10027-33-5Relevant academic research and scientific papers
Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces
Shi, Yanhui,Sánchez-Molina, Irene,Cao, Changsheng,Cook, Timothy R.,Stang, Peter J.
, p. 9390 - 9395 (2014/07/21)
Multicomponent self-assembly, wherein two unique donor precursors are combined with a single metal acceptor instead of the more common two-component assembly, can be achieved by selecting Lewis-basic sites and metal nodes that select for heteroligated coordination spheres. Platinum(II) ions show a thermodynamic preference for mixed pyridyl/carboxylate coordination environments and are thus suitable for such designs. The use of three or more unique building blocks increases the structural complexity of supramolecules. Herein, we describe the synthesis and characterization of rectangular prismatic supramolecular coordination complexes (SCCs) with two faces occupied by porphyrin molecules, motivated by the search for new multichromophore complexes with promising light-harvesting properties. These prisms are obtained from the self-assembly of a 90° Pt(II) acceptor with a meso-substituted tetrapyridylporphyrin (TPyP) and dicarboxylate ligands. The generality of this self-assembly reaction is demonstrated using five dicarboxylate ligands, two based on a rigid central phenyl ring and three alkyl-spaced variants, to form a total of five free-base and five Zn-metallated porphyrin prisms. All 10 SCCs are characterized by 31P and 1H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry, confirming the structure of each self-assembly and the stoichiometry of formation. The photophysical properties of the resulting SCCs were investigated revealing that the absorption and emission properties of the free-base and metallated porphyrin prisms preserve the spectral features associated with free TPyP.
The advantage of covalent capture in the combinatorial screening of a dynamic library for the detection of weak interactions
Martin, Marco,Gasparini, Giulio,Graziani, Matteo,Prins, Leonard J.,Scrimin, Paolo
scheme or table, p. 3858 - 3866 (2010/09/05)
In this paper we address the advantage of screening a dynamic library by covalent capture in comparison with an approach in which the target is not covalently bound to the molecular receptor. The aim is the selection of recognition units for the binding of an anion (or polyanion) by relatively weak binding interactions, a situation typically found in supramolecular chemistry. To compare the two approaches, two model systems have been studied both based on the functionalization of a molecular platform, by reversible imine formation. In the case of the noncovalently bound substrate, the platform P1 is a trisubstituted benzene unit, 2,4,6-trimethylbenzene-1,3,5-tricarbaldehyde, to select: three recognition arms for the binding of the trisodium salt of benzene-1,3,5tricarboxylate. For the covalent-capture-based approach the platforms P2 and P4 are benzene derivatives with a tethered phosphonate target (tetrabutylammonium 2-formylphenyl ethylphosphonate) for the selection of a single recognition unit. The library of recognition elements comprises phenyl and ammonium-functionalized amines. We show that the selection of recognition units for the binding of the substrate with weak to medium, binding constants may encounter, by using a noncovalently bound substrate, serious problems. This is because the best conditions for the amplification of the library, that is, a large excess of variable recognition elements and target, lead also to competitive binding of the elements not bound to the platform, with the target. This may result in negligible amplification of the best-fit members of the library. In contrast, upon tethering the target to the platform and using the covalent-capture strategy for the selection of the recognition elements, significant amplification is observed, even for systems with much lower binding constants. Although competition with excess recognition units may also become an issue in the case of the tethered target, there is a way to overcome the problem by working at low concentrations.
