2961
S[ Ranjan and S[ K[ Dikshit
Luminescence Spectrophotometer LS49B[ Correction the reaction mixture was reduced in a rotatory evap!
of the luminescence intensity pro_le was performed orator[ While removing the solvent\ a white precipitate
by ~uorescence data manager software[ Luminescence
quantum yields fs were evaluated by comparing areas
under the corrected luminescence spectra on an energy
scale and by using the following equation]
dissolved and a thick viscous liquid appeared[ It was
cooled and then treated with benzene "39 cm2# which
resulted in super_ne white crystals[ These were then
_ltered and washed with dry ether and then dried in
vaccuo[
f
Fs[Ar
s ꢀ
0[0[1[
Cyanobipyridine"triphenylarsine#copper"I#^
fr Fr[As
Cu"AsPh2#"bpy#CN ð1Ł To a suspension of Cu"A!
sPh2#1"CN# "9[690 g\ 0 mmol# in benzene "29 cm2# was
added a solution of bipyridine "9[045 g\ 0 mmol# in
benzene "29 cm2# with constant stirring[ The resulting
yellow solution was re~uxed for 1Ð2 hours[ The clear
solution thus obtained was cooled\ the volume was
reduced to half and excess petroleum ether "59Ð79>C#
was added\ which resulted in the precipitation of a
where the Fs and Fr are the integrated ~uorescence
intensities of the sample and ðRu"bpy#2Ł1¦[ As and Ar
are the absorbance of the sample and ðRu"bpy#2Ł1¦ at
excitation of same wavelength[ fr for ðRu"bpy#2Ł1¦ is
taken as 9[917[
For the lifetime measurements a coherent synchron!
ously pumped cavity dumped dye laser "691!0#
pumped by a coherent CW mode!locked Nd]YAG pale!yellow compound[ It was _ltered\ washed several
laser "Antares 65s# was used[ The fundamental laser
light at 599 nm was frequency doubled to produce
exciting light at 299 nm[ The emissions were detected
at a magic angle of 43[6> polarisation using a Ham!
amatsu MCP photomultiplier tube "1798U#[ The
response time of the setup is 49Ð59 ps[
The FAB mass spectra were recorded on a JEOL
SX 091:DA!5999 system using Xenon "5 kV\ 099 mA#
as the FAB gas and mÐnitrobenzyl alcohol as a matrix[
Cyclic voltammograms were recorded on a Bio!
Analytical System!16 electrochemical analyser\ uti!
lizing a three electrode con_guration\ consisting of a
glassy carbon working electrode\ Pt wire auxiliary
electrode and Ag:AgCl reference electrode[ An omni!
graphic model 099X!Y recorder was used to record
the current!voltage output[
times with petroleum ether and dried in vaccuo[ It was
recrystalized from a CHCl2Ðxylene mixture "0]0#[
0[0[2[ Cyano0\09Ðphenanthroline"triphenylarsine#
copperðIŁ^ ðCu"AsPh2#"phen#CNŁ ð2Ł To a suspension of
Cu"AsPh2#1CNŁ "9[690 g\ 0 mmol# in benzene "29 cm2#
was added a solution of 0\09[ phenanthroline "9[087 g\
0 mmol# in benzene "29 cm2# with constant stirring[
Immediately an orangeÐred precipitate appeared\ the
resulting mixture was re~uxed for an hour[ After
cooling\ excess petroleum ether "59Ð79>C\ 099 cm2#
was added to ensure complete precipitation of the
complex[ The complex was centrifuged and washed
several times with petroleum ether and dried in vaccuo[
It was recrystalized from a CHCl2Ðxylene mixture
"0]0#[
0[0[3[
chlorobisÐ"1\1?Ðbipyridine#ruthenium"II#hexa!
~uorophosphate^ ð""AsPh2#1CuÐCNÐRu"bpy#1ClŁ
PF5[ð3Ł mixture of ðCu"AsPh2#1CNŁ "9[690 g\
BisÐ"triphenylarsine#copper"I#"mÐcyano#!
RuCl2[xH1O was obtained from Loba Chemie and
triphenylarsine\ 1\1?Ðbipyridine and 0\ 09Ðphen!
anthroline from E!Merck and used as received^ Ace!
tonitrile "Qualigens# used in electrochemical and
spectroscopic studies was dried over molecular sieves[
All other chemicals used were either AnalaR grade
or chemically pure[ Manipulations were invariably
performed under oxygen free dry nitrogen atmosphere
using standard schelnk line and other techniques ð8Ł[
The solvents were dried using standard procedures
before use[
A
0 mmol# and Ru"bpy#1Cl1[1H1O "9[401 g\ 0 mmol# was
suspended in ethanol "49 cm2# and the suspension was
re~uxed for an hour[ The solution was cooled and
_ltered[ A highly concentrated solution of NH3PF5 in
water "9[9953 g in 0 cm2# was added\ which caused the
immediate precipitation of a complex[ The precipitate
was washed thoroughly with water and then with
ether\ and dried over P3O09 for several hours[ It was
recrystalized from a CHCl2ÐCH2CN mixture "0]0#[
Ru"bpy#1Cl1[1H1O ð09Ł and ð"h4−cp#Ru"PPh2#1ClŁ
ð00Ł were prepared according to methods in literature[
CuCN\ Cu"AsPh2#1CN and their substituted ana!
logues were prepared by modifying the literature pro!
cedures ð6\ 01Ł[
0[0[4[
BisÐ"triphenylarsine#copper"I#"mÐcyano#!
cyclopentadienylbisÐ"triphenylphosphine#rutherium
"II#hexa~uorophosphate^ ð"AsPh2#1CuÐCNÐRu"h4Ð
cp# "PPh2#1ŁPF5 ð4Ł ðCu"AsPh2#1CNŁ "9[690 g\ 0 mmol#
and "h4−cp#Ru"PPh2#1ClŁ "9[614 g\ 0 mmol# were
taken in methanol "49 cm2# and the mixture was stirred
vigorously[ NH3PF5 "9[063 g\ 0[1 mmol# was added to
this solution and re~uxed for an hour\ which upon
cooling gave a pale yellow precipitate[ The solvent
was evaporated to dryness in vaccuo and the residue
was extracted with a small amount of dichlo!
romethane and _ltered[ On addition of excess pet!
roleum ether "59Ð79>C#\ a complex precipitated\
0[0[ Syntheses
0[0[0[ CyanobisÐ"triphenylarsine#copper"I#^ ðCu"A!
sPh2#1CNŁ ð0Ł To a suspension of CuCN "9[784 g\ 9[90
mole# in chloroform "49 cm2# was added a solution of
triphenylarsine "01[147 g\ 9[93 mole# in chloroform
"69 cm2#\ and the reaction mixture was stirred con!
stantly for an hour[ During the course of the reaction
the desired complex was precipitated[ The volume of which was centrifuged and washed several times with