An Expanded Porphycene with High NIR Absorptivity That Stabilizes Two Different Kinds of Metal Complexes

Abstract

A new expanded porphycene with 26 π-electrons has been prepared by the McMurry coupling of 1,4-bis(3,4-diethyl-2-pyrryl)benzene dialdehyde. Expansion of the porphycene framework provides a ligand capable of stabilizing a bis(rhodium) and a monoruthenium complex. These new porphycene derivatives absorb strongly in the NIR spectral region, with appreciable absorptivity up to 1300 nm. On the basis of their ground- and excited-state spectroscopic features and structural parameters, both the free-base system and the bis(rhodium) complex are considered to be Hückel-type aromatic systems. This conclusion is supported by DFT calculations.

Expanding the Porphycene Core: Modification and Metalation

“…Our efforts towards obtaining an expanded porphycene with a larger central cavity and extended π-electronic pathway began with the use of para-substituted dipyrrolyl benzene (6) precursor previously prepared by Setsune and coworkers (Scheme 2). [40][41][42] Compound 6 was formylated using Vilsmeier-Haack conditions and then subjected to a modified reductive McMurry coupling, followed by oxidation with 2,3-dichloro-5,6-dicyano-para-benzoquinone (DDQ).…”

An Expanded Porphycene with High NIR Absorptivity That Stabilizes Two Different Kinds of Metal Complexes

“…Taken in concert, these spectroscopic features provide further evidence for the [4 n+ +2] Hückel-type aromaticity proposed for 5 and 8. [27] In af urther test of 5 as al igand, it was treated with [Ru(Cp*)(CH 3 CN) 3 ][PF 6 ]. In analogy to prior work, [26] this was expected to afford as andwich-type organometallic complex.…”

“…Displacementellipsoids set at 50 %probability.Substituents and hydrogen atoms have been omitted for clarity. [27] Angewandte Chemie Communications 2578 www.angewandte.org…”

Mechanistic Study on Ring‐Contracting Skeletal Rearrangement from Porphycene to Isocorrole by Experimental and Theoretical Methods

“…There have been several reports on ring contraction of aromatic compounds in the field of porphyrinoids, 1) porphyrin to corrole contraction by the complexation of rhenium(V)[3a] or silver(III)[3b] 2) 21‐oxaporphyrin to 21‐oxacorrole contraction by the addition of phosphoryl chloride, 3) ring contraction from porphycene to meso ‐formyl isocorrole, 4) ring contraction of the expanded porphycene upon ruthenium metallation, 5) ring contraction of pyrihexaphyrin upon UO 2 + complexization, etc . However, such examples are limited and most of the reaction mechanisms of these unique reactions have not been revealed.…”