Abstract
A number of complexes of the type [M
II
(LL)
2
] [Pt
IV
(LL)
2
Cl
2
] [ClO
4
]
4
, where M = Ni, Pd or Pt and LL = 1,2-diaminoethane (en) or 1,2-diaminopropane (pn), as well as the monomers [Pt
IV
(LL)
2
Cl
2
] Cl
2
and [M
II
(LL)
2
] Cl
2
have been studied using Fourier transform infrared (f.t.i.r.) and resonance Raman spectroscopy. Under conditions of low tem perature and moderate resolution (
ca
. 0.5 cm
-1
) it has proved possible to observe chlorine isotopic splitting in bands due to both the symmetric and the antisymmetric stretching modes of the linear Pt
IV
Cl
2
units in the chains. On the basis that the one-dimensional electronic properties of these chains are likely to be related to the in-chain Pt
IV
-Cl stretching force constants, a simple vibrational model is presented, which is able to reproduce the observed splitting patterns to well within experimental error. A comparative study of the Pt
IV
-Cl stretching force constants for the series of en complexes shows the trend:
trans
-[Pt
IV
(en)
2
Cl
2
] Cl
2
(monomer) > Pd
II
- Pt
IV
> Ni
II
- Pt
IV
> Pt
II
−Pt
lV
. This trend is in line with that of the M
II
…Pt
IV
intervalence band maxima, namely Pd
II
- Pt
IV
(25000 cm
-1
) > Ni
II
- Pt
IV
(22200 cm
-1
) > Pt
II
- Pt
IV
(20800 cm
-1
), indicating an increase in M
II
… Cl chain interaction (and an expected increase in conductance) along the series.
Reference31 articles.
1. Allavena M. Rysnik R. White D. Calder V. & Mann D. E. 1969 Phys. 50 3399-3410.
2. Molec. Cryst. liq;Aoki R.;Cryst.,1982
3. molec;Barraclough C. G.;Struct.,1982
4. Clark R. J. H. 1984a In Advances in infrared and raman spectroscopy (ed. R. J. H. Clark & R. E. Hester) vol. 11 pp. 95-132. Chichester: Wiley.
5. bJ. molec;Clark R. J. H.;Struct.,1984
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