Peripherally η¹-Platinated Organometallic Porphyrins as Building Blocks for Multiporphyrin Arrays

Abstract

The modification of peripherally metalated meso-η 1 -platiniometalloporphyrins, such as trans-[PtBr(NiDAPP)(PPh 3 ) 2 ] (H 2 DAPP ) 5-phenyl-10,20-bis(3′,5′-di-tert-butylphenyl)porphyrin), leads to the analogous platinum(II) nitrato and triflato electrophiles in almost quantitative yields. Self-assembly reactions of these meso-platinioporphyrin tectons with pyridine, 4,4′-bipyridine, or various meso-4-pyridylporphyrins in chloroform generate new multicomponent organometallic porphyrin arrays containing up to five porphyrin units. These new types of supramolecular arrays are formed exclusively in high yields and are stable in solution or in the solid state for extended periods. They were characterized by multinuclear NMR and UV-visible spectroscopy as well as high-resolution electrospray ionization mass spectrometry.

Electrocatalysis on tetraruthenated nickel and cobalt porphyrins electrostatic assembled films

“…M(4-TRPyP) and M(3-TRPyP) were prepared by reacting M(3-or 4-TPyP) and [Ru(bpy) 2 Cl 2 ], where bpy = 2,2 0 -bipyridine (1:4 molar ratio) in glacial acetic acid, following the previously described procedure [37].…”

“…The coordination of [Ru(bpy) 2 Cl] + to the pyridyl Natoms of nickel or cobalt meso-tetra(3-pyridyl)porphyrins, M(3-TPyP), is a convenient way to enhance the electrochemical and electrocatalytic properties of these compounds. In contrast with the M(4-TRPyP) [34] species in which the ruthenium complexes are always in plane, these peripheral groups are more stabilized in an out-of-plane conformation in the M(3-TRPyP) isomer.…”

“…Supramolecular chemistry [1][2][3][4][5][6][7][8][9][10] is contributing to the advancement of nanotechnology [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] providing the most effective bottom-up strategy for the preparation of nanomaterials. Among the classes of compounds that can be used to build-up such systems, metalloporphyrins are particularly relevant considering the great variety of functions they play in biological systems [27][28][29].…”

[1,2,3]Triazolo[4,5‐b]porphyrins: New Building Blocks for Porphyrinic Materials

“…[25] These fully conjugated porphyrin systems have planar structures and display drastically red-shifted absorption spectra that reach into the far-IR region, which reflects the extensive p conjugation over the molecules. Other very interesting linear, [26][27][28][29] dendritic, [30] and cyclic [31,32] multiporphyrin systems, as well as organometallic porphyrin arrays [33] have been published in recent years. All of these well-defined multiporphyrin arrangements are interesting for application such as molecular photonic and electronic wires.…”

Selective meso-monobromination of 5,15-diarylporphyrins via organopalladium porphyrins

“…Recently we reported the first examples with chelating diamines [6] and the use of this fragment for the generation of multi-porphyrin coordination arrays [7] The NBS bromination [1a] of the unsubstituted 5,15-diphenylporphyrin free base H 2 DPP, while very rapid, is not selective, and use of one equivalent of NBS results in a mixture of the desired 5-bromoporphyrin, the 5,15-dibromoporphyrin and unreacted H 2 DPP. On the other hand, dibromination of most diarylporphyrin substrates can be readily achieved in near quantitative yields using 2.1 equivalents of NBS.…”