10 Functional molecules and hybridized materials

1. -2005272-842. 200569-1052.2008

20 -/

10.1 10.1.1 02060Mc Conell2080

2p -

- - TCNQFe(Cp*)2Ni(dmid)2-CH3CNdmidS3C3O1,3--4,5--2-2 -D+A-D+A-

A-X-BABSASB1/2XXABS=0S1.JE(S0)-E(S1)J < 0J > 0 -

2(Cat)2Mn2[Cu(opba)]2opbaCu(II)(S=1/2)Mn(II)(S=5/2)TC22.5K RISFe(Cp)2Ni(dmid)2-CH3CN(A)(D+)- A-D+ D+A- D+D+A--100001[Ni(S4C3O)2]6011100J5.5cm1JDASS

CsNi[Cr(CN)6]2H2OCrt2gNiegTc90K[Fe(Cp)2]2[Fe(mnt)2]2Fe(mnt)22Fe(Cp*)2Fe(Cp*)2ac0.8382nm 1991CHONNONsp2C

10.1.2 9.1.2.1 - 1. TEMPONIT R

1Tc0.38K2Tc0.65K3Tc1.48K 1972Veyret1TANOLTN0.38K 19912NITPNKonoshitaTN0.65K 1993Chiarelli3TDDTc1.48KTc

Ovchinnikov Ovchinnikov TC-NITPN4TC

2. - Lewis2080-[Mn(hafc)2-NITR] M:R1:11:2Cu()Ni()Co()Mn()RE()REEuGdDy--4f-Ni()Mn()

1990Caneschi[CuCl2(NITP-Py)2]2ClPyCu1995[Cu(hfac)2]3(NITPhoMe)2-1,3 -1987Caneschi[Cu(hfac)2NITMe]1988Mn(hafc)2NIT(iPr)Mn(hafc)2NIT(nPr)iPr nPrMn(hafc)2NITPhNEt21994Inoue4Mn(hafc)2[Mn(hafc)2]3L2n-C7H110.358nmTc3.4K4

-Tc(Rad)2Mn[Cu(opba)]3(DMSO)22H2OTc22.5K1996IwamuraMn(hafc)2Tc46K2001Luneau D.Mn(hafc)2{[ Mn(hafc)2]2(tetranitroxide)},10.1

10.1.2.2 1. 1956Bozorth5.6K:CN:-CN

10.2 ABANCBAB {CnAp[B(CN)6]H2O}

2080KlenzeBabelTcCu3[Fe(CN)6]212H2O14K Ni3[Fe(CN)6]214H2O23KNi3[Mn(CN)6]212H2O30KNi3[Cr(CN)6]215H2O53KCu3[Cr(CN)6]215H2O66K CsNi [Cr(CN)6]2H2O90K 2090 K0.5V/[Cr(CN)6]0.951.7H2O350K K0.058V/[Cr(CN)6]0.79(SO4)0.0580.93H2O376K Okawa1994 [M(CN)6]: [A(chelate)n]3 [B(CN)6]2nH2O [A(chelate)n]2 [B(CN)6]2 XnH2OchelateX>100nm

2.

10.4 EEEO108Tc1840K MN1N2N3N1N2N3MN1N2N310.4

EEEO EE-[Ni2(L)(H2O)(-N3)](CF3SO3)2LMNNNMcryptate-MNNNM EEMJAF EE[Ni2L2(-N3)3](ClO4)L1,4,7--1,4,7-EE-NiNN115.6119.2JAF67.9cm1

EO[Cu2L2(N3)2]L1-(N)-2-CuNCu89.1EO2 EE-EO-EE-EO-

EE-EE-trans-cis- {[NiL4(N3)]n}(ClO4)nnH2OL5-1.8KClO 4 PF6 EE- [NiL2(-N3)]n (PF6)nL1,2--2-ClO 4 PF6EE-[Mn(pyOH)2(N3)2]n (PF6)npyOH2-Mn4MnEE-EE-

EO-3[Ni(L)(-N3)2]nL1,3-2,2--1,3- Co(bt)(N3)2bt2,2- [Cu(Me-L) (N3)4]nMe-L2-(3--1-)4Me-L3EO-EO-

EE-EO-A EE-M2(1,1-N3)2 [Mn(bpy) (1,1-N3) (1,3-N3)]n EE-M2(1,1-N3)2[Mn(L)(N3)2]n(L2-(-1-)

B{[Mn2(3-Et,4-Mepy)6(1,1-N3)2(1,3-N3)]n}(PF6)n (3-Et,4-Mepy3--4-{[Mn2(3-ampy)4(1,1-N3)2(1,3-N3)(N3)(H2O)4H2O]n}3-ampy3- C:trans-{[Mn(N3)(3-Mepy)2]n}

D:[Ni(N,N-dmen)(-N3)2]nE:trans-{[Mn(N3)(Menic)2]n}Menic

EE-EO- EE-EO-EE-EO-EE-EO- EE-[Mn(4-acpy)(N3)2]4-acpy4-,Mn4EE-Mn4-acpyTc28K2K EO-[M(1,1-N3)2]4,4-2,2- [Mn2(1,1-N3)4(-bipym)]nbipym()[Mn2(1,1-N3)2][Mn(1,1-N3)2(pyz)]npyz 4,4-bipyridine[Fe(N3)2(4,4-bpy)]n[Fe(N3)2]Hc34kG

EE-EO- [Ni(-N3)2(N,N-Et2-N-Me-en)]nN,N-Et2-N-Me-enN,N--N-EO-EE-RO-EE-NiNN90 [Ni(-N3)2(2,2-mettn)]n2,2-mettn2,2-50K EE-EO-[Mn2(L)(N3)4]nL1,4-(2-)-2,3--1,3-Mn2Mn2EO-EE-Mn44Mn4EE-EO-Mn44EE-4EO-1.5kGTc110.1KTc214.6K200GTc110.7KTc214.7K500GTc110.4KTc215.0K1kG

EE-EE-EO- EE-4EE-[Mn(N3)2(pzdo)]pzdoN,N-60KNeelTN62K[Mn(N3)2(4-PMK)]n4-PMK-4-Tc22K EE-EO-[Mn2(N3)(1,1-N3)(1,3-N3)(-bipym)]nbipym,EO-EE-(Mn1,3-N3-1,1-N3) 2LL4,5--9-SchiffSchiffLEE-EO-SBU

10.1.2.3 1. / D

quantum tunneling of magnetization Tbblocking temperature KT

SHZeeman- 1993Sessoli R. Mn10.6SMMssingle-molecular magnets10.6 Mn12O12(OAc)164H2O

2. MnFeVCoNi3d-4fspin frustration Mn [Mn12O12(O2CMe)16(H2O)4]2CH3COOH4H2OLis1980MnO21993Christou G.Hendrickson D.N.MnMnMn4Mn12Mn21Mn26Mn30[Mn12O12(O2CMe)16(H2O)4]Tb 8MnIIIMnIIIMnIV3-O

10.7 Mn[Mn3O]Mn

Fe FeFeIIFeIIIFeFeFe4Fe8Fe10Fe11Fe13Fe19 [Fe19(metheidi)10(3-OH)6 (-OH)8(3-O)6(H2O)12]metheidiN-(1-)FeS33/21Fe6Fe3-OFe12FeFeO [V4O2(O2CEt)7(bpy)2][ClO4]3-O(butterfly)S3D-1.52cm-113.68cm-1

Co4[Co4(hmp)4(MeOH)4Cl4]3-OS6D2.78cm-11.8K100.45cm-1CoCo6II [(NMe4)3Na-{Co4(cit)4[Co(H2O)5]2}]11 H2Ocit[C(O-)(CO2-)(CH2CO2-)2]CoII4CoII Ni [Ni12(chp)12(O2CMe)12(H2O)6(THF)6]chp6--2-2-OS12D0.047cm-10.4K6.7cm-1NiCo21 { Na2 (NMe4)14[Ni21(cit)12 (OH)10( H2O)10] }(cit[C(O-)(CO2-)(CH2CO2-)2]S3D0.22cm-10.2K2.01cm-1

10.1.2.4 1. -M(OH)2MCoCuOH-M(OH)2M2(OH)3XXM2(OH)3XMCoM2(OH)3X9.8KMCuCnH2n+1COOCnH2n+1SO4dn

n

2. - - 3. - --TTF-

4. /BDET-TTF BDET-TTF[CoCr(C2O4)3]-[BDET-TTF]3[CoCr(C2O4)3]NITRBDET-TTFp-rad[MnCr(C2O4)3]2H2O,6K160emu/mol50G 5. BDET-TTF Keggin[Xn+W12O40](-n)-(XW12)Dawson-Wells[P2M18O62]6-(MWMo)XW12X[XW12]XHZnBIIISiIVXFeIIICoIICuII

10.2 10.2.1

p-n2030nmSiO24nm107A/cm2 157nm

bottom up 2080Langmuri-Blodgett(LB)(SAMs)(OMBE)(SPM)(molecular rectifiers)(molecular transistors)(molecular switches)(molecular diodes)

10.2.2 (molecular wires)DNA

1. --sp2pz E19.2(N+1)/N2(eV)N10.8 E0.025eV800

pz10.8aPeiers--10.8b10.910.10

10.9 10.10

10.10A1/2-

2. 10-3 S cm-11/

PEO708560657/2TTG193nm LiN 720kJ/molPEO[CH2-CH2-O]n [CH2-CH2-O-CO-(CH2)m-CO]n[CH2-CH2-NR]n[(CH2)m-S]n 10.12 PEO

10.2.3 (molecular switches)

Wasielewki --HPN,N--3,4,9,10-PBDCIPBDCI546713nmPBDCI713nm546nmWasielewki101008600

IrieBranda-KopelmanTian10.144,4-

- C=CN=N

10.15IZnIIIII 10.15

2000CollierLB2V

-Irie10.16-10.16

BottariBrown10.17110.172--

10.2.4 (molecular ) p-np-npn p-np-np-nelectron-rich,n-typeelectron-poor,p-type AviramRatner1974TTFDTCNQA3R10.18a-

10.18 (a)bC16H33-Q3CNQ 1990AshwellC16H33-Q3CNQ10.18bLB1997MetzgerD-ALB

10.2.5 (molecular ) 102bit/cm2RAM1081010bit/cm2DNA1014bit/cm21020bit/cm2 1012bit/cm201

6V >105

-- EQCEQC500nmEEQC500500nmE 9-sp3

- M()MM

10.2.6 (molecular )

1. 10.19aCPL

10.19bMeaxMeeqPMMeaxMeeqPPMMMMPP

2. a b3Hg2N4EDTA43c

10.2110.21c10.21d12010.21f

4. 2001BrouwerStoddart10.23

9.2.7 (molecular ) 2001

1. pn1025nmPDMSp-nFET 2. 2001AvourisDekker 3. 01Tb(III)INHIBTDNA