Versatile Behavior of [Pt2Ag4(CC-t-Bu)8]: Synthesis, Structures, and Properties of [{Pt2
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- 作者：Irene Ara ; Juan Fornié ; s ; Julio Gó ; mez ; Elena Lalinde ; and M. Teresa Moreno
- 刊名：Organometallics
- 出版年：2000
- 出版时间：August 7, 2000
- 年：2000
- 卷：19
- 期：16
- 页码：3137 - 3144
- 全文大小：122K
- 年卷期：v.19,no.16(August 7, 2000)
- ISSN：1520-6041
文摘
An unusual adduct, [{Pt2Ag4(C
C-t-Bu)8·(bipy)}]
(3), has been obtained from the reactionof the hexanuclear cluster [Pt2Ag4(CC-t-Bu)8] (1) with 2,2'-bipy independently of the molarratio (1:1 or 1:excess) employed. The crystal structure of 3 shows the presence of an extendedpolymeric chain constructed by long-range, secondary misdirected Ag···N interactionsbetween the cluster units and the 2,2'-bipy ligand. 3 is highly emissive in the solid stateand in frozen solution. A considerable enhancement of the luminescence and a notable redshift in the emission maximum of 3 (
max 513 nm) relative to [Pt2Ag4(CC-t-Bu)8] (1) (max476 nm) is observed. In an attempt to obtain an analogous polymeric chain based on highernuclearity building blocks, the reaction between [{Pt2Ag8(CC-t-Bu)8}(OClO3)2(OCMe2)2](O2ClO2)2} (2) and 2,2'-bipy was also examined. Treatment of 2 with 2,2'-bipy (molar ratio 1:4,Ag:bipy 1:0.5), however, produces [{Pt2Ag4(CC-t-Bu)8}{Ag(bipy)}4](ClO4)4 (4), in which thecluster unit acts as an octadentate bridging ligand toward four Ag(bipy) fragments. The useof a higher proportion of 2,2'-bipy (1:6 or 1:8 molar ratio) produces [Pt2Ag8(CC-t-Bu)8(bipy)6](ClO4)4 (5).
C-t-Bu)8·(bipy)}] (3), has been obtained from the reactionof the hexanuclear cluster [Pt2Ag4(CC-t-Bu)8] (1) with 2,2'-bipy independently of the molarratio (1:1 or 1:excess) employed. The crystal structure of 3 shows the presence of an extendedpolymeric chain constructed by long-range, secondary misdirected Ag···N interactionsbetween the cluster units and the 2,2'-bipy ligand. 3 is highly emissive in the solid stateand in frozen solution. A considerable enhancement of the luminescence and a notable redshift in the emission maximum of 3 (max 513 nm) relative to [Pt2Ag4(CC-t-Bu)8] (1) (max476 nm) is observed. In an attempt to obtain an analogous polymeric chain based on highernuclearity building blocks, the reaction between [{Pt2Ag8(CC-t-Bu)8}(OClO3)2(OCMe2)2](O2ClO2)2} (2) and 2,2'-bipy was also examined. Treatment of 2 with 2,2'-bipy (molar ratio 1:4,Ag:bipy 1:0.5), however, produces [{Pt2Ag4(CC-t-Bu)8}{Ag(bipy)}4](ClO4)4 (4), in which thecluster unit acts as an octadentate bridging ligand toward four Ag(bipy) fragments. The useof a higher proportion of 2,2'-bipy (1:6 or 1:8 molar ratio) produces [Pt2Ag8(CC-t-Bu)8(bipy)6](ClO4)4 (5).