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. 2014 Jan 22;7(1):611-622.
doi: 10.3390/ma7010611.

A Self-Assembled Electro-Active M8L4 Cage Based on Tetrathiafulvalene Ligands

Sébastien Goeb  1 , Sébastien Bivaud  2 , Vincent Croué  3 , Vaishali Vajpayee  4 , Magali Allain  5 , Marc Sallé  6
Affiliations

A Self-Assembled Electro-Active M8L4 Cage Based on Tetrathiafulvalene Ligands

Sébastien Goeb et al. Materials (Basel). .

Abstract

Two self-assembled redox-active cages are presented. They are obtained by coordination-driven self-assembly of a tetra-pyridile tetrathiafulvalene ligand with cis-M(dppf)(OTf)₂ (M = Pd or Pt; dppf = 1,1'-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both species are fully characterized and are constituted of 12 electro-active subunits that can be reversibly oxidized.

Keywords: metal-driven; metalla-cages; redox; self-assembly; tetrathiafulvalene.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1.
Figure 1.
X-Ray structure of ligand L1: (a) side view and (b) top view.
Figure 2.
Figure 2.
1H NMR (CD3NO2): (a) L1 (*); (b) cis-Pt(dppf)(OTf)2; (c) 2; (d) 1; and (e) DOSY NMR of 1. (*) 1H NMR of ligand L1 was recorded in a mixture of CD3NO2/CDCl3 (2/1).
Figure 3.
Figure 3.
ESI-MS of self-assembly 1 in CH2Cl2 (C = 10−3 M).
Figure 4.
Figure 4.
Molecular force field (MM+) model of square 1: (a) front view and (b) side view.
Figure 5.
Figure 5.
(a) Cyclic voltammogram and (b) deconvoluted cyclic voltammogram of ligand L1 (C = 10−3 M, CH3CN/CH2Cl2, 0.1 M nBu4NPF6, 100 mV·s−1, Cgr) and of squares 1 and 2 (C = 5 × 10−4 M, CH3CN, 0.1 M nBu4PF6, 20 mV·s−1, Cgr), V vs Fc/Fc+.
Scheme 1.
Scheme 1.
Synthesis of ligand L1: 4-Iodopyrine (5 equiv.), Pd(OAc)2 (0.25 equiv.), P(tBu)3·HBF4 (0.75 equiv.) Cs2CO3 (5 equiv.), Dioxane, reflux, 24 h, 71%.
Scheme 2.
Scheme 2.
Synthesis of polygons 1 and 2: (A) cis-M(dppf)(OTf)2 (2 equiv.), nitromethane, 50 °C; for 1: M = Pt, 2 h, 91%; for 2: M = Pd, 5 min, 87% and (B) Hypothetical alternative structure
See this image and copyright information in PMC

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