Preparative Routes to Luminescent Mixed-Ligand Rhenium(I) Dicarbonyl Complexes

Abstract

A series of mixed-ligand 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) rhenium(I) dicarbonyl complexes that are emissive in fluid solution has been prepared, which includes a new class of the type cis-[Re(CO)2(P-P)(N-N)]+ (where P-P is a chelating diphosphine and N-N is a chelating polypyridine ligand). The four synthetic routes that have been developed rely on either reactive triflate displacement or abstraction of labile chloro ligands, followed by the use of the strong trans-labilizing effect of P donors or direct use of the trans effect of P donors. The spectroscopic, photophysical, and electrochemical properties of these new complexes systematically vary with the net donor ability of the ligands in the coordination sphere, as shown by correlations with Lever's E(L) parameters. Lifetimes and quantum yields of the bipyridine complexes encompass a broad range, 25-1147 ns and ca. 0.002-0.11, respectively.

The photochemistry of rhenium(i) tricarbonyl N-heterocyclic carbene complexes

“…10 In comparison to their photophysics, the photochemistry of these complexes has received relatively limited attention. [12][13][14][15][16][17][18] By exploiting the strong trans effect of phosphine and phosphite ligands, examples of rhenium(I) dicarbonyl species were photochemically synthesized. [12][13][14][15][16][17][18] By exploiting the strong trans effect of phosphine and phosphite ligands, examples of rhenium(I) dicarbonyl species were photochemically synthesized.…”

Dual Emission of a Novel (P,N) ReI Complex: A Computational and Experimental Study on [P,N-{(C6H5)2(C5H4N)P}Re(CO)3Br]

“…50 In this context, both factors may be associated with an increase of the vibrational overlap between the ground-and excited-state, resulting from the combination of stretching modes present in this molecule: ν(Re-P), ν(Re-N), ν(Re-Br) and ν(C-O), with the concomitant faster radiationless decay. 2,51 Taking into account all the possible deactivation pathways upon excitation described above, a schematic energy diagram is proposed (Scheme 2).…”

“…[1][2][3][4] These structural changes have direct effect on the excited states character. 5 Compared to N,Ndiimines, P,N-mixed complexes have been less studied so far, despite the fact that the presence of an heteroatom with different properties, i.e.…”

Synthesis and reactivity of [ReBr2(NCCH3)2(CO)2]−: A new precursor for bioorganometallic chemistry

“…In these studies the substitution chemistry of fac-[Re(CO) 3 (L)] + was explored under vigorous reaction conditions [14]. In our case we prepared a new precursor with which we investigated several substitution reactions with mono-or bidentate ligands to understand its binding properties and chemical behaviour.…”