体では，ヒドラゾン配位子の窒素原子上のプロトンの付加・解離によって錯体の電子状態を変化させて，イオウ原子上の t

Bu 基の解離を制御できると考えられる。本研究では，図 1 に示す配位子 HL

1を用いた金属錯体において，ヒドラゾンの窒素原子上のプロトンの付加に連動してイオウ原子上の t

Bu 基が解離する系を見出した。この反応は中心金属イオンの種類によりまったく異なる。また，ヒドラゾン配位子上にフェロセン部位を有する錯体を合成し，フェロセン部位の酸化還元にともなう t

Bu 基の解離についても検討した。

N

S

N

O

tBu

H

N

S

N

O

tBu

Pd

Cl

N

S

N

O

H

Pd

Cl

N

S

N

O

H

Cu

Cl

tBu

N

S

N

O

tBu

Cu

Cl

N

S

tBu

N

O

FcH

HL1

HL2

図 1

錯体 1 錯体 4 錯体 3 錯体 2 図 2

1 PB-125

ヒドラゾン化合物が配位した Pd(II)錯体

における多様な配位様式と配位子上の

置換基の立体効果

（愛教大化・北大院理）○北村双美・森麻美・藤澤佐知恵・小林厚志・張浩徹・加藤昌子・中島清彦

Preparation and Structure of Pd(II) Complexes with Hydrazone Ligands -Steric Effects of the

Substituent on the Ligand for Coordination Modes（Dept. Chem., Aichi Univ. of Edu.）○KITAMURA, Fumi; MORI, Asami; FUJISAWA, Sachie; KOBAYASHI, Atsushi; CHANG,

Ho-chol; KATO, Masako; NAKAJIMA, Kiyohiko

Abstract：Pd(II) complexes containing tridentate hydrazone ligands with N and O donor atoms

were prepared, and the structures were determined by an X-ray method. The complexes have a

variety of coordination modes. We investigated the conversion of the coordination modes, which

was sensitive to the proton concentration in the solvent and also the bulkiness of substituents on

the ligands.

Keywords：Hydrazone; Coordination Mode; Steric Effect; Proton Concentration; Pd Complex

【緒言】ヒドラゾン配位子を用いた錯体は酸・塩基を加えると N

原子上のプロトンの付加・解離が起こる。本研究では図 1 に示す配位可能な部位を複数有するヒドラゾン化合物 mpapH、papH を配位子に用いて Pd(II)錯体を合成し、ヒドラゾン化合物の多様な配位様式を見出した。これらの Pd(II)錯体の配位様式が、溶液中のプロトン濃度変化や時間経過、また配位子上の置換基のかさ高さによりどのように影響されるか検討した。【実験】[Pd(cod)Cl2]と mpapHをアセトニトリル中で反応させると、錯体 1 が得られた。トリエチルアミン存在下において同様の反応を行うと、錯体 2 が得られた。一方、[Pd(cod)Cl2]と papH をアセトニトリル中で反応させると、錯体 3 が得られ、さらに 2 日間反応溶液中に静置すると錯体 4 を得ることができた。また、トリエチルアミン存在下において同様の反応を行うと、錯体 5が得られた。【結果と考察】X線構造解析により、錯体 1-3は図 2に示す構造であることを明らかにした。錯体 1では mpapHが、アミド基の N原子とピリジン環の N 原子の二座で配位していた。一方、錯体 3では papH のピリジン環の N原子とイミノ基の N原子で Pdに配位していた。錯体 1 はピリジン環上のメチル基と Pd に配位した Cl

-との間の立体障害により、6-メチルピリジン側での配位が困難であるものと考えられる。また、吸収スペクトルの測定から錯体 1 をアセトニトリルに溶かして 1 日静置すると、錯体 2 に変化することがわかった。錯体 3-5 は互いに異なる構造を持つことが示唆され、mpapH を配位子に用いた錯体と吸収スペクトル等を比較して錯体 4および 5の構造を帰属した。

図 2

N N

O

NH N

Pd

Cl Cl

N

N

N

O

Me

NPd

Cl

錯体 1 錯体 3 錯体 2

N(H) N

O

N(H) N

Me Pd

Cl Cl

N N

O

NH N

Me

N N

O

NH N

mpapH

papH

図 1

1 PB-126

四座のシッフ塩基を配位子とする

Eu(III)単核錯体の PMMA 中の発光特性

（千葉工大・日本原子力研究開発機構・愛教大化）○外口良平・中塩屋貴寛・槌本昌信・寺本直純・柴田充弘・渡邉雅之・中島清彦 Photoluminescence properties of mononuclear europium(III) complexes with tetradentate Schiff

base ligands in PMMA（Chiba Inst. of Tech.; Nucl. Sci and Eng., JAEA; Aichi Univ. of Edu.）

○SOTOGUCHI, Ryouhei; NAKASHIOYA, Takahiro; TSUCHIMOTO, Masanobu;

TERAMOTO, Naozumi; SHIBATA, Mitsuhiro; WATANABE, Masayuki; NAKAJIMA,

Kiyohiko

Abstract：Photoluminescence studies of mononuclear europium(III) complex with tetradentate

Schiff base ligands in PMMA films were investigated. The complex displays a strong emission

band at 614 nm by excitation at 365 nm in PMMA.

Keywords：Europium Complex; Schiff Base; Poly(methyl methacrylate); Photoluminescence

[目的] ランタニド錯体には紫外線を照射するとf-f 遷移に基づく発光を示すものがあ

り、発光材料として研究が盛んに行われている。近年、我々は四座のsalen タイプのシッ

フ塩基を配位子とするEu(III)単核錯体、(C2H5)3NH[Eu(3,5Clsalen)2]を合成し、その構造と

発光特性について調べた。この単核錯体はEu 原子に2 個のシッフ塩基配位子がmeridional

型に配位した8 配位の構造をとる（図１）。また、この錯体に360 nm 付近の紫外線を照

射すると、固体中、溶液中でf-f 遷移に基づく強い赤色の発光を示す。本研究では、キャ

スト法により、このEu(III)単核錯体を含むPMMAフィルムを作成し、その発光特性につい

て検討を行った。

[結果] Eu(III)錯体とPMMAをジクロロメタンに溶解し、キャスト法により、錯体濃度

0.5－10 mmol/kg、厚さ0.3 mm の透明のPMMAフィルムを作成した。そして発光スペクト

ルの測定を行ったところ、この錯体はPMMA中において、溶液中や固体中と同様に、

614 nm に5D0→7F2 の遷移に基づく強い発光バンドを示すことが明らかになった（図1)。

そして、錯体の濃度の増加とともに発光強度が増加し、5 mmol/kg 以上ではほぼ一定の発

光強度となった。また、濃度の増加とともに励起スペクトルの形状も変化することが明

らかとなった。

1 PB-169

配位可能な部位を複数有するヒドラゾン

－Ru(II)錯体の合成と配位様式の変換

（愛教大化・北大院理）○森麻美・小林厚志・張浩徹・加藤昌子・中島清彦

Preparation, Structure, and the Conversion of Ligand Coordination Modes in Ru(II) Complexes

with Hydrazone Ligands（Dept. Chem., Aichi Univ. of Edu., Dept. Chem., Hokkaido Univ.）○MORI, Asami; KOBAYASHI, Atsushi; CHANG, Ho-chol; KATO, Masako; NAKAJIMA,

Kiyohiko

Abstract：We prepared several Ru(II) complexes with hydrazone ligands with N and O donor

atoms, and determined the structures by an X-ray method. The complexes have a variety of

coordination modes. The stability and the conversion of coordination modes were investigated.

Keywords：Hydrazone; Coordination Mode; Ru complex; Synthesis

【序】プロトン濃度変化や中心金属の酸化還元などの外部刺激に対して配位様式が変化する金属錯体は、基礎と応用の両面から興味が持たれ、様々な分野において研究が行われている。我々はこれまでに、配位子にヒドラゾン化合物を導入した各種金属錯体について精力的に研究を行ってきた。配位子に導入されたヒドラゾン化合物は溶液中において、プロトン濃度変化に連動した可逆的なプロトンの付加・解離挙動を示すことから、電子状態を容易にスイッチングすることが可能である。そこで、本研究では N,O など配位可能な部位を複数有する、Scheme 1 に示すヒドラゾン化合物を配位子に用いて Ru(II)

錯体を合成し、配位様式の制御および変換について検討した。【実験】配位子 HL

1と[RuCl2(PPh3)3]を極性の異なる溶媒中で加熱条件を変えて反応させ、錯体 1-3を得た。(Scheme 1) 【結果と考察】構造解析の結果、錯体 1-3は Figure 1 に示す構造であることを明らかにした。溶媒にエタノールを用いた場合とジクロロエタンを用いた場合では、Ru(II)に配位する HL

1の配位様式が異なり、また、加熱条件が異なると Ru(II)に配位した 2 つの PPh3の立体配置が異なる錯体が得られた。このように、溶媒の極性や熱力学的安定性がこれらの異なる配位様式の錯体を発現させたものと考えられる。

Figure 1

Scheme 1

HL1

N

H

NN

N

O

Complex 2

Complex 3

Complex 1

[RuCl2(PPh3)3], 1,2-dichloroethane

80℃, 9h

[RuCl2(PPh3)3], ethanol

rt, 9h

[RuCl2(PPh3)3], ethanol

80℃, 3h

NN

HN

ON Ru

Cl

Cl

PPh3

PPh3

NN

HN

ON Ru

PPh3

Cl

Cl

PPh3

N

HN

N

N

O

Ru

Cl

Cl

PPh3

PPh3

Complex 2 Complex 3 Complex 1

3 A5-16

光照射・電位変化等の連続した環境変化に対し，繰り返し応 …p3 photo and...

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