Evidence for Extended Interactions between Metal Atoms from

18 Evidence for Extended Interactions between Metal Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on April 26, 2016 | http://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/bk-1974-0005.ch018

Atoms from Electronic Spectra o f Crystals with Square Complexes DON S. MARTIN, JR. A m e s L a b o r a t o r y of the U . S . A . E . C . , I o w a State U n i v e r s i t y , A m e s , I o w a 50010

Abstract

Frequently, the square-planar molecular or ionic complexes of platinum(II) or palladium(II) in crystals are aligned directly over one another in one dimensional stacks. The electronic ab sorption spectra of the crystals for polarized light in favorable circumstances provide information about the crystal interactions and possible intermolecular electron transfers in the solid state. For crystals with large metal-metal separations, >4.1Å, the d-d spectra correlate closely in energies and intensities with solu tion spectra. The spectra of crystals with Pt Br 2- ions indi cate metal-metal electron transfer between metals at 3.55Å, al though the transfer may be influenced by the bromide bridges. For Magnus green salt the spectral changes of PtCl 2- are con sistent with large energy shifts of Frenkel excitons by crystal effects. However, for some molecular complexes with separations of 3.4-3.5Å, electron transfers to ionic exciton states occur. 2

6

1

4

Introduction The electronic absorption spectra have been measured recently for single crystals of a number of ionic or molecular square planar complexes of platinum(I I). Frequently, such complexes stack face to face in linear arrays in crystals to provide strong anisotropics in the absorption of polarized light and in the electrical conductivities. Our concern here will be for the ev idence of transfer of electrons between the platinum atoms. If such electron transfer transitions can be identified, their wave lengths provide directly the energy required for the transfer. Our work to the present has been restricted to the complexes with halide and amine ligands. The absorption bands for the platinum complexes at room tem perature are rather broad; half-widths of approximately 2,000 cm"* are common at 300°K. A transition bandais normally characterized by the wave length, λ, or wave number, v, of the maximum, by the 254 Interrante; Extended Interactions between Metal Ions ACS Symposium Series; American Chemical Society: Washington, DC, 1974.

18.

Crystals

MARTIN, JR.

with

Square

Complexes

255

intensity, € , m o l a r a b s o r p t i v i t y a t t h e maximum o r as t h e o s c i l l a t o r s t r e n g t h : f = 4.32 χ 10" J*e dv and by t h e t e m p e r a t u r e dependence o f t h e i n t e n s i t y . For s i n g l e c r y s t a l s t h e r e i s a l i m i t upon t h e i n t e n s i t y imposed by t h e p r a c t i c a l lower l i m i t s o f c r y s t a l t h i c k n e s s , w h i c h has been e x t e n d e d down t o 1-20μ. T h u s , t h e s t u d i e s a r e l i m i t e d t o bands w i t h e l e s s t h a n 1,000-2,000 cnP-M" . These a r e the n o r m a l l y f o r b i d d e n t r a n s i t i o n s . Hence, t h e a l l o w e d t r a n s i t i o n s a r e not c h a r a c t e r i z e d by c r y s t a l a b s o r p t i o n s p e c t r o s copy except i n t h e i r absence. The t e m p e r a t u r e dependence o f i n t e n s i t y i s an e s p e c i a l l y powerful d i a g n o s t i c property. For t h e d«-d t r a n s i t i o n s , f o r exam p l e , w h i c h a r e symmetry f o r b i d d e n , an a s y m m e t r i c v i b r a t i o n may s e r v e as a p e r t u r b a t i o n t o g i v e a v i b r o n i c wave f u n c t i o n i n t o w h i c h i s mixed an a s y m m e t r i c e l e c t r o n i c wave f u n c t i o n . Thus t h e t r a n s i t i o n s may o b t a i n a n o n - z e r o t r a n s i t i o n moment and o b s e r v able intensity. Since the average amplitude of the v i b r a t i o n , w h i c h s e r v e s as t h e p e r t u r b a t i o n , d e c r e a s e s a t lower t e m p e r a t u r e s , t h e r e i s n o r m a l l y a d e c r e a s e i n i n t e n s i t y . £or a b a n d , e x c i t e d vibronic ly by a v i b r a t i o n o f wave number, V j , t h e i n t e n s i t y dependence (\) i s g i v e n by t h e e q u a t i o n : m a x

9

Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on April 26, 2016 | http://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/bk-1974-0005.ch018

1

f ( T ) = f(0°K) c o t h ( h V j / 2 k T ) .

(I)

However, f o r a band w i t h a n o n - z e r o t r a n s i t i o n d i p o l e , s i n c e t h e i n t e g r a t e d i n t e n s i t y i s not t e m p e r a t u r e d e p e n d e n t , t h e peak height, e , w i l l i n c r e a s e as t h e band n a r r o w s a t l o w e r t e m p e r a ture. F o r t h e h a l i d e and a m i n e - h a l i d e c o m p l e x e s o f p l a t ? n u m ( 1 1 ) t h e c r y s t a l s p e c t r a have i n d i c a t e d t h e o n e - e l e c t r o n o r b i t a l o r d e r i n g i n F i g u r e 1, w h i c h a p p l i e s t o t h e t e t r a g o n a l symmetry 4hThe l o w e s t u n o c c u p i e d o r b i t a l i s t h e σ" o r b i t a l b a s e d on the d _ y 2 w i t h b symmetry. W i t h t h e o t h e r d - o r i b t a l s f i l l e d , t h e g r o u n d s t a t e w i l l be a A i g ; and d-d t r a n s i t i o n s t o t h e s i n g l e t and t r i p l e t s t a t e s o f A g , Eg and B i g r e s p e c t i v e l y s h o u l d o c c u r , the t r i p l e t s t a t e s l y i n g below the corresponding s i n g l e t s . W i t h t h e h i g h s p i n - o r b i t c o u p l i n g o f a heavy P t - a t o m t h e s p i n d e s i g n a t i o n s a r e not e x a c t , and t h e s t a t e s must be d e s c r i b e d by t h e d o u b l e symmetry g r o u p , i n t h i s c a s e D4. Interactions along a s t a c k of square p l a n a r ions w i l l normally i n v o l v e the d s o r b i t a l , which possesses sigma c h a r a c t e r about the s t a c k i n g a x i s . F o r c o m p l e x e s w i t h low e n e r g y π a c c e p t o r o r b i t a l s s u c h as c y a n i d e and o x a l a t e , t h e d o r b i t a l may be much h i g h e r , and i n d e e d has been c o n s i d e r e d by S c h a t z and c o w o r k e r s (2) t o be t h e h i g h e s t f i l l e d orbital for Pt(CN) ". Even i n t h e h a l i d e c o m p l e x e s t h e assignment of the t r a n s i t i o n t o s t a t e (σ * - d 2 ) i s somewhat mx

n

x 2

i g

1

2

z

z 2

3

4

z

open t o q u e s t i o n s i n c e t h e a s s i g n e d band i s s u r p r i s i n g l y weak. B e l o w t h e d o r b i t a l s i n F i g u r e 1 a r e shown t h e o r b i t a l s d e r i v e d f r o m π and σ o r b i t a l s on t h e l i g a n d s . O n l y t h e odd o r b i t a l s a r e d e s i g n a t e d f o r t h e s e can p r o v i d e i n t e n s e P t ( a " ) g * ~ L t r a n s i t i o n s . A p o s s i b l e a l t e r n a t i v e a s s i g n m e n t o f i n t e n s e t r a n s i t i o n s may u

Interrante; Extended Interactions between Metal Ions ACS Symposium Series; American Chemical Society: Washington, DC, 1974.

256

EXTENDED

INTERACTIONS

BETWEEN

METAL

IONS

be 6p «-5d, f o r t h e 6 p o r b i t a l i s t h e s e c o n d l o w e s t u n f i l l e d orb i t a l . F u l l y a l l o w e d m o l e c u l a r t r a n s i t i o n s i n D^h must be A s ( z p o l a r i z a t i o n ) or Ε (χ,ν^ p o l a r i z a t i o n ) . A l l o t h e r t r a n s i t i o n s a r e s e e n a s a c o n s e q u e n c e o f v i b r o n i c and s p i n - o r b i t p e r t u r b a t i o n s , w h i c h m i x t h e s e s t a t e s i n t o t h e wave f u n c t i o n s . In a c o n s i d e r a t i o n of a l l t h e v i b r a t i o n s o f an i o n such as P t B r " i t i s found t h a t t h e ΙΚ2^ s t a t e i s v i b r o n i c l y forbidden i n z-polarization but a l l o w e d i n x , ^ . The E and * B i g t r a n s i t i o n s a r e a l l o w e d i n t h e t h r e e p o l a r i z a t i o n s x , ^ and z. Since the s i n g l e t spin func t i o n s have t h e symmetry, Α χ , and t r i p l e t s a r e A^ and E i în t h e d o u b l e g r o u p , Oi, t h e t r i p l e t s t a t e s e l e c t i o n r u l e s a r e d i f f e r e n t from those o f the s i n g l e t s t a t e s . For c r y s t a l l i n e s t a t e s i n which extended i n t e r a c t i o n s a r e s m a l l , t h e r e i s n e g l i g i b l e o v e r l a p between o r b i t a l s on d i f f e r e n t c o m p l e x e s , and e l e c t r o n s a r e l o c a l l i z e d . E x c i t a t i o n s a r e not l o c a l l i z e d , however, and o t h e r members o f t h e c r y s t a l i n f l u e n c e t r a n s i t i o n energies. In s u c h c a s e s t h e t h e o r y o f F r e n k e l t y p e e x c i t o n s f o r m o l e c u l a r c r y s t a l s c a n a p p l y . The c r y s t a l ground s t a t e wave f u n c t i o n w i l l have t h e f o r m z

z

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τ

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2

4

τ


1

Φ°

0

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,— e

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l

b

2

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( 2

2)

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Figure 1. Molecular orbital scheme for platinum(II) complex under D symmetry as in PtClf- or FtBrf: Only the ρ orbitals of the halides are included, and gerade orbitals aris ing from ligand π and σ orbitals are omitted. On the right are excited symmetry states aris ing from d « - d transitions from the A ground state. Both singlet and triplet states will occur for each indicated symmetry state. } h

1

lg

Figure 2. Unit cell for the tetragonal K PtCl, structure. Κ ions are at ζ = Vi; others at ζ = 0. x

f


IONS

18.

Crystals

MARTIN, JR.

with

Square

Complexes

259

1

t r i p l e t s t a t e the B g s t a t e i s e x p e c t e d t o l i e a t some 9,0ftù 12,000 cm" higher energy. Consequently, the t r a n s i t i o n seen at 33,800 cm i n £-polarization i s a s s i g n e d t o t h i s B i g t r a n s i t i o n . However, t h e i n t e n s i t y o f t h i s t r a n s i t i o n a p p e a r s uncomfortably small f o r t h i s assignment. I t i s h a r d l y more i n t e n s e t h e n t h e s p i n - f o r b i d d e n t r a n s i t i o n s d e s p i t e i t s g r e a t e r p r o x i m i t y t o the s t r o n g bands f r o m w h i c h i n t e n s i t y i s b o r r o w e d , and t h e a s s i g n m e n t c l e a r l y i s subj'ect t o q u e s t i o n . T h e r e i s a c l o s e c o r r e s p o n d e n c e between t h e d*-d s p e c t r a o f KsPtBr and K P t C l w h i c h i s c l e a r f r o m F i g u r e 4 where t h e e n e r g i e s o f t h e t r a n s i t i o n s a r e c o m p a r e d . The t r a n s i t i o n i n t e n s i t i e s a r e i n d i c a t e d by t h e l e n g t h o f l i n e s d e s i g n a t i n g t h e s t a t e s , which f o r the c r y s t a l s are p r o p o r t i o n a l t o log e a t 15°K. It c a n be s e e n t h a t e a c h d«-d t r a n s i t i o n i n K P t B r f a l l s 1,500-2,200 cm" below a corresponding t r a n s i t i o n i n KjaPtCU. In a d d i t i o n , t h e v i b r a t i o n a l s t r u c t u r e i s o b s e r v e d a t 15°K on c o r r e s p o n d i n g transitions. However, t h e i n t e n s e bands o f t h e two a n i o n s a r e quite different. F i ^ r s t o f a l l , t h e s o l u t i o n s p e c t r u m P t B r " has a band a t 31 ,500 cm" , e - 600 c m ^ M " . S i n c e t h e c r y s t a l s p e c t r a f o r b o t h p o l a r i z a t i o n s have a deep v a l l e y a t 29,000 cm" , this band i s p r e s e n t l y a s s i g n e d t o a s o l u t i o n s p e c i e s o t h e r t h a n P t B r " , probably P t B r " . The s o l u t i o n does e x h i b i t s t r o n g bands a t 34,200 and 37,200 cm" with e o f 3,000 and 8 , 5 0 0 cm" M r e s p e c t i v e l y . The c - p o l a r i z e d c r y s t a l s p e c t r u m , w h i c h can be r e c o r d e d t o 37,000 cm" , r e q u i r e s t h a t b o t h t h e s e t r a n s i t i o n s be p o l a r i z e d x,^. The p r e s e n t a s s i g n m e n t a t t r i b u t e s them t o s i n g l e t and t r i p l e t s t a t e s o f t h e same i r r e d u c i b l e r e p r e s e n t a t i o n i n D , v i z . Eîg, w i t h n e a r l y t h e same e n e r g y w h i c h m i x , a r e s p l i t and share i n t e n s i t y . The s e p a r a t i o n o f 3,000 cm" f o r these are c o n s i s t e n t w i t h the expected s p i n - o r b i t c o u p l i n g f o r the Pt i o n . The s i n g l e t s t a t e i s p r o b a b l y t h e E a r i s i n g f r o m M(a' )*~L. A c c o r d i n g t o J o r g e n s e n ( 8 ) , t h e ^-Ey t r a n s i t i o n g a i n s i n t e n s i t y by m i x i n g o f π and σ c h a r a c t e r i n t h e e l i g a n d o r b i t a l s . . There s h o u l d be a A s t a t e c o r r e s p o n d i n g t o Μ(σ*)Η- a t r o u g h l y t h i s e n e r g y . However, i t a r i s e s f r o m Q * ( b i g ) * - b u . Since b i s pure π i n c h a r a c t e r , t h e t r a n s i t i o n s h o u l d be, a c c o r d i n g t o J o r g e n s e n , much w e a k e r . I t may l i e j'ust above 37,000 cm" . However, t h e r e can not be a s t r o n g A u t r a n s i t i o n b e l o w 48,000 cm" . With P t C l " t h e MCD s t u d i e s o f S c h a t z and c o w o r k e r s (2) show t h a t a s h o u l d e r a t 43,000 cm is E w h e r e a s an i n t e n s e p e a k a t 46,000 cm" must be ^-Asu- The d i f f e r e n c e between P t C l " and P t B r " suggests that the intense t r a n s i t i o n s i n P t C l " are p r i m a r i l y 6pH>d. The A u s t a t e w o u l d c o r r e s p o n d t o 6p «-5d . The v e r y weak peak a t c a . 3 0 , 5 0 0 cm" seen i n both p o l a r i z a t i o n s d e s e r v e s some comment. In c - p o l a r i z a t i o n , a t l e a s t , i t seems t h a t a v i b r o n i c l y e x c i t e d t r a n s i t i o n w o u l d be a p p a r e n t i n t h e 300°K s p e c t r u m . Even t h o u g h t h e a b s o r p t i o n i s r i s i n g r a p i d l y i n t h i s r e g i o n , i t can not be d i s c e r n e d a t a l l . I t a p p e a r s t h e r e f o r e t o have a s m a l l but n o n - z e r o t r a n s i t i o n d i p o l e , and i t i s a s s i g n e d as E . The t r a n s i t i o n t o t h i s s t a t e i s d i p o l e - a l lowed 1

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260

EXTENDED

ι ι ι ι I

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I

I

I

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1

I

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I

I

!

I

INTERACTIONS

BETWEEN METAL

IONS

!

Kj>PtBr

4


100

300

H

15

Figure

3.

20

Polarized

25

crystal absorption

30

35

spectra for

K PtBr 2

k

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45

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2

u

40 :,

E - B, (E,' ); U

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U

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235 χ

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B,u

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υ - — 'A2a . - B , Q (Ei )

la

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fl

25 20 h

K PtBr 2

4

K PtCI 2

4

Figure 4. Excited states for K PtBr,, and KjPtCl,. Length of the line for each state is 15 proportional to log €„,„, (15°K) for the crystal transitions and log «,„„, (soin) for the intense transitions. 2


18.

Cry stab with

MARTIN, JR.

by

Square

Complexes

virtue of the spin-orbit coupling

Magnus

1

Green S a l t .

261

i n both p o l a r i z a t i o n s .

PtÇNHaUPtCU.

I t h a s l o n g been r e c o g n i z e d t h a t t h e r e must be s t r o n g c r y s t a l e f f e c t s on t h e s p e c t r a i n Magnus' g r e e n s a l t (MGS), Pt(NH3) PtCl . The component c a t i o n , P t ( N H 3 ) , i s c o l o r l e s s i n aqueous s o l u t i o n o r h a l i d e s a l t s w h e r e a s t h e a n i o n , P t C l " , i s r e d . A s t h e name i m p l i e s t h e MGS i s a d a r k g r e e n , v e r y i n s o l u b l e salt. I t p o s s e s s e s a t e t r a g o n a l c r y s t a l s t r u c t u r e (9) w i t h two of each ion p e r u n i t c e l l . There a r e s t a c k s o f a l t e r n a t i n g ions w h i c h a r e i l l u s t r a t e d i n F i g u r e 5 w i t h a s p a c i n g o f 3.24A between t h e a n i o n s and c a t i o n s i n t h e c h a i n s . The p o l a r i z e d c r y s t a l s p e c t r a a r e p r e s e n t e d i n F i g u r e 6. The c r y s t a l s a r e h i g h l y d i c h r o i c . A c r y s t a l w h i c h a p p e a r s d a r k g r e e n i n c_-polar i z a t i o n i s p a l e y e l low i n ^ - p o l a r i z a t i o n . A t a l l wave l e n g t h s t h e a b s o r p t i o n i s much h i g h e r i n t h e c - p o l a r i z a t i o n t h a n i n t h e a . The g r e e n c o l o r r e s u l t s f r o m a window a t a b o u t 20,000 c m " . The waves i n t h e r e c o r d i n g a t l o w a b s o r b a n c e a r e due t o i n t e r f e r e n c e by m u l t i p l y r e f l e c t e d l i g h t (10). A l t h o u g h t h e i n s t r u m e n t a t i o n d i d n o t p e r m i t measurements b e l o w 17,000 c m " , i t i s c l e a r t h a t t h e l o w e n e r g y band i n £-polarization i s v i b r o n i c i n c h a r a c t e r . A t h i g h e r e n e r g i e s t h e a b s o r p t i o n i n c r e a s e s beyond a n ε o f 700 cm" Μ " , t h e l i m i t o f t h e measurements. In a_-polar i z a t i o n t h e s p e c t r u m i s d o m i n a t e d by a s i n g l e peak a t a b o u t 25,000 c m " , a l t h o u g h t h e r e i s a s h o u l d e r a t 23,000 cm" and a weak s p i n - f o r b i d d e n band b e l o w 17,000 c m " . The wave numbers o f t h e t h r e e p e a k s i n K s P t C l s o l u t i o n a r e shown by t h e 3 a r r o w s i n F i g u r e 6. I t i s concluded t h a t t h e s p i n - f o r b i d d e n p e a k o f P t C l " has been r e d - s h i f t e d b y a b o u t 4,000 cm" i n MGS. The AQQ t r a n s i t i o n and t h e trans i t i o n s have c o a l e s c e d t o t h e s i n g l e peak a t a b o u t 25,000 cm" . T h i s c o r r e s p o n d s t o a r e d s h i f t o f n o t more t h a n 1,000 cm" f o r t h e ^ g s t a t e a n d a b o u t 4000-5000 cm" f o r t h e ^-Eg s t a t e . The r e l a t i v e s h i f t o f t h e s e t r a n s i t i o n s i s a t t r i b u t a b l e t o t h e D' t e r m o f e q u a t i o n 5. The a n g u l a r d e p e n d e n c e o f t h e d o r b i t a l s i n v o l v e d i s shown i n F i g u r e 7 . T h u s , f o r t h e t r a n s i t i o n t o t h e A s g s t a t e , a"(d 2_y2)*~d y, both o r b i t a l s a r e concentrated i n the plane o f t h e i o n and t h e i r e l e c t r o n s s u f f e r s i m i l a r i n t e r a c t i o n s w i t h t h e e l e c t r o n c l o u d s o f t h e adj'acent i o n s . For the d o r b i t a l , however, t h e r e i s a c o n s i d e r a b l e e l e c t r o n d e n s i t y o u t o f t h e p l a n e o f t h e i o n . The e n e r g y o f t h e e l e c t r o n i n t h i s o r b i t a l i s t h e r e f o r e r a i s e d by t h e e l e c t r o n - e l e c t r o n r e p u l s i o n s , and a red s h i f t f o r t h e t r a n s i t i o n o c c u r s . The h i g h a b s o r p t i o n i n t h e c - p o l a r i z a t i o n i s c l a r i f i e d f r o m d i f f u s e r e f l e c t a n c e s p e c t r a f o r K P t C l and MGS w h i c h a r e shown i n F i g u r e 8. I t c a n be s e e n t h a t t h e maximum, w h i c h c o r r e s p o n d t o a v e r y i n t e n s e t r a n s i t i o n , has been s h i f t e d f r o m c a . 44,000 cm" i n K P t C l t o 35,000 cm" i n MGS. T h i s band i s a p p a r e n t l y i n t h e c - p o l a r i z a t i o n . Such a l a r g e r e d s h i f t must be l a r g e l y c a u s e d b y t h e I t e r m o f e q u a t i o n 5. I t w o u l d r e q u i r e s t r o n g 2 +

4

4

4

2


4

1

1

1

1

1

1

1

4

2

4

1

1

1

1

1

X

X

y

2

1

4

1

2

4

1


z

262


EXTENDED

Figure

Figure 6. Polarized crystal absorption trum for Magnus' green salt

INTERACTIONS

5.

Alternate Magnus'

BETWEEN

METAL

stacking of green salt

spec-


IONS

ions

in


18.

MARTIN, JR.

Figure

7.

Angular

Crystals

with

Square

Complexes

portions of ά-orbitals involved tral transitions of MGS

Figure

8.

263

in spec

Diffuse reflectance spectra and K.FtCh, at 300°Κ


for

MGS

264

EXTENDED

INTERACTIONS

BETWEEN

METAL

IONS

2

2 +

t r a n s i t i o n s o f c o m p a r a b l e e n e r g y i n b o t h P t C l ~ and P t ( N H 3 ) . T h i s i s the a l l o w e d t r a n s i t i o n from which the v i b r o n i c e x c i t a t i o n s i n c - p o l a r i z a t i o n b o r r o w i n t e n s i t y , and t h e p r o x i m i t y o f t h i s band e n h a n c e s t h e i r i n t e n s i t y by a b o u t an o r d e r o f m a g n i t u d e . The s p e c t r a o f MGS t h e r e f o r e i n d i c a t e t h a t t h e s t r i k i n g c o l o r changes r e s u l t f r o m c r y s t a l i n t e r a c t i o n s , p r i m a r i l y w i t h a d j a c e n t n e i g h b o r s , w h i c h m o d i f y t h e m o l e c u l a r t r a n s i t i o n s but w i t h o u t d e l o c a l i z a t i o n of e l e c t r o n s . Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on April 26, 2016 | http://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/bk-1974-0005.ch018

4

Pt Br 2

2 6

"

4

Spectra

A d i m e r complex p r o v i d e s an o p p o r t u n i t y f o r t h e d e m o n s t r a t i o n o f e l e c t r o n d e l o c a l i z a t i o n on a l i m i t e d s c a l e by a b s o r p t i o n spectroscopy. The d i m e r i c a n i o n c r y s t a l l i z e s i n t h e t e t r a e t h y l ammonium s a l t w h i c h i s t r i c l i n i c w i t h a m i c a c e o u s c l e a v a g e f o r w h i c h t h e s t r u c t u r e was r e p o r t e d by S t e v e n s o n ( 1 1 ) . The p r o j e c t i o n o f d i m e r i c i o n on t h e c l e a v a g e f a c e i s shown i n F i g u r e 9 . T h e r e i s one a n i o n p e r u n i t c e l l . The p l a t i n u m atoms i n a d i m e r a r e s e p a r a t e d 3.55Â, and t h e a n i o n s a r e s e p a r a t e d 7 . 6 i f r o m t h e i r n e a r e s t n e i g h b o r s by t h e b u l k y c a t i o n s . The l i g h t beam t h e r e f o r e e n t e r s d i m e r a n i o n n e a r l y end on. The m o l e c u l a r a x e s o f heavy a n i o n a p p a r e n t l y e s t a b l i s h the axes of the i n d i c a t r i x , so t h e r e i s v e r y l i t t l e d i r e c t i o n a l change o f t h e s e a x e s w i t h wave l e n g t h . One e x t i n c t i o n f o r c r y s t a l s was a l i g n e d , as a c c u r a t e l y as c o u l d be d e t e r m i n e d , w i t h t h e p r o j e c t i o n o f t h e y m o l e c u l a r a x i s upon t h e c r y s t a l f a c e o v e r t h e e n t i r e wave lengtTh r e g i o n w h i c h was s t u d i e d . The a b s o r p t i o n i n t h i s e x t i n c t i o n d i r e c t i o n gave a v e r y c l e a n intermediate a x i s or ^ - p o l a r i z a t i o n . The o t h e r e x t i n c t i o n p r o v i d e d p r i m a r i l y the s h o r t a x i s or x - p o l a r i z a t i o n . Preliminary s p e c t r a a r e shown i n F i g u r e 10. The a b s o r p t i o n i n ^ - p o l a r i z a t i o n i s much h i g h e r t h a n i n t h e x - p o l a r i z a t i o n . T h u s , a t room tempera t u r e t h e r e i s a peak i n γ p o l a r i z a t i o n a t 2 3 , 5 0 0 cm" very c l o s e t o t h e 24,000 cm" f i r s t spin-allowed transition in K P t B r . However, t h e e f o r t h e band a t t h i s V i n K P t B r was o n l v c a . 100 c n P - M . In t h e P t B r " s a l t i t was 800 cm' /H(?t Br ~J7 But when t h e c r y s t a l was c o o l e d , t h e peak h e i g h t i n c r e a s e d t o 1600 c n T V M , w h i c h i n d i c a t e d t h a t t h e t r a n s i t i o n was d i p o l e a l l o w e d r a t h e r than v i b r o n i c . In t h e x - p o l a r i z a t i o n t h e r e was not much i n d i c a t e d s t r u c t u r e i n t h e s p e c t r u m b u t t h e a b s o r p t i o n i n c r e a s e d as ν i n c r e a s e d . A peak a t 3 6 , 5 0 0 cm" occurs j u s t where t h e MH. c h a r g e t r a n s f e r band o c c u r s i n P t B r " s o l u t i o n . T h i s may be t h e n an x - p o l a r i z a t i o n o r o u t - o f - p l a n e M*-L w h i c h a p p a r e n t l y i s v e r y weak i n P t B r " as w e l l . A t 15°K, band maxima a t 29,000 cm" and 32,000 cm" a r e s e e n as w e l l , and t h e r e i s a s h o u l d e r a t 26,000 cm" . In c o n s i d e r a t i o n o f t h i s s p e c t r u m e a c h p l a t i n u m atom can be c o n s i d e r e d t o b r i n g i n t o t h e d i m e r i t s complement o f f i v e 5 d orbitals. M o l e c u l a r o r b i t a l s f o r t h e d i m e r a r e c o n s t r u c t e d by t a k i n g t h e sum o r d i f f e r e n c e o f c o r r e s p o n d i n g d - o r b i t a l s on d i f f e r e n t p l a t i n u m atoms. W i t h t h e c h o i c e o f a x e s t h e σ'* o r b i t a l s o

1

1

2

m a x

2

- 1

2

2

1

2

6

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u

e

Cry stab with

MARTIN, JR.

Square

Complexes

[N(C H ) ]JPt Br ] 2

5

4

2

6


b

Figure

9.

Projection

of the dimeric ions, Pt Br ~ of[N(C H )J [Pt Br l

I

2000 "

1

1

1

I

J

1

1

5

2

1

2

upon the 001 cleavage

2

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(

1

ι

ι

l—ι

j

ι

ι

ι

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4

2

2

ι

Ϊ

1

6

300°Κ/^

- x polarization ^-

Evidence for Extended Interactions between Metal Atoms from

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