, .

, "

, ,-.-

-. ..: . :

, .:

-, -'1 ':""'".1."'1,' A" 77o~i.., ~lu ..J ............ u"' ....... _.. ,u,

by

'\)

A l'hcsis )

~~bnittcd to the 2chool of 4raduate Studies

i~ 2~rti~1 fulfil~ent of the rtequirements

1'or the d~bree

~octor of Philosophy

c

;"c;,iaster University

.,.ay. 1976

[ HAL V!DAR SINGH 1976

•

,.c:

)

j

'.

. ".

- ,

:;

,

•

".-- ...._-- ..

'. .

-.

..

..-;; -

-' In /l;emory of hly Parents

'.

.< •

•

' .

....!" L

~- .

•

r

~(

,

.Shivprasad

I\t

and Rajdaya

, "

,;

" .'. ' ~- .

-~ ' ..

Rami"-t'<ln,-Ontario,' ... ' - .

, ." ,

.'..

.~ '.

-, ,~

•• J '.

". . '":. .

.,' ...... '.' ..~

~ .-'

...', .. ~.

, ,. ".

1._ .. • "

,. "

.' . ~ .. '

" '

"

'IlOCTQa :-- oFFHnbSOPHY·' ,".... ..•. : >

-..... :-.

,... .. ,

'. ~ ~-', '" '

· .. ...

•

'. __.-.'. .'-~',.' • - ..... ;. -'¥~. v-- .: .' .,', _ . .- '_ . ;~:. :',- :.

The LUL1111eSCenG!l. '.6£:Pe~hydro,;' Deutero,. and Halo-.~ . ~. ~---:. ,'~_. - .•• ' ': . , ..'~'~. ,_•... ' ~ ' •. -c' .....'. _:

Pl)enyl<LciltYlenes, in;'Rigi~ '591utions 'at~77°ic, ' . -. . ..: .. -~ '." '" ~.' '.' .... -

· -:: ....

, ..

, -.

.-." '-4'-

AUTHOR, HalVidar 3-ihgh,' iL~c,.~ - . '"

". . ~.

(t.i~i:.:ei=ii~Y<lr Guyana)\ "

r-- '.<~... '.

" J

, ..... "

,

, I

/

ii

ABSTRACT·

..

~,,- j

I

o

--1'.. The fluor~scence, and phosphorescence spectra of

..phenylacety=!-ene-H6' ':'D1, -D:S and -;)6 as dil1ite (10-Ji'i or less)

solutions-at'77°K are'reported.

Vi-brational analyses of the fluorescence al'1d phos'­

phore!;cence spectr~ of these co~pounds-in'polycrystalline

m~thylcyclohexane indicate that the geometries of the emitting

singlet (Sl), and triplet (Tl) states are. different. The fluores­

cence spectra are interpreted in terms of a we~~ allowed com­

ponent and a strong forbidden one; the latter based on one

1't~t.,"

't > quantum of non-totally symm~tric b2 vibrations. The main

progression in up to··five quanta of the ring breathing fu!lda­

mental is ~xplained to signify a planar, slightly. expanded

regular ring geometry of Sl' The phosphorescence spectra show

a relative~y long progression in the totally symmetric c~c

ring.st~etchingmorjJindicating a Planar,~on-regular-hexa-

gonal nng in the ~ sta!e,' .' . , . . '

Polarization of the fluorescence and phosphorescenceo

spectra of phenylacetylene-H6 in a rigid glass at 77 K are ,

used to assign the orbital s~etries of.the Tl state as well

~s.the s~~etries of the major bands of these spectra.• G

The phospnorescence lifetimes of -H6' -~1. -DS and -96

in rigid glasses at 77°rc sho\'! that deuterium substi tu'tion for

the single acetylenic hydrogen has aloost the same effect as

deuterium substitution for all five ring hydrogens in altering/

iii

,

[

theradi~tionlcss cteictivaiion of rl' These r~su~are in­

terpreted u~ the ~a~is' of a curre~t theory of radiationless, ,

transitions.

Th~effect of halo~sub$titutton in the ring on radia­..tive and non-radiative rates is investigated' for seven mono~

halophen~'lacetylenes;'The: phosphorescence lifetiraes (in'l 0- >',i(

.glassy solutions) decrease mar:-:edly \'lith incr~asing mass of the

..

halogen, and the e~ect is greatest for the nara

H~aV".f atoiTl perturb~tion affects the J(dfl values

nosition.. "

.... , .

'fu~d 31 ~30 absor~tions'o~y slightly. Inter~ysten crossing

yields are also found to increase with halogen mass. The

vib~t~onal analyses of the .phosphorescence spectra of the

halophenylacetylenes (in ri;id solutions at 77 0 ;C) indicate the

presence of ~vo subspectra. Subspectrum I consists of the 0,0

band and bands due to in~plane nodes (mainly totally-sy6metric)

wh~le 3ubspectrun II arises from out-of-plane modes.· 3ub­

spectrum II is found ,to increase relative to Subspectrum I

•with halogen'substitution. Polariz~tion measurements of the

ma~n,ba~ds ~f the,phosphorescence spectra are ,interpreted in

terms of contrib~tions fron several spin-orbit mechanisms.

~.

--_.... _.

iv

I

"Jr. J .. J. ~3.~"'o~::'.;. ~o~ :lcl \~..., . .,

I w.l 'COI~~1ivcrcit~r -~~o:> ,'inn:r'lci::l ~ :"\..... r.1. -

, ~ i', .'

. •.: i 1(', ' ...

- , ... , .. ~ \.. l •

,. .1 :

. ~. (... ~ ' •. ' 1. .. 1.

Condirston.

.rOi"

'1· .~ .. ~

<.

.~\( ....... .i. ! 1 '.

i~ >• ~'" ' 1.

"., .i"'l \..': : .~ .

I; J.. '...

>..

.."-,. _r~·\.()':i ••

.....l}t>":'C ...

............

.~:.;' ..'<,

,I

Ol'~th::l~"::,:.

Or.1~. ':.

3 inc C 1"0

1~

the. )C ,3:?cc"tr2.. '~nd .I-.::~~ •.l.~::e.. :...:cl.!: ~2, ,~

fino.l draft· or thi~ -chc~') i:-:,.

'contrihutcll i'1 .

'~l',,~ /." '" l'J_. •

'..

v

,

i.f !

i

Introduction , .. -[- ..~ .

Theoretic:lJ.. .I .I

CIL>\?T:c:a 1.

Cj{,·!,i'TZR 2:

TA:aLZ uF

!I,Ii

- I

CO;;TENk3

1

·•~•

3ections.

2.2 Cl:tssificstion of!Zlectronic 3t:ltes ....

5 ,y

7

8

10

13

16

18

19'

20

2:)

26

27

:'0

29

31

1:-.-3:'

36

... . .. . .... . . ...~. . . .. . . . . . . . .

.. . . .... . . . . ... . . .. . . .. . . . .....

Polarization of Luminescence .

Assif3T1lller.t of Or'tli t~l 3.\TlT:Ie tl'Y .

3pin-Orbit COUplini>' , , .

Inter":"'.al Jlc:lvy-atom Zffect , ' ..

;)euterium Isoto::,e :ffectr; .' ':/' .

:nviroru,le:lt:ll 2ffects , .

I

32;~111ctry classifictltion of the"h '11"1., ",o""!l~ne'~ (::' ...... ,~ \·l'\.,.~ 0",\'" nIl'S).... t • .J _" .......... c .....· i..... l".~\.~ •• '-' u\W.~.~~- t;: •••••

2lectronic Absorp,tion and Emiss ion .....!

The Theory' of :Slectro'?:ic 3uectr3. ..... "I •I

~he Fr~nck-Con~o~ ?rincinle ~./. 4t. .Radiationless' Tt.msi tions in Con-d d " d' ! .ense ,.,e la ·.. , " \ ..

Experimellt:ll Jctails .

301vents , " . " , , .

(::ampie ?renan. tion .

App:lra tu", , ..

2.7

2.11

2.4

2.12

2.9

2.10

2.8

2.6

2.1

2.;

::<?erimental .., 3ections I

Chemicals ..

, 2.3

3,1..3.2

3·3

3.4

3.5

•CHr\PTE:1 3 I

,

vi

Vibr~\tiol1~1 ;~n~1::~~0~~ of '~1.~lor~~~c~1~~

":;I'Icctr:.~ 0" -i' •••.••••••• : ••• , ,

..!: 1

41. . . ".

. . . .. . . . . . . . .. . .

~U;;1ine::;cc:1ce oi' rerh:,·J.ro :::'.11 Deutcr:::.tcdPhenylacetylenes .•....•...........•....

:ections:

Gener~l ..I, .1

!~. 2

l !~ . 3

Jiscu~~ion of the i·'luor~.:cc~c2 0~

i']wnyl:,.cet:'l'-':1e ......•............

/1

L' rr' ....: Vibr3tion;11 :\.:1::1y~~..·,~: .Jf ..l. >.o~:"~",o:·,~.;~·, :-'.cc

3,lectrj .

Ji~~cus~ic.l __,~' ~]):: _;;O_~~<1'':'''l:: '. \ ::,...,..):'.r'hcnyl:lC'L'~.:·lcr.c .

-'

.r"hG;·(;·1:1ct:-:~,-ler:'2-~~.~,...•. ... .. .. ... .... . . " ...•

JeuteriLu::' '::ffect O!l th,' l·ho:::']Wl'·.";Cc'llCc'Lifetime 0': .L~:len.;.·}_:-:("_:"'"l:.rlL'lh·..•••••.•.•.

I

"

I, , ..­

I

C]l.\PT~? 5: L~ine::;cencc of tile _"11o"'''·::,d::r.L·t::.lc'''c'': ... 11

3cction:

'rhe ":;ffcr.~ 0f !~L):l\", - 1tO:,1 ";t;~'.- ti tIl t i0.~ l1;'

fdV )' / l'

i·hosphore~c'-'l1ce Lil'c·ti::1L"· (. ~. 11

Relative ;,atios of til<? .·hOSll;~"'C.·,,'.·to' ;;'luore<c,cencc"\ Yi c'1 1 r-- • "-'1 1.11• ..... .~ _ .L:~ •••••••• 00-0_ ••••

5.15.2

5.3• 5.4

:':cneral .... ,....... ... l'

...

5.5 Vibr:'ltion:"!.l "nal:lsL'ccnce ':I.h-,C'tra of t)h~

1 '1yf th1.2 ~ hO~~~"1h~I:'L'<-~::~ lo.\ih"\;1<:1"'lc\"\t.',·lt,t~~·:·

5.6 Interpretation of tl:L' fho.::~)hol:t"'.~(,\"\l:('~'

rol3.ri::':lti.oll~) : ------1'

CHAPTi::R 6: 2nviron..'ncnt:ll 2ff~'r.t~ 011 the .ull:Hllh-': CC,l('l'

....;pcctr~:l.. : .. 0 •••••••••••• 1

1

KZFER2NC~":

\".u

Figu:!"e 2.1

Figure 2.?

Figure 2.3

Figure '3.1,

Fi.::ure 3.2

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Fi£Ure 4.5

Figure 4.6

,FiGUre 4.7

Figure 4.8

?i.:::ure 4.9

Definition of~he coordinate (x, Y, z)"" f C un,!!"" d h C .. C~ .-a;,::es ,or 6"5" ~ll an -:- 6t'4- -Cn .••••.•••.

Schematic enerGY levels with radiative andnon-radiative in~ramolecul~ encr~y loss ...

I ~

Franck-Condon and stationary electronicstates ~ - .

5loc:c diagram of :::pp:lratus .

Sensitivity cor,cctiQn curve of ~hoto-

multiplier-rr.onochrur:lil "'.;or - .

Non:ml vibration:; of monosubstituted. benzeneG(schenatic) ...............•........ " ...•....

The 'Fluorescence .3')ectrum of 10-31" ::>hcnvl­acetylene-H6 in P8~YCr:ist<:lline methyl--c'yclohe)~ane at 77 -.l,. •••••••••••••••••••••••••

, -4,The Fluorescence Spectrum of 10 r.; phen~'l-

acetylene-Dl in '')8~~'crystalline meth:,l-cyclohexane at 77 l\ .,'The Fluorescence SpectrUtl of 10-\, r>hcnyl­acetylene-DSoin polycrystallir.c meth~'lcyclo-

hexane at 77 K.'..........................•..

The fluorescence Spectrum of 10:4~; vh0nyl­acetylene-l)6oin polJ'crystall·ine m<;lthylcyclo-hexane at 77 i~...........................•..

The Phosphorescence Spectrum of 10-3;" pheny1­acetylene-H60in ?olycrystallir.e raethylcyclo-hexane at 77 :: " ...............••.

_L;.The Fhos1Jhorescence, ':;,)ectrum of 10 h: ;1henyl-acetylene-Dloi:l ,ole-crystalline nethY1c,'clo-he::al:.e at 77 :: .

_l~ ,'rhe E'hosphoreGcence ':;!'lectrum of 10 j,. ?henyl-2c~~Ylene-l)So~n ~olycrYGtalline rnethylcyc1o-he.,~ne at 77 ' , ..

"

The :'hOf;"0horc~~C2nC'c .31"~ctr\.~r.: C'f ~C-"':,_ ',):1l;)n\"l-

::.ret':le:1c-J,~, in 1)01 '"Cl":st:'.J li:~0 metll\'1~"'\'('1~-, 0 ' " • .11l':':,' l\~' :\ t 77 .~ .

\' i ; 'i.

15

JJ

51

51

•

Figure 4.10

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Pigure 5.5

Figure 5.6

Figure 5.7

- \The polarizations ,of the fluorescence,and phos~horeGcence ofo~heny12_cetYlehc

in a r:i.gl.'! class -at 77 1\. •••••• ", •••••••••••

The fhosph0F;escence 3pectrum, of 10-3", p-F.%CCH at 77 1:; (J,) In trans-l, 4:"'dimethyl­cyclohexanc. (3):1:n u ri,sid c;lass ......••.

'," I

, 'The Ph06phorescen8e 3pectruI:) of 10-311,

p-Cl % CCI, at 77 :~. (A) In tr:ans-1, L~,_

dincth:rlcyclohexo.ne, (D):;:n a r:iGid;:;lass.

The ?hoGp~oresceBE:.e 3-6ectr..unOfl0;:;:3J,;,

~-i3r t CCl: at 77 ", '( A) In trans-l, -,­C:imethylcyclohe;~2.ne. (!3), In a riGid ::lass.

The PhosPhor,Gcllnce Spectrum of 10-3;,: 'p-I %CCH atJ77 ;~. (A) In tr:ms-l, 4­dimethylcyclohexane. (D) In a riCid zlass.

The PhosphoresceBce Spectrum of 10-:\.,m-Cl %CCH at 77 K, tA) In methylcyclo-hexane. (B) In a rigid g12.ss ', ' ..

The PhosphoresceBce 3J?ectrum of 10-3r,;m-Br %CCH at 77 K. (A) In methylcyclo-hexane. (B) In a rie;id ~lass , . , ,

• 1 -1The PhosphoresceBce .:>,?e~trt1m of 0 -t,;o-Cl %CCH ~t 77 ;~, (A) In ~ ri.,hl :'b!';,~ .

99

126

1~8

12?

141

1 )I '?- .,-

"

.... .d

O"--"" '" •• ou • .-' .-'

.,' ...

, ',•\

/•

2.1

LpT OF 'rAi)LE3

,•

3pin-Orbital I;lixing of Singlet arid Triplet 3tates

1J

__-------;--:----'---,-e.----4.1 The Symmetry, DeSi~atiOl1and...\pprO):imate:De~'- '

cription of. the Normal Vibrational i·.lodes of' ~

. PhenYlacety lene-H.6 · ' ~ .. , ...• , ., ,'..- l' • . . ' •

4.2 ~requencies (cm- ) of the Fundamental Vibration 1'I.lodes of ?erhydro- and ::leuterated ihenylacetylen'~sObserved in the Flourescence (1'), and i'ho3chorescence

, (P) 3Be;ctra in p'olycrystalline i,iethylcyci"ohexar.eat 77 i, ...• " ••••......•...••.•••...• " .•...•....•

44

47

4.)

4.4

Vibrat~onalAnalyses'ofthe Fluores£~nce ~pectraof 10~ J,l Phenylacetylene-;{6, ane. 10 M rhE'nylace­tylene -)1, -;:) 'i' -311' ii1 ,,'ol:;cryst:llline i<,e th:'l-cy~lohexane at 77 K.•.••.•..••.•.•.•. , •••.•..•.••••

Vibra~~onal Analyses of the .i:'hos:,ho!:!lcscence 3pectraof 10 i,I Phenylad'etylenc-il6, :o,nd 10 r,; l'hcnylacety-'lene-::ll' -;)Cib••-;)6, in Polj'crystallinc lIiethylcyclo-hexane 0..t 77 .\. ' 0' ••••••••••••

52

76

4.5

4.6

5.1

5.2

5.3

5,.. ,

Ratios of the Intensities- of the i<.ainVibration..'llFrog~essions Compared to the 0,0 Gand in the £hos­

,phores,?ence 3pectra of l'henylacetylenec at 77 j~.... ,107

30me Properties of the .3 0 - Tl :md 30~'ri 'rransi- 4tions for Protonaten and Deute~:J.ted~jhenYlacetYl:nes109

. "'" \.'30me Triplet and Sin[let ParQIDeters of the -~~lo-

Phenyla~tylenes ' : .. , .. , . : ..,. , . . 11 i f

Fundamentals observed in the PhoCnhorescencc '::;nectl':)·of the Para'-Halophen;:)'~cetYlene:;.:.. , . , , , , .. , , : . , .. , 1.2 J

Vibra~~onal Analyses uf, the l;hosph~rescenC'e 3i',:,ct:-.of 10 i'l Para-Fluoro-, .-Chloro-, -r,romo- :ene'. - H,jO­

pheny~acetYlcne' in l']-'(;1,,·-1, 4-Jil:ll'th:dc:, cloh"~,,':1""t 77 K " . . .. 1JO

l·'nndnmcnt.:!l Vi.br;\tll..lll:'{ ·~'·,l'I'h':~ \,lhd'l"\'l'd ill tlh'l'h0~phol"'C.'{'~'l\Cl.· ~~'l'\"l \'! 'I..'f ~II..' t:1,-ClllOI"O-, ,~-:;~"'l:h'-,

'\nd Orth0-CjllorO~11"'11,\1:H'l' t~·l('t":'." .. " ... " ... " .. " .. '" t I~l.}

J

5,5

6.1"

;

Vi!?5.a"tional .-\.na.l.yses of the ~'hosphorescence of10 .•; ~-chloro-, r.;e"ta-brono- anC: Or"thci-ghloro­?henylacc tylene in •..eth:rlcyclohcx2.nc at 77 ;-c •••••••

•.'

C . f·h 0 0 - - '" ·h - ."." .o:np~~son 0 ... e '. ~~'"1.G. .1.0:::- e ..;Jo - ~l .Lra.ns~-

tion i:1 so:ne benzenes " .

145

171

,..-

~,•

~Iolecular spectroscopy dc~ls with the int~r~ct~o~ a~

,'

electrbwa;:netic .radiation with ::lolecales.

e~ission spectroscopy Give i~sichts into the cec~~t~~ 2~~

~ature of the ground ~~d excited st~tes of ~olecule~.

escence is lisht ecissio~ r::olecules

or ultraviolet liCht. £'>.0 to 1:l:::i:;,~::; ce :"'.C C

on the chenical cOr:lposi tion of ~}';.e c::.:' ttinc ~~.. ::;~e~ ::.:-.20 of t;";-'-.'

, ,ttprocesses, whic.'1 takes pla~ after tl1c 3bsorptio~ of the exc~:-

ation enerf:Y. These processes ~r0 closely associ~tcJ

•,that result in photocher..ical reactio:1s,

Benzene and substituted benzenes have ~ecn s~b:cctc2

to intensive spectrbscopic research within rece~t ycar~. :hc

absorption spectra of phenylacetylene-::6 (C6E Sec;:) :-.::::c O;:'C:.

stUdied in the near 1- J anc fG.:- 4 ult:-2··:iolct, 2.:1:"r:lrcj) 2..:-:.2

~icrowa"e6 '"' • reel.ons.,

EI:1ission in riCid sol',ltio:1s "";::lS i~~vc~ tieD. ted b~,' _h:..l:'2. \"ll~ V~-)

The deuteriun substi tutcd tl.cct~'lcnic hydroccn de r i V:l ti ve r

acetylefle-J 1 (C,~ii<CCJ) ',';:l'- "tHeli,'::

ques 9 : Kine and .3010-1:: l'ccently

-- ; n r,.-_, "-.~.~~""'_""_~U

to include the rinc deutc,~ted phe ny 1 :i.e!? t.\" 1eilC -J [, ( C".J c,C C. ~-

the completely deuterated phc:1ylacct:,.le,,~- ",Cu-lc;:::CJ).

- 1 -•

--,,- ..-.---..---..•- -- ---

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