From Vauquelin's and Magnus' Salts to Gels, Uniaxially Oriented Films, and Fibers: Synthesis, Characterization, and Properties of Tetrakis(1-aminoalkane)metal(II) Tetrachlorometalates(II)
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- 作者：Juliane Bremi ; Dorothee Brovelli ; Walter Caseri ; Georg H鋒ner ; Paul Smith ; Theo Tervoort ; and R. Y. Yee
- 刊名：Chemistry of Materials
- 出版年：1999
- 出版时间：April 1999
- 年：1999
- 卷：11
- 期：4
- 页码：977 - 994
- 全文大小：334K
- 年卷期：v.11,no.4(April 1999)
- ISSN：1520-5002
文摘
Complexes of the type [Pt(NH2R)4][PtCl4] with R = (CH2)nCH3, where n is 3, 6, 7, 8, 9, 11,or 13, were synthesized and characterized with various methods (e.g., IR spectroscopy, SAXS,XPS, NEXAFS, TEM, DSC, and TGA). For comparison, the classical Magnus' green andpink salt (where R = H) were also prepared. The designated alkyl-substituted platinumcompounds are pink, but their structure seems to be related rather with Magnus' greenthan with the pink salt. However, the Pt-Pt distance in the pink alkyl-substituted compoundsis most likely larger than in Magnus' green salt. This result is in agreement with the lowelectrical conductivity (<10-10 S/cm) in the alkyl-substituted complexes. Because the Pt-Ptinteractions in the [Pt(NH2R)4][PtCl4] compounds are presumably weak, these substancesmay be regarded as self-assembled supramolecular structures. Nonetheless, the preparedcomplexes show some characteristics of rigid-rod polymers with flexible side chains; forexample, they are insoluble when the alkyl chains are short but become soluble for longeralkyl chains, and they are able to form two-dimensional hexagonal or sheet structures. Thecomplexes melt under decomposition above 100 
C. The soluble [Pt(NH2R)4][PtCl4] complexesform gels with fibrillar structures at temperature ranges that depend on the length of R.Films and fibers with uniaxially oriented fibrils were prepared from gels by drawing andelectrostatic spinning. The mixed-metal complexes [Pd(NH2R)4][PtCl4] and [Pt(NH2R)4][PdCl4](R = octyl) were also synthesized. The chemical and physical properties of the compoundswith palladium differed significantly from those of [Pt(NH2R)4][PtCl4]. In particular, one ofthese complexes is insoluble, whereas the other one decomposes relatively quickly in solution.
C. The soluble [Pt(NH2R)4][PtCl4] complexesform gels with fibrillar structures at temperature ranges that depend on the length of R.Films and fibers with uniaxially oriented fibrils were prepared from gels by drawing andelectrostatic spinning. The mixed-metal complexes [Pd(NH2R)4][PtCl4] and [Pt(NH2R)4][PdCl4](R = octyl) were also synthesized. The chemical and physical properties of the compoundswith palladium differed significantly from those of [Pt(NH2R)4][PtCl4]. In particular, one ofthese complexes is insoluble, whereas the other one decomposes relatively quickly in solution.