Article
Organometallic Oligomer Resolved by Radial Distribution Function of X-ray Diffraction Analysis
Universit di Roma “Sapienza”.
Universit degli Studi di Palermo.
Universit di Tor Vergata.
Abstract
Platinum−organic oligomers are actively studied for their large physical and functional properties such as solubility, processability, color, luminescence, and optoelectronics related to the different metal groups and auxiliary coligands around the metal coordination spheres. Previous studies on nanotechnology devices have shown that the structural organization of handled metallopolymer generates several 2D or 3D nano-objects, but only based on trans polymorph chains. Here we report the first self-assembly of powder cis-Pt-DEBP oligomers that shows great self-assembling ability to form nanoscale supramolecular architectures. As a powder is obtained that shows a poor crystalline organization of the aggregates, the energy-dispersive X-ray diffraction is the nondestructive technique of choice to obtain short-range order structural parameters of a single nano-object by radial distribution function analysis. The supramolecular architecture of 8-units-long chains reveals a self-assembling organization of 18 chains exhibiting an overall linear inverted open square structure. The ensemble of oligomer chains form a parallelepiped shape with small internal square cavities of 3.2 nm diameter capable of hosting smaller molecules, which opens up to all applications where sieving and sensing is important. This structural investigation of short-range order materials has provided a substantial additional impetus to the field by opening up the area of self-assembled supramolecular materials based on metallopolymers for technological applications.
Introduction
Experimental Section
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Figure 1. (A) Experimental structural function (SF) of Pt-DEBP obtained with energy dispersive X-ray diffraction, and (B) the corresponding experimental Diff(r).
Distance range (nm) | σ |
---|---|
0.00![]() ![]() ![]() ![]() | 0.071 |
0.25![]() ![]() ![]() ![]() | 0.142 |
0.41![]() ![]() ![]() ![]() | 0.212 |
0.78![]() ![]() ![]() ![]() | 0.267 |
1.05![]() ![]() ![]() ![]() | 0.301 |
1.56![]() ![]() | 0.357 |
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Results and Discussion
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Figure 2. Experimental radial distribution Diff(r)s (black dots) and theoretical curves (red solid lines) calculated for a single nano-object of 18 assembled Pt-DEBP oligomers. The theoretical curves correspond to the following models: (A) linear rigid rodlike chains in trans-configuration, (B) linear zigzag chains in cis-configuration, (C) linear open square chains in cis-configuration, and (D) linear inverted open square in cis-configuration.
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Figure 3. Structural models of the cis-Pt-DEBP sample. (A) Oligomeric chain model of 8 repeating units lying in the zx plane. Butyl groups are omitted for clarity. The main values of the structural parameters are shown, i.e., the Pt−Pt distances, the C−Pt−C angles, and the positions where a change of torsional angle α is applied along the chain. The inset represents the chemical structure of Pt-DEBP monomeric unit. In the model, the platinum is red, phosphorus yellow, carbon black, and hydrogen gray. (B) 3D view of six chains model packed in parallel configuration along the y-axis, where the green selected chains are shifted by one unit with respect to the intercalated one. (C) 3D view of 18 chains.
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N | x | y | z | N | x | y | z | N | x | y | z |
---|---|---|---|---|---|---|---|---|---|---|---|
1 | 0.000 | 0.000 | 0.000 | 7 | −0.110 | 0.020 | 2.871 | 13 | −0.020 | −0.010 | 5.787 |
2 | 0.008 | −0.478 | −0.145 | 8 | −0.102 | −0.458 | 2.642 | 14 | −0.012 | −0.488 | 5.454 |
3 | 0.041 | −1.012 | 0.107 | 9 | −0.069 | −0.992 | 3.061 | 15 | 0.023 | −1.022 | 5.935 |
4 | 0.106 | −1.512 | −0.001 | 10 | −0.004 | −1.492 | 2.744 | 16 | 0.086 | −1.522 | 5.465 |
5 | 0.188 | −2.067 | 0.224 | 11 | 0.078 | −2.047 | 3.091 | 17 | 0.168 | −2.077 | 6.022 |
6 | 0.008 | −2.554 | 0.088 | 12 | 0.092 | −2.534 | 2.841 | 18 | 0.183 | −2.564 | 5.757 |
Conclusions
Acknowledgment
We gratefully acknowledge Lorenzo Gontrani for software assistance and CASPUR (Consorzio Interuniversitario per le Applicazioni di Supercalcolo Per Universit e Ricerca) for supplying the computing facilities.
Closed square-planar theoretical model in the Diff(r) form compared with the experimental one (Figure 1S), theoretical data of the atomic cartesian coordinates (Å) of the Pt-DEBP unit and of the trans-[Pt(PBu3)2Cl] head/tail of the oligomer. This material is available free of charge via the Internet at http://pubs.acs.org.
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History
- Published In Issue February 25, 2010
- Article ASAPJanuary 29, 2010
- Received: October 19, 2009
Revised: January 4, 2010