TY - JOUR
T1 - Observation of the properties of a single unit of a limited CDW structure in a PtIIPtIV host-guest binary system based on a square-shaped complex
AU - Hirahara, Eri
AU - Takaishi, Shinya
AU - Yamashita, Masahiro
PY - 2009/9/1
Y1 - 2009/9/1
N2 - A macrocyclic tetranuclear platinum(II) complex [Pt(en)(4,4′bpy)] 4(NO3)8 (1-(NO3)8; en = ethylenediamine, 4,4′-bpy = 4,4′-bipyridine) and a mononuclear platinum(IV) complex [Pt(en)2Br2]Br2 (2-Br 2) formed two kinds of PtII/PtIV mixed valence assemblies when reacted: a discrete hostguest complex 1.2.Br10 (3) and an extended 1-D zigzag sheet 1.(2)3.Br8 (NO 3)6 (4). Single crystal X-ray analysis showed that the dimensions of the assemblies could be stoichiometrically controlled. Resonance Raman spectra suggested the presence of an intervalence interaction, which is typically observed for quasi-1-D halogen-bridged MII/MIV complexes. The intervalence interaction indicates the presence of an isolated {PtII-X-PtIV-X-PtII} moiety in the structure of 4. On the basis of electronic spectra and polarized reflectance measurements, we conclude that 4 exhibits intervalence charge transfer (IVCT) bands. A Kramers-Kronig transformation was carried out to obtain an optical conductivity spectrum, and two sub-bands corresponding to slightly different Pt II-PtIV distances were observed.
AB - A macrocyclic tetranuclear platinum(II) complex [Pt(en)(4,4′bpy)] 4(NO3)8 (1-(NO3)8; en = ethylenediamine, 4,4′-bpy = 4,4′-bipyridine) and a mononuclear platinum(IV) complex [Pt(en)2Br2]Br2 (2-Br 2) formed two kinds of PtII/PtIV mixed valence assemblies when reacted: a discrete hostguest complex 1.2.Br10 (3) and an extended 1-D zigzag sheet 1.(2)3.Br8 (NO 3)6 (4). Single crystal X-ray analysis showed that the dimensions of the assemblies could be stoichiometrically controlled. Resonance Raman spectra suggested the presence of an intervalence interaction, which is typically observed for quasi-1-D halogen-bridged MII/MIV complexes. The intervalence interaction indicates the presence of an isolated {PtII-X-PtIV-X-PtII} moiety in the structure of 4. On the basis of electronic spectra and polarized reflectance measurements, we conclude that 4 exhibits intervalence charge transfer (IVCT) bands. A Kramers-Kronig transformation was carried out to obtain an optical conductivity spectrum, and two sub-bands corresponding to slightly different Pt II-PtIV distances were observed.
KW - Charge transfer hostguest systems
KW - Mixed valence
KW - Platinum
KW - Supramolecular chemistry
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U2 - 10.1002/asia.200900114
DO - 10.1002/asia.200900114
M3 - Article
AN - SCOPUS:69649086042
SN - 1861-4728
VL - 4
SP - 1442
EP - 1450
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 9
ER -