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Dinuclear Rhenium Complexes with a Bridging Helicene-bis-bipyridine Ligand: Synthesis, Structure, and Photophysical and Chiroptical Properties.

ABSTRACT: By attaching pyridine groups to a diaza[6]helicene, a helical, bis-ditopic, bis-N N-coordinating ligand can be accessed. Dinuclear rhenium complexes featuring this bridging ligand, of the form [{Re(CO)₃ Cl}₂ (N N-N N)], have been prepared and resolved to give enantiopure complexes. These complexes are phosphorescent in solution at room temperature under one- and two-photon excitation. Their experimental chiroptical properties (optical rotation, electronic circular dichroism and circularly polarized emission) have been measured. They show, for instance, emission dissymmetry factors of c.a. ±3x10^-3 . Quantum-chemical calculations indicate the importance of stereochemistry on the optical activity, pointing towards further design improvements in such types of complexes.

SUBMITTER: Saleh N

PROVIDER: S-EPMC7745256 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPT) bridged dinuclear rhenium(I) tricarbonyl halide complexes with the composition (mu-TPT)[ReX(CO)(3)](2) (3, X = Cl; 4, X = Br) can be made either by one-pot reaction of TPT with 2 equiv of [ReX(CO)(5)] (X = Cl and Br) in chloroform or by reacting mononuclear [ReX(CO)(3)(TPT)] (2) (1, X = Cl; 2, X = Br) with an excess amount of [ReX(CO)(5)]. Crystal data are as follows. 1: monoclinic, P2(1)/c, a = 11.751(1) A, b = 11.376(1) A, c = 15.562(2) A, beta = 103.584(2) degrees, V = 2022.0(4) A(3), Z = 4. 2: monoclinic, P2(1)/c, a = 11.896(1) A, b = 11.396(1) A, c = 15.655(1) A, beta = 104.474(2) degrees, V = 2054.9(3) A(3), Z = 4. 3: triclinic, P1, a = 11.541(2) A, b = 12.119(2) A, c = 13.199(2) A, alpha = 80.377(2) degrees, beta = 76.204(3) degrees, gamma = 66.826(2) degrees, V = 1642.5(4) A(3), Z = 2. Crystals of 4 crystallized from acetone: triclinic, P1, a = 11.586(5) A, b = 12.144(5) A, c = 13.364(6) A, alpha = 80.599(7) degrees, beta = 76.271(8) degrees, gamma = 67.158(8) degrees, V = 1678.0(12) A(3), Z = 2. Crystals of 4' are obtained from CH(2)Cl(2)-pentane solution: monoclinic, C2/c, a = 17.555(4) A, b = 15.277(3) A, c = 13.093(3) A, beta = 111.179(3) degrees, V = 3274.0(12) A(3), Z = 4. By contrast, similar reactions in the presence of methanol yielded complexes with the composition [mu-C(3)N(3)(OMe)(py)(2)(pyH)][ReX(CO)(3)](2) (5, X = Cl; 6, X = Br). Crystal data for 5: monoclinic, C2/c, a = 26.952(2) A, b = 16.602(1) A, c = 14.641(1) A, beta = 116.147(1) degrees, V = 5880.5(8) A(3), Z = 8. 6: monoclinic, C2/c, a = 27.513(3) A, b = 16.740(2) A, c = 14.837(2) A, beta = 116.925(2) degrees, V = 6092.8(10) A(3), Z = 8. An unusual metal-induced methoxylation at the carbon atom of the triazine ring of the bridging TPT ligand was observed. The nucleophilic attack of MeO(-) on C(3) results in a tetrahedral geometry around the carbon atom. Concomitantly, the uncoordinated pyridyl ring is protonated and rotated into a perpendicular orientation relative to the central C(3)N(3) ring. Reaction of TPT with [NEt(4)](2)[ReBr(3)(CO)(3)] in benzene-methanol resulted in an unexpected dinuclear complex 7, with formulation [mu-C(3)N(3)(OMe)(py)(3)][Re(CO)(3)][ReBr(CO)(3)]. The methoxylated TPT ligand functions simultaneously as a tridentate and bidentate ligand with two fac-Re(CO)(3)(+) cores. Crystal data for 7: monoclinic, P2(1)/n, a = 12.114(1) A, b = 14.878(1) A, c = 15.807(1) A, beta = 104.601(1) degrees, V = 2756.9(3) A(3), Z = 4.

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Dinuclear Rhenium Complexes with a Bridging Helicene-bis-bipyridine Ligand: Synthesis, Structure, and Photophysical and Chiroptical Properties.

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