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Kazuya KuboResearch Institute for Electronic Science, Hokkaido UniversityResearch Institute for Electronic Science, Hokkaido University
3rd International Conference and Exhibition on Materials Science & Engineering
San Antonio, USA
6 October 2014
Chapter 1Chapter 1Chapter 1Chapter 1Motivation of development of multifunctional materials based on [MnIICrIII(oxalate)3]-complexes including supramolecular cations
Hybridized complexes including the supramolecular cations and [MnIICrIII(oxalate)3]- complex
• (3-fluoro-4-methoxyanilinium+)([18]crown-6)[MnIICrIII(oxalate)3]- (acetone) (1)
• (anilinium+)(benzo[18]crown)[MnIICrIII(oxalate)3]- (2)
• (m-fluoroanilinium+)(dicyclohexano[18]crown-6) [MnIICrIII(oxalate)3]- (3)
Chapter 2Chapter 2Chapter 2Chapter 22222----1.1.1.1. Synthesis of (anilinium)(benzo[18]crown-6) [MnIICrIII(oxalate)3]- (2222)2222----2. 2. 2. 2. Crystal structure of 22222222----3.3.3.3. Magnetic susceptibility of 22222222----4444. Solid state 2H-NMR of 22222222----5. 5. 5. 5. Potential energy calculation for molecular motions in 22222222----6. 6. 6. 6. Dielectric property of 2222
Chapter 3Chapter 3Chapter 3Chapter 3Summary and future plans
Chapter 1Chapter 1Chapter 1Chapter 1Motivation ofMotivation ofMotivation ofMotivation of development of multifunctional materials development of multifunctional materials development of multifunctional materials development of multifunctional materials
based on [based on [based on [based on [MnMnMnMn CrCrCrCr (oxalate)(oxalate)(oxalate)(oxalate) ]]]] complexes complexes complexes complexes including including including including Motivation ofMotivation ofMotivation ofMotivation of development of multifunctional materials development of multifunctional materials development of multifunctional materials development of multifunctional materials
based on [based on [based on [based on [MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]---- complexes complexes complexes complexes including including including including supramolecularsupramolecularsupramolecularsupramolecular cationscationscationscations
Introduction: Introduction: Introduction: Introduction: FerroelectricityFerroelectricityFerroelectricityFerroelectricity based on the based on the based on the based on the supramolecularsupramolecularsupramolecularsupramolecular cationcationcationcation(m-fluoroanilinium)(dibenzo[18]crown-6)[Ni(dmit)2]
[Ni(dmit)2]- S
SS
Ni
S
S
S
S
S
S
S
(m-fluoroanilinium+)(dibenzo[18]crown-6)
E
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
P /
μμ μμC
cm
-2
-4 -2 0 2 4
E / kV cm-1
[Ni(dmit)2]-(m-fluoroanilinium+)(dibenzo[18]crown-6)
FerroelectricityFerroelectricityFerroelectricityFerroelectricity
T. Akutagawa et al. Nature Materials., 2009 8888, 342
Weak antiferromagnetic interaction between S = ½
spins on the anion
Advantage of the supramolecular cationsVarious salts of the cation including functional anions can be obtained.
Tc = 345 K
Strategy: Strategy: Strategy: Strategy: Combinations of the Combinations of the Combinations of the Combinations of the SupramolecularSupramolecularSupramolecularSupramolecular cationscationscationscations and and and and ferromagnetsferromagnetsferromagnetsferromagnets
Coexistence?Coexistence?Coexistence?Coexistence?
[MnIICrIII(ox)3]ferromagnetferromagnetferromagnetferromagnet
SupramolecularSupramolecularSupramolecularSupramolecularcationcationcationcation
ferroelectricityferroelectricityferroelectricityferroelectricity
o-fluoroanilinium m-fluoroanilinium H2PPD2+cis-syn-cis-DCH[18]Crown-6 Trans-syn-trans-DCH[18]Crown-6
benzo[18]Crown-6 dibenzo[18]Crown-6
This work: Three crystals were synthesized.This work: Three crystals were synthesized.This work: Three crystals were synthesized.This work: Three crystals were synthesized.• (3-fluoro-4-methoxyanilinium+)([18]crown-6)[MnIICrIII(oxalate)3]
- (acetone) (1)
• (anilinium+)(benzo[18]crown)[MnIICrIII(oxalate)3]- (2)
• (m-fluoroanilinium+)(dicyclohexano[18]crown-6)[MnIICrIII(oxalate)3]- (3)
Crystal 1 Crystal 3Crystal 2
Space group: Cc
Magnetic behavior:
Ferromagnetic
Dielectric response:
Not observed(Chem. Lett. 2013, 42, 137)
Space group: P21Magnetic behavior:
Ferromagnetic
Dielectric response:
Observed
Space group: P212121Magnetic behavior:
Ferromagnetic
Dielectric response:
Not observed
Chapter 2Chapter 2Chapter 2Chapter 22222----1111.... Synthesis of (anilinium)(benzo[18]crown-6)[MnIICrIII(oxalate)3]- (2222)2222----2. 2. 2. 2. Crystal structure of 22222222----3.3.3.3. Magnetic susceptibility of 22222222----4444. Solid state H-NMR of 22222222----4444. Solid state 2H-NMR of 22222222----5. 5. 5. 5. Potential energy calculation for molecular motions in 22222222----6. 6. 6. 6. Dielectric property of 2222
2222----1. Preparation of1. Preparation of1. Preparation of1. Preparation of ((((aniliniumaniliniumaniliniumanilinium)()()()(benzobenzobenzobenzo[18]crown[18]crown[18]crown[18]crown----6) [6) [6) [6) [MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]---- (1)(1)(1)(1)
Precursors of Supramolecles
Precursors of [MnIICrIII(oxalate)]-
Supramolecles
ConditionsConditionsConditionsConditionsDiffusion method; Temperature: 25 ºC; Period: 1 week; solvents: CH3OH and CH3CN mixtures
Confirmation of the formulaConfirmation of the formulaConfirmation of the formulaConfirmation of the formula: X-ray crystallographic, elemental, and Thirmogramometric analyses
2222----2. Crystal structure of 2. Crystal structure of 2. Crystal structure of 2. Crystal structure of ((((aniliniumaniliniumaniliniumanilinium)()()()(benzobenzobenzobenzo[18]crown[18]crown[18]crown[18]crown----6666)[)[)[)[MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]----
The two dimensional honeycomb structureDiameter of the ring ca. 10 ÅDistance between the layers ca. 11 Å
Crystal data of 2222Monoclinic; P21 (#4); a = 8.7986(8) Å; b = 23.315(3) Å; c = 9.4749(13) Å; β = 115.483(3)°;V = 1754.6(3) Å3;T = -100 °C; R1 = 0.0725; Rw = 0.1706
Distance between the layers ca. 11 Å
Hydrogen bonds between N and O atoms: 2.782-2.957 ÅFormation of the supramolecularcation
Magnetic susceptibility of Magnetic susceptibility of Magnetic susceptibility of Magnetic susceptibility of ((((aniliniumaniliniumaniliniumanilinium)()()()(benzobenzobenzobenzo[18]crown[18]crown[18]crown[18]crown----6) [6) [6) [6) [MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]---- (2)(2)(2)(2)120
100
80
60
40
20
0
χm
T /
em
u K
mo
l-1
30025020015010050
60
50
40
30
20
10
0
1 / χ
m
Ferromagnetic transition at 5.0 K
(1) Crystal 2222 exhibits ferromagnetic behavior.(2) Crystal 2222 is a good candidate of a multifunctional material with coexistence of a ferromagnetism and a ferroelectricity.
T / K
Solid state Solid state Solid state Solid state 2222HHHH----NMR of (aniliniumNMR of (aniliniumNMR of (aniliniumNMR of (anilinium----d5d5d5d5)()()()(benzobenzobenzobenzo[18]crown[18]crown[18]crown[18]crown----6) [6) [6) [6) [MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]---- (2)(2)(2)(2)
Anilinium-d5
Nuclear spin of 2H: I = 1electrical field gradient of anilinium-d5: C-D direction
Previous work
2H-NMR of (anilinium-d5)([18]crown-6) [Ni(dmit)2]-S. Nishihara et al., Chem. Asian J. 2007200720072007, 2, 1083
170 K185 K200 K215 K230 K245 K293 K large
flip-flop motion
small
CCCC
DDDD
S. Nishihara et al., Chem. Asian J. 2007200720072007, 2, 1083
Weak flipWeak flipWeak flipWeak flip----flop motionflop motionflop motionflop motionlarge fliplarge fliplarge fliplarge flip----flop motionflop motionflop motionflop motion
Another peak is Another peak is Another peak is Another peak is observed. observed. observed. observed. Another Another Another Another
molecular molecular molecular molecular motion ?motion ?motion ?motion ?
Potential energy calculations of (Potential energy calculations of (Potential energy calculations of (Potential energy calculations of (aniliniumaniliniumaniliniumanilinium)()()()(benzobenzobenzobenzo[18]crown[18]crown[18]crown[18]crown----6) 6) 6) 6) [[[[MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]---- (2)(2)(2)(2)
300
250
200
150
100
50
0
∆E
/ k
J m
ol-1
3002001000
flip-flop motion
3002001000
φ / degreecf. Energy barrier for the flip-flop motion in the ferroelectric salt, (m-fluoroanilinium)(dibenzo[18]crown-6)(Ni(dmit)2): ca. 250 kJ mol-1
Pendulum motions
motion A motion B
Small energy barrier for the pendulum motion B
Temperature and field dependence dielectric constants of Temperature and field dependence dielectric constants of Temperature and field dependence dielectric constants of Temperature and field dependence dielectric constants of ((((aniliniumaniliniumaniliniumanilinium)()()()(benzobenzobenzobenzo[18]crown[18]crown[18]crown[18]crown----6) [6) [6) [6) [MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]---- (2)(2)(2)(2)
800
600
ε 1
100 Hz
320 Hz
1 kHZ
3.2 kHz
10 kHz
32 kHz
100 kHz
The flip-flop motion of anilinium+ dose not cause an inversion of the dipole-moment.These large dielectric
400
200
400380360340320300
T / K
100 kHz
320 kHz
1 MHz
These large dielectric responses would correspond to the pendulum motions.
Development of multifunctional materials based on the MOF system with the supramolecular cations.····(organic ammonium)([18]crown-6 derivative)[MnCr(oxalate)3] were synthesized.···· Salt 2 exhibits a ferromagnetic transition at 5.0 K.· · · · Dielectric responses were observed due to the pendulum motion of anilinium in the solid state of 2222.· · · · Crystal 2 is a model compound for the molecular multifunctional materials.Crystal 2 is a model compound for the molecular multifunctional materials.Crystal 2 is a model compound for the molecular multifunctional materials.Crystal 2 is a model compound for the molecular multifunctional materials.
Future Plan(anilinium)(bebzo[18]crown-6)[MnCr(oxalate)3] (2222)
A good candidate for the multifunctional materials with coexistence of ferromagnetism and ferroelectricity such as multiferroic materials.
Future plans: ·Development of the multifunctional materials such as multiferroiccompounds based on the molecular system.
Professor Takayoshi Nakamura (Hokkaido University)Professor Tomoyuki Akutagawa (Tohoku University)Professor Shin-ichiro Noro (Hokkaido University)Professor Sadamu Takeda (Hokkaido University)Dr. Toru Endo (Chisso Cooperation, Hokkaido University)Mr. Masashi Yoshitake (Hokkaido University)Mr. Masashi Yoshitake (Hokkaido University)Professor Kunio Awaga (Nagoya University)Dr. Hirofumi Yoshikawa (Nagoya University)Professor Jun Kawamata (Yamaguchi University)Professor Sadafumi Nishihara (Hiroshima University)Dr. Yasutaka Suzuki (Yamaguchi University)Dr. Ryo Tsunashima (Yamaguchi University)
Crystal structure of Crystal structure of Crystal structure of Crystal structure of (3(3(3(3----fluorofluorofluorofluoro----4444----methoxymethoxymethoxymethoxy----anilinium)([18]crownanilinium)([18]crownanilinium)([18]crownanilinium)([18]crown----6) [6) [6) [6) [MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]----(CH(CH(CH(CH3333OH)OH)OH)OH)2222 (1)(1)(1)(1)
The two dimensional honeycomb structureHydrogen bonds between N and O atomsFormation of the supramolecular cation
Shortest N···O distance of 2.810 ÅA mean plane of the six oxygen atoms of the crown ether was close to right angle (89.32°)
Crystal data of 1111Monoclinic; Space group, Cc; a = 16.1878(10) Å; b = 9.4716(5) Å; c = 22.6967(13) Å; b = 97.847(2)°; V = 3447.4(3) Å3; Z = 4.
The two dimensional honeycomb structureDiameter of the ring ca. 10 ÅDistance between the layers ca. 13 Å
·Space group without inversion center·No disorder of F and MeO groups
Magnetic susceptibility of Magnetic susceptibility of Magnetic susceptibility of Magnetic susceptibility of (3(3(3(3----fluorofluorofluorofluoro----4444----methoxymethoxymethoxymethoxy----anilinium)([18]crownanilinium)([18]crownanilinium)([18]crownanilinium)([18]crown----6) 6) 6) 6) [[[[MnMnMnMnIIIIIIIICrCrCrCrIIIIIIIIIIII(oxalate)(oxalate)(oxalate)(oxalate)3333]]]]---- (CH(CH(CH(CH3333OH)OH)OH)OH)2222 (1)(1)(1)(1)
Ferromagnetic transition at 5.5 K
(1) Crystal 1111 exhibits ferromagnetic behavior.(2) Salt 1111 is a good candidate of a multifunctional material with coexistence of a ferromagnetism and a ferroelectricity.
Crystal structure of Crystal structure of Crystal structure of Crystal structure of ((((mmmm----fluoroaniliniumfluoroaniliniumfluoroaniliniumfluoroanilinium)()()()(transtranstranstrans----synsynsynsyn----transtranstranstrans----DCH[18]crownDCH[18]crownDCH[18]crownDCH[18]crown----6)[6)[6)[6)[MnCrMnCrMnCrMnCr(oxalate)(oxalate)(oxalate)(oxalate)3333] at 25 ºC ] at 25 ºC ] at 25 ºC ] at 25 ºC
Crystal data of orthorhombicP212121a = 9.1025(5)Åb = 25.0202(12) Åc = 33.5384(15) ÅV = 7638.2(7) Å3
T = 25 °C
Two dimensional honeycomb structureFerromagnetic behaviour
Two dimensional honeycomb structure including the supramolecular cations
No solvent molecule in the salt
Pores of the anion layers are filled with cyclohexane moieties of the crown ethers
Air stable compound
Molecular arrangements of Molecular arrangements of Molecular arrangements of Molecular arrangements of ssssupramolecularupramolecularupramolecularupramolecular cationscationscationscations of (of (of (of (mmmm----fluoroaniliniumfluoroaniliniumfluoroaniliniumfluoroanilinium)()()()(transtranstranstrans----synsynsynsyn----transtranstranstrans----DCH[18]crownDCH[18]crownDCH[18]crownDCH[18]crown----6)[6)[6)[6)[MnCrMnCrMnCrMnCr(oxalate)(oxalate)(oxalate)(oxalate)3333] ] ] ]
Column A Column BC-F:1.273 Å C-F:1.043 Å C-F:1.335 Å
cColumn A Column B
Two crystallographically independent supramolecular cations in this crystal
Disordered fluorine atoms on the cations
Flat conformationsThis complex is a good candidate for This complex is a good candidate for This complex is a good candidate for This complex is a good candidate for the multifunctional material coexisting a the multifunctional material coexisting a the multifunctional material coexisting a the multifunctional material coexisting a ferromagnetism and a ferromagnetism and a ferromagnetism and a ferromagnetism and a ferroelectricityferroelectricityferroelectricityferroelectricity....
Debatable points(1) The C-F Bond lengths in column A are
shorter than the typical bond length.(2) The cyclohexane moieties in column A
are not trans-syn-trans conformation.
Highly steric hindrances
Magnetic susceptibility Magnetic susceptibility Magnetic susceptibility Magnetic susceptibility of the saltof the saltof the saltof the saltinflection point
Ferromagnetic transition at 5.5 KFerromagnetic transition at 5.5 K
(1) The exhibits a ferromagnetic behavior.(2) Ferromagnetic transition at 5.5 K(3) Saturated magnetization of the salt is about 8 µB.(4) In 1/χ vs. T plot, inflection point was observed at 110 K. →Interaction between the supramoleculer
cation and the oxalete complex?
Organic ammonium and crown ether derivatives
Anilinium derivatives
[18]crown-6 derivatives
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