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SELFPHOS Report Summary

Project ID: 339072
Funded under: FP7-IDEAS-ERC
Country: Germany

Mid-Term Report Summary - SELFPHOS (Design and Self-Assembly of Organometallic-Based Polypnictogen Materials and Discrete Nano-sized Supramolecules)

In principle, the project focusing the self-assembly of phosphorus-rich coordination compounds to supramolecular aggregates as extended networks and as molecular supramolecules is divided into two major parts, with a more general, introductory, part (i) facilitating the access to the two subsequent, specialized, parts: (ii) the charged moiety approach, and, (iii) the neutral moiety approach. In the following, a brief description of the general achievements during the first 30 months of this project is presented.
(i) In the introductary, general, part – on top of the specialized scopes - the synthesis of new starting materials for the tasks (ii) and (iii) is focused. To this purpose, in an extensive study, we succeeded in introducing a new class of polyphosphorus ligand complexes containing, instead of the usual cyclopentadienyl (CpR) ligands, ß-diketaminato (nacnac) ligands (paper no. 10). The potential of these compounds for supramolecular aggregation will be a topic for future research. Moreover, for the first time, we gained access to unprecedented triarsolyl and tetraarsolyl salts, which will be introduced as CpR analogous ligands for supramolecular purposes (paper no. 9).
(ii) Also for the first time, we were able to show that our unique concept to generate organometallic-organic hybrid materials (OM-O-HM) starting from organic linkers, metal cations and En ligand complexes (E = group 15 element) successfully resulted in the formation of unprecedented 3D networks (paper no. 2). Moreover, we also succeeded in the selective synthesis of a series of new ‘ladderlike’ 1D OM-O-HM by using, for the first time, flexible organic linkers (usually these linkers do not give selective material formation; paper no. 13). Additionally, we could extend our novel approach to organometallic-organic hybrid materials with inorganic notes to synthesize a 2D organometallic-inorganic-organic hybrid polymer (paper no. 15). Furthermore, we extended this chemistry by introducing different linking nodes to generate 3D polymers. Therefore, as a new 3D linker, the novel complex [(CpMn)4(µ3-P)4] was synthesized and used for aggregations (paper no. 3). Beyond that, the 1,2,4-triphospholyl anions themselves (paper no. 1) and the 1,3-diphosphaferrocens as the 1,1´,2,3´,4-pentaphosphaferrocens (paper no. 14) were successfully applied for a 2D and 3D linkage, respectively, of self-assembled aggregates with Cu(I) halides.
(iii) In the field of supramolecular nanospheres and aggregates, we could publish a full paper focusing the encapsulation and release of guest molecules in a spherical ball changing its porosity and the shape by external stimulations (published as a HOT paper in the journal Chem. Eur. J.; paper no. 5, and serving as the proof-of principle of one important background of our project). Moreover, we could report on three different principles to construct huge superspheres that do not follow the Fullerene topology: The first one based on the use of Cu(I)iodide as a building block in the reaction with pentaphosphaferrocenes to give a superball consisting of 12 pentaphosphaferrocenes and 54 CuI moieties (paper no. 4). Due to the extended CuI network, no 6-membered rings are located around the 5-membered rings of the P atoms of the pentaphosphaferrocenes and also no larger guest molecules could be enclosed (only solvent molecules). The second approach based on the use of Cu(II) halides, namely CuBr2, in the reaction with pentaphosphaferrocene to give the first rugby-ball-like supersphere revealing a soluble molecular aggregate with an outer dimension of 3.7 x 4.6 nm, coming close in size to small proteins like hemoglobin (cited by the Forbes journal USA; paper no. 6). The third principle based on the use of bulky CpBig (pentaphenylcyclopentadienyl) containing pentaphosphaferrocene in the reaction with CuBr to give a unique multi-shell (onion-like) cluster revealing an unprecedented fullerene C140 topology, a molecule which has so far been unknown in carbon chemistry (paper no. 8). The diameter of this sphere reaches 3.5 nm. This paper was cited by the GDCh journal ‘Nachrichten aus der Chemie’ (issue 12, 2015). A review article was written and published (paper no. 12) to report on all our achievements in spherical supramolecular chemistry. Furthermore, by using [(Cp*Mo)2(P6)] as a starting material in the reaction with ‘naked’ cations such as Cu, Ag and Tl, we were able to obtain, for the first time, aggregations of the cyclo-P6 rings with the Tl cations showing a graphene-like arrangement in a monolayer, covert by Cp* ligands from both sides (paper no. 7 in Angew. Chem. Int. Ed.). Unprecedented graphene-like arrangements were also obtained by using the same starting material ([(Cp*Mo)2(P6)]) in the reaction with Cu(I) halides (paper no. 11). Therefore, the possibility of mimicking monolayered graphene by cyclic-P6 moieties was impressively shown.

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