Vibrational and electronic spectra of (Pt sub 2 (SO sub 4 ) sub 4 ) sup 2 minus complexes. [(Pt sub 2 (SO sub 4 ) sub 4 L sub 2 ) sup n- where L=OH sub 2 , DMSO, n=2 and L=Cl, Br, n=4]

Journal Article · Wed Nov 27 04:00:00 EST 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00024a037· OSTI ID:7017591

Newman, R A; Martin, D S ^[1]; Dallinger, R F ^[2]; Woodruff, W H ^[3]; Stiegman, A E; Che, Chiming; Shaefer, W P; Miskowski, V M; Gray, H B ^[4]

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1. Iowa State Univ., Ames (United States)
2. Wabash Coll., Crawfordsville, IN (United States)
3. Los Alamos National Lab., NM (United States)
4. California Inst. of Tech., Pasadena (United States)

The vibrational and electronic spectra of axially ligated sulfate-bridged binuclear platinum complexes ((Pt{sub 2}(SO{sub 4}){sub 4}L{sub 2}){sup n{minus}}: L = OH{sub 2}, DMSO, n = 2; L = Cl, Br, n = 4) have been studied. Raman spectra acquired with near-UV excitation show bands assigned to Pt-O(sulfate) stretching (300-350-cm{sup {minus}1} region) for all complexes, while bands assigned to Pt-Pt and pt-L stretching are seen for complexes (L = Cl, Br) that display preresonance Raman scattering within intense near-UV absorption bands assigned to the {sigma}(L) {r arrow} {sigma}{sup {star}}(Pt{sub 2}) electronic transition. Weaker electronic absorptions are assigned as metal-metal {sup 1}({sigma} {r arrow} {sigma} {sup {star}}) (near 220 nm for L =OH{sub 2}, Cl) and d{pi} {r arrow} d{sigma}{sup {star}}(Pt{sub 2}) (350-500 nm). Single-crystal polarized absorption spectra (L = OH{sub 2}, DMSO) show that the weak absorption system in the 350-500-nm region consists of three z-polarized (metal-metal axis) bands and an x,y-polarized band. The L = OH{sub 2}, Cl complexes show weak emission bands in the 695-750-nm region when excited at 77 K with near-UV light. These emission bands are similar to those observed for (Pt{sub 2}(HPO{sub 4}){sub 4}L{sub 2}){sup n{minus}} (L = OH{sub 2}, n = 2; L = Cl, n = 4) complexes. The emission lifetimes for the sulfate-bridged complexes (450 {plus minus} 50 ns, L = OH{sub 2}; 290 {plus minus} 20 ns, L = Cl) are much shorter, and the emission intensities are much weaker, than the corresponding properties of the phosphate-bridged complexes.

• OSTI ID: 7017591
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:24; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTRA
BOND ANGLE
BOND LENGTHS
COHERENT SCATTERING
COMPLEXES
CRYSTALS
DIFFRACTION
DIMENSIONS
ELECTROMAGNETIC RADIATION
ELECTRON SPECTRA
EMISSION SPECTRA
ENERGY-LEVEL TRANSITIONS
EXCITATION
INFRARED SPECTRA
LENGTH
MONOCRYSTALS
PLATINUM COMPLEXES
RADIATIONS
RAMAN SPECTRA
SCATTERING
SPECTRA
SPECTROSCOPY
TEMPERATURE RANGE
TEMPERATURE RANGE 0065-0273 K
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET RADIATION
X-RAY DIFFRACTION