Do the bridging angle affect the luminescent properties of [(CO)3(phen)Re(µ-OH)Re(phen)(CO)3]+?. An experimental and computational study on three polymorphs

C. Muñoz (1) , M. Saldías (1) , P. Oyarzún (1) , J.-Y. Saillard (2) , J.-R. Hamon (2) , G. Calvez (2) , N. Pizarro (1) , A. Vega (1)

1 UNAB - Universidad Andrés Bello [Santiago]
2 ISCR - Institut des Sciences Chimiques de Rennes

The reaction of [ReIBr(CO)3(THF)]2 with phenanthroline in solution leads to the diimine rhenium(I)tricarbonyl [(phen)Re(CO)3Br] and the dimer [(CO)3(phen)Re(µ-OH)(phen)Re(CO)3]+Br− (1+Br−) as a by-product (~5% yield). This latter bimetallic compound crystallizes as a mixture of three polymorphs, with variable amount of solvent 1+Br−·CHCl3 (triclinic and orthorhombic) and 1+Br−·2(CHCl3) (triclinic). Rietveld analysis showed 38, 54 and 8% of 1+Br−·CHCl3 (triclinic), 1+Br−·CHCl3 (orthorhombic) and 1+Br−·2(CHCl3) (triclinic) respectively. The 1+ cation shows two [ReI(phen)(CO)3]+ units connected by means of a central hydroxyl group. Noteworthy, the bridging Re–O–Re angle varies between 130.9(7)° to 140.7(2)° along the polymorphic series. UV–Vis spectrum for the 1+ shows a broad absorption band around 390 nm in CH2Cl2 which has been attributed to has MLCT character (Re(dπ) → π*(phen)) as confirmed by DFT. Excitation at 405 nm in solution leads to emission at 595 nm (DCM), 605 nm (DMF) and 625 nm (CH3CN). The emission follows a mono-exponential law of decay and has lifetime of 405.8 ns (DCM). The solid-state polymorphic mixture absorbs around 460 nm. Excitation of the solid at 320 nm leads to emission with a maximum at 575 nm, which follow a bi-exponential law of decay with two components, a short one τ1 of 27.0 ns and longer one τ2 of 178.5 ns. These results suggest that the emitting state does not vary as function of the molecular geometry.

Keywords: Rhenium; Bridging angle; Density functional calculations; Luminescence; Polymorphism

Domains: Chemical Sciences; Coordination chemistry; Chemical Sciences; Theoretical and/or physical chemistry

C. Muñoz, M. Saldías, P. Oyarzún, J.-Y. Saillard, J.-R. Hamon, et al.. Do the bridging angle affect the luminescent properties of [(CO)3(phen)Re(µ-OH)Re(phen)(CO)3]+?. An experimental and computational study on three polymorphs. Polyhedron, 2019, 173, pp.114150. ⟨10.1016/j.poly.2019.114150⟩. ⟨hal-02367954⟩