OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group...

24
* About OMICS Group About OMICS Group About OMICS Group About OMICS Group About OMICS Group About OMICS Group About OMICS Group About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international science conferences and events. Established in the year 2007 with the sole aim of making the information on Sciences and technology ‘Open Access’, OMICS Group publishes 400 online open access scholarly journals in all aspects of Science, Engineering, Management and Technology journals. OMICS Group has been instrumental in taking the journals. OMICS Group has been instrumental in taking the knowledge on Science & technology to the doorsteps of ordinary men and women. Research Scholars, Students, Libraries, Educational Institutions, Research centers and the industry are main stakeholders that benefitted greatly from this knowledge dissemination. OMICS Group also organizes 300 International conferences annually across the globe, where knowledge transfer takes place through debates, round table discussions, poster presentations, workshops, symposia and exhibitions.

Transcript of OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group...

Page 1: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

**About OMICS GroupAbout OMICS GroupAbout OMICS GroupAbout OMICS GroupAbout OMICS GroupAbout OMICS GroupAbout OMICS GroupAbout OMICS Group

OMICS Group International is an amalgamation of Open Accesspublications and worldwide international science conferences andevents. Established in the year 2007 with the sole aim of making theinformation on Sciences and technology ‘Open Access’, OMICSGroup publishes 400 online open access scholarly journals in allaspects of Science, Engineering, Management and Technologyjournals. OMICS Group has been instrumental in taking thejournals. OMICS Group has been instrumental in taking theknowledge on Science & technology to the doorsteps of ordinarymen and women. Research Scholars, Students, Libraries,Educational Institutions, Research centers and the industry are mainstakeholders that benefitted greatly from this knowledgedissemination. OMICS Group also organizes 300 Internationalconferences annually across the globe, where knowledge transfertakes place through debates, round table discussions, posterpresentations, workshops, symposia and exhibitions.

Page 2: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

**About OMICS Group ConferencesAbout OMICS Group ConferencesAbout OMICS Group ConferencesAbout OMICS Group ConferencesAbout OMICS Group ConferencesAbout OMICS Group ConferencesAbout OMICS Group ConferencesAbout OMICS Group Conferences

OMICS Group International is a pioneer and leading science

event organizer, which publishes around 400 open access

journals and conducts over 300 Medical, Clinical, Engineering,

Life Sciences, Phrama scientific conferences all over the globe

annually with the support of more than 1000 scientific

associations and 30,000 editorial board members and 3.5 millionassociations and 30,000 editorial board members and 3.5 million

followers to its credit.

OMICS Group has organized 500 conferences, workshops and

national symposiums across the major cities including San

Francisco, Las Vegas, San Antonio, Omaha, Orlando, Raleigh,

Santa Clara, Chicago, Philadelphia, Baltimore, United Kingdom,

Valencia, Dubai, Beijing, Hyderabad, Bengaluru and Mumbai.

Page 3: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 4: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 5: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 6: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 7: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 8: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 9: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 10: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 11: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 12: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 13: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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 ?

Page 14: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 15: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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.

Page 16: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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.

Page 17: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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)

Page 18: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 19: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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.

Page 20: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 21: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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

Page 22: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

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?

Page 23: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

Organic ammonium and crown ether derivatives

Anilinium derivatives

[18]crown-6 derivatives

Page 24: OMICS Group International is an amalgamation of Open Access · **About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international

*Let Us Meet AgainLet Us Meet AgainLet Us Meet AgainLet Us Meet Again

We welcome you all to our future conferences of OMICS Group We welcome you all to our future conferences of OMICS Group International International

Please Visit:Please Visit:Please Visit:Please Visit:

httphttp://materialsscience.conferenceseries.com://materialsscience.conferenceseries.com//

Contact Contact us atus at

materialsscience.conference@[email protected]

[email protected]@omicsgroup.com