Global climate change urgently demands development of carbon-zero/neutral energy sources.¹ The conversion of energy-poor feedstock such as water to energy rich molecules like H₂, driven by renewable energy, has emerged as a promising pathway for producing future fuels. As these conversions are energy intensive, catalysts are required for effective conversion of such feedstock into eco-fuels.²

The di-copper(II) analogue, [Cu^II₂(bis-L^Et)](BF₄)₂ (2), of the previously reported mono-copper(II) complex [Cu^IIL^Et]BF₄ (1) which resulted in long lived electrocatalytic hydrogen evolution reaction (HER)³, has been prepared, characterised and tested for electrocatalytic HER (Figure). The new bis-macrocycle, bis-HL^Et, was formed from two HL^Et Schiff base macrocycles being connected by selective alkylation of the less sterically hindered secondary alkyl amine group (NH) of each, using α,α’-dibromo-para-xylene to form a linker between them. The desired dicopper(II) complex, [Cu₂^II(bis-L^Et)](BF₄)₂⋅4H₂O (2⋅4H₂O), was readily prepared, as a yellowish brown solid in 82% yield. SCXRD on yellow-brown crystals of [Cu^II₂(bis-L^Et)](BF₄)₂⋅2MeCN (2⋅2MeCN) revealed both copper(II) centres are square planar with a very similar copper(II) coordination environment to that of square planar 1. Although dicopper(II) complex 2 is easier to reduce than the analogous monocopper(II) complex 1 in MeCN (E_1/2(ΔE): 2 -1.20(0.12) V, 1 -1.39(0.09) V, vs 0.01 M AgNO₃/Ag), electrocatalytic HER testing of dicopper complex 2⋅4H₂O, in MeCN with 80 equivalents of acetic acid, revealed it was inactive, in stark contrast to the high and ongoing activity of 1 under the same conditions. So two is definitely not better than one metal ion in this case. Rather, it may be that the presence of an NH group in the macrocycle of 1, which is absent in the bis-macrocycle of 2 (due to alkylating that NH to link the two macrocycles), may be key to the HER activity seen for 1.

References

1. Duan, C.; Yu, Y.; Xiao, J.; Li, Y.; Yang, P.; Hu, F.; Xi, H., Recent advancements in metal–organic frameworks for green applications. Green Energy Environ. 2021, 6 (1), 33-49.
2. Dalle, K. E.; Warnan, J.; Leung, J. J.; Reuillard, B.; Karmel, I. S.; Reisner, E., Electro- and Solar[1]Driven Fuel Synthesis with First Row Transition Metal Complexes. Chem. Rev. 2019, 119 (4), 2752-2875.
3. Abudayyeh, A. M.; Schott, O.; Hanan, G. S.; Brooker, S., Copper catalysts for photo- and electro-catalytic hydrogen production. Inorg. Chem. Front. 2021, 8, 1015-1029.