Unique Type of BF₂‐Capped Tetraoxobenzene π‐Complexes of “Cp*M”: Novel Organometallic Backbones for the Self‐Assembly of Porous Networks

Abstract

The synthesis of two novel organometallic π complexes of a BF 2 -capped tetraoxobenzene (TOB) of the general formulae [Cp*M-η 6 -{BF 2 -TOB-BF 2 }] (M = Ir, 2a; M = Rh, 2b) is reported together with their molecular structures ascertained by single-crystal X-ray diffraction studies. Complexes 2a and 2b are isostructural and show the formation of 3D porous supramolecular networks. Interestingly the supramolecular net-[a]

Organocopper(III) Phenanthriporphyrin—Exocyclic Transformations

“…Significantly, the C(5)–O (1.208(3) Å) and C(6)–O (1.211(3) Å) distances of 2 -H + are markedly shorter than the C(5)–O (1.300(8) Å) and C(6)–O (1.315(9) Å) bond lengths of 2 ‑Cu‑BF 2 + . These values are in the low range limit of bond length values detected for catecholborates, which vary from 1.310 to 1.389 Å. − Thus, the boron­(III) coordination converts the double CO bonds into essentially single bonds via an intramolecular rearrangement.…”

Serendipitous Self-Assembly of Cyclometalated Complexes through Hydrogen Bonds: Dimers or Chains within Compact or Porous Networks

“…A PLATON analysis allowed us to estimate the potential free volume as 8.3%. To our knowledge, examples in the literature of such hexagonally shaped hydrophobic channels are rather scarce. , In the case of 8b , it seems probable that there is a link between the intermolecular CH/π interactions mentioned above and this original channeled structure. Indeed, the striking difference between the networks generated respectively by 8a , b is surprising, given the close structural similarities usually observed between the isoelectronic Rh III and Ir III cations (such as those that were found with 7a , b ).…”