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. 2009 Sep 18;74(18):7067-74.
doi: 10.1021/jo9013589.

Facile self-assembly of neutral dendritic metallocycles via oxygen-to-platinum coordination

Hai-Bo Yang  1 , Brian H Northrop, Yao-Rong Zheng, Koushik Ghosh, Peter J Stang
Affiliations

Facile self-assembly of neutral dendritic metallocycles via oxygen-to-platinum coordination

Hai-Bo Yang et al. J Org Chem. .

Abstract

A new approach for the fabrication of neutral dendritic metallocycles is described. By combining rigid 120 degrees dicarboxylate donor linkers funtionalized with [G0]-[G3] Frechet-type dendrons and complementary rigid 60 degrees and 120 degrees di-Pt(II) acceptor subunits, neutral rhomboidal metallodendrimers and hexagonal metallodendrimers, respectively, were prepared under mild conditions in high yields. The assemblies have well-defined shapes and sizes and were characterized by multinuclear NMR ((1)H and (31)P), mass spectrometry (ESI (+)-TOF-MS and APPI(+)-TOF-MS), and elemental analysis. Isotopically resolved mass spectrometry data support the formation of the neutral [2 + 2] rhomboidal, and [3 + 3] hexagonal metallodendrimers, and NMR data are consistent with the formation of all ensembles. The structures of the [G0] and [G1] neutral rhomboidal metallodendrimers (3a and 3b) were unambiguously confirmed via single-crystal X-ray crystallography. The shape and size of [G3] neutral hexagonal metallodendrimer 5d was established with MMFF force-field simulations.

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Figures

FIGURE 1
FIGURE 1
Schematic and chemical structures of 120° dendritic dicarboxylate donor subunits 1.
FIGURE 2
FIGURE 2
The partial 1H NMR (top) and 31P{1H} NMR (bottom) spectra of [G3] neutral rhomboidal metallodendrimer 3d (See Figure 1 and Scheme 1 for the structures of building blocks 1a-d and 2).
FIGURE 3
FIGURE 3
Calculated (top) and experimental (bottom) ESI-MS spectra of [G0] rhomboidal metallodendrimer (A) and [G1] rhomboidal metallodendrimer (B).
FIGURE 4
FIGURE 4
Crystal structure of [G0] neutral rhomboidal metallodendrimer 3a. Hydrogen atoms have been removed for clarity.
FIGURE 5
FIGURE 5
Crystal structure of [G1] neutral rhomboidal metallodendrimer 3b. Hydrogen atoms have been removed for clarity.
FIGURE 6
FIGURE 6
The partial 1H NMR (top) and 31P{1H} NMR (bottom) spectra of [G3] neutral hexagonal metallodendrimer 5d (See Figure 1 and Scheme 2 for the structures of building blocks 1a-d and 4).
FIGURE 7
FIGURE 7
Calculated (top), experimental ESI(+)-TOF-MS (middle), and experimental APPI(+)-TOF-MS (bottom) spectra of [G0] neutral hexagonal metallodendrimer 5a (column A shows the [M + Na]+ peak and column B shows the [M + 2Na]2+ peak).
FIGURE 8
FIGURE 8
Simulated molecular model of [G3] neutral hexagonal metallodendrimer 5d (C = grey, O = red, P = purple, Pt = yellow; hydrogen atoms have been removed for clarity).
SCHEME 1
SCHEME 1
Self-Assembly of [G0]–[G3] 120° Angular Dendritic Linkers 1a–d with 60° Di-platinum Acceptor 2 to Afford Neutral Rhomboidal Metallodendrimers 3a–d
SCHEME 2
SCHEME 2
Self-Assembly of [G0]–[G3] 120° Angular Dendritic Linkers 1a–d with 120° Di-platinum Acceptor 4 to Afford Neutral Hexagonal Metallodendrimers 5a–d
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