Università degli Studi di Milano
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Transcript of Università degli Studi di Milano
Università degli Studi di MilanoDipartimento di Chimica Inorganica, Metallorganica e
Analitica
SYNTHESIS OF NEW ALKYNYL Ru(II) SYNTHESIS OF NEW ALKYNYL Ru(II) ORGANOMETALLIC COMPOUNDS WITH EXTENDED ORGANOMETALLIC COMPOUNDS WITH EXTENDED DIPOLAR CHAINS FOR SECOND ORDER NONLINEAR DIPOLAR CHAINS FOR SECOND ORDER NONLINEAR
OPTICAL APPLICATIONSOPTICAL APPLICATIONS
The Australian National University (ANU)Department of
chemistry
Luca RigamontiLuca Rigamonti
conjugated organic bridgeO2N [Ru]
[Ru] = RuCl(dppe)2
12-15 giugno 12-15 giugno 20072007
VI Convegno Nazionale sulla VI Convegno Nazionale sulla Scienza e Tecnologia dei MaterialiScienza e Tecnologia dei Materiali
Mark G. HumphreyMark G. Humphrey
PD1PD144
n = 0, 1, 2 (preceding work)
for example: Hurst et al. Organometallics 2001, 20, 4664-4675
Nonlinearity increases in and 0 in proceeding from n = 0 to 1 and 2
Increase in values due to the substitution of yneyne linkage with an eneene one
[Ru] = RuCl(dppm)2
Powell, C. E.; Humphrey, M. G. Coord. Chem. Rev. 2004, 725-756[Ru] = RuCl(dppm)2
FIRSTFIRST
O2N [Ru]
n
O2N [Ru]
[Ru]
O2N
SECONDSECOND
OBSERVATIONSOBSERVATIONS
O2N
Ru Cl
P
P
P
P
Ph
Ph
Ph
Ph
Ph
PhPh
Ph
O2N
Ru Cl
P
P
P
P
Ph
Ph Ph
Ph
PhPh
PhPh
O2N
Ru Cl
P
P
P
P
Ph Ph
Ph Ph
PhPh
Ph Ph
O2N
O
O
O
O
Ru Cl
P
P
P
PPh
Ph
Ph
Ph
Ph
Ph
Ph
Ph
COMPOUNDSCOMPOUNDS
Introduction of Introduction of eneene linkages in three-ring linkages in three-ring chainschains
Increase of chain length to ascertain the saturation of Increase of chain length to ascertain the saturation of values values
Introduction of ‘greasy groups’ to ensure sufficient
solubility to ligands
terminalterminal
‘‘middle’ middle’
two double bondstwo double bonds
Electronic effects of the double bond vs triple bond
cor
r (10
-30
esu)
[Ru] = RuCl(dppe)2 or RuCl(dppm)2
NO2
[Ru] [Ru]
NO2
[Ru]
NO2
[Ru]
NO2
[Ru]
NO2
[Ru]
NO2
HRS HRS MEASUREMENTSMEASUREMENTS
129161
235
365
468 485
0
100
200
300
400
500
600
Enhancement of values increasing the chain length
Second-order nonlinearity increased by eneene linkages
HRS = Hyper Rayleigth Scattering technique
Department of Chemistry of the Katholièke Universiteit Leuven
(Professor Koen Clays)
g
vec
(10-4
8 es
u)EFISH EFISH
MEASUREMENTSMEASUREMENTS
348
485590 630
717
1220
0
200
400
600
800
1000
1200
1400
NO2
[Ru] [Ru]
NO2
[Ru]
NO2
[Ru]
NO2
[Ru]
NO2
[Ru]
NO2
[Ru] = RuCl(dppe)2 or RuCl(dppm)2
EFISH = Electric Field Induced Second Harmonic
generation technique
Enhancement of values increasing the chain length
Second-order nonlinearity increased by eneene linkages
Dipartimento CIMA of the Università degli Studi di Milano
(Dott.ssa Stefania Righetto)
THANKS TO…THANKS TO…
Professor Mark G. Humphrey and Professor Mark G. Humphrey and coworkerscoworkers