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