Photoinduced behaviour of N,N-bidentate manganese(I) and rhenium(I) tricarbonyl complexes for singlet oxygen generation and CO release.

Abstract

The combined action of singlet oxygen (1O2) and photoinduced carbon monoxide (CO) released by tricarbonyl metal complexes is a promising synergic treatment against multi-resistant bacterial infections. In this work, we explore the use of a polydentate ligand (bpm = 2,2-bipyrimidine) that offers the opportunity to accommodate two metal centers exhibiting both singlet oxygen generation and carbon monoxide releasing properties in a single molecule. A series of monometallic ([(bpm)M(CO)3Br]; M = Mn, Re) and homo or hetero bimetallic ([Br(CO)3M(bpm)M'(CO)3Br]; M = Mn, Re) compounds were synthesized in moderate to good yields by modulating the metal precursor or the stoichiometry, also the syn:anti isomers ratio for the bimetallic complexes was dependent on the experimental conditions used. DFT modelling shows the anti-isomer is more stable than the syn-isomer by less than 8 kJ mol-1, which is consistent with those experimentally observed in terms of majority product and the effect of experimental conditions over the anti-syn ratio. The HOMO-LUMO gap is lower for the mono and bimetallic rhenium(I) compounds compared to the values for the manganese(I) analogues, while the heterometallic complex shows intermediate values for the anti-isomer. The photophysical characterization shows typical absorption and emission bands with MLCT character. In addition, CO-release and 1O2 generation quantum yields were evaluated for the monometallic Mnbpm and Rebpm homologues and compared with values obtained for the homo- and hetero-bimetallic complexes. Interestingly the replacement of a Mn(CO)3Br moiety in MnbpmMn by a Re(CO)3Br one makes the heterometallic MnbpmRe molecule a molecular oxygen sensitizer and partially retaining its carbon monoxide releasing ability.