Reacting the dipp NBA ligand with 1 equiv of Mg 0 turnings in THF (Scheme 2) led to the slow formation of a dark red solution, from which 1 was isolated as a red solid in 73% yield. Analysis of the 1 H-NMR spectrum revealed full conversion of the ligand, along with several resonances consistent with the two halves of the naphthyridine motif being equivalent (see ESI Section 1.2). The singlet at δ = 6.61 ppm, attributed to the methine linker, and the two doublets at δ = 5.70 and 4.99 ppm ( 3 J H,H = 7.6 Hz), attributed to the naphthyridine protons, are all significantly shifted upfield, consistent with a reduced character of the naphthyridine backbone. A single septet for the methine protons of the dipp i-Pr groups at δ = 3.43 ppm was observed and two doublets at δ = 1.53 and 0.98 ppm ( 3 J H,H = 6.8 Hz) were observed for the magnetically inequivalent methyl group protons of the dipp substituents. THF, 48 h, RT Single crystals suitable for analysis by X-ray diffraction were grown by layering a saturated THF solution of 1 with pentane. The dimeric nature of 1 was revealed in the solid-state structure (Figure ), with the two naphthyridine motifs being twisted at 67.9(10)° (dihedral angle between the two planes defined by N11-C61-N21 and N12-C62-N22, see ESI Figure ) with respect to each other to accommodate a Mg centre on each side. The two-electron reduction of each ligand is evident through the bond metrics, showing a contraction of the C methine -C napy and an elongation of the C methine -N dipp bonds compared to the free ligand (see ESI Table ). The C methine -C napy bond lengths on either side of both naphthyridine moieties are identical within error, consistent with the delocalised nature of the ligand-centred reduction, which agrees with the 1 H-NMR spectrum and is also found in related twoelectron reduced naphthyridine systems. With the reduced dipp NBA-synthon 1 in hand, we set out to install the germylene in the reduced naphthyridine pocket. Treatment of a 3:1 1,4-dioxane:Et 2 O solution of 1 with 2 equiv of the Ge(II) precursor GeCl 2 •diox (diox = 1,4-dioxane) resulted in the formation of polymeric MgCl 2 diox and compound 2, which was isolated as a red solid in 68% yield. H-and 13 C{ 1 H}-NMR analysis of 2 in C 6 D 6 revealed a resonance count consistent with the loss of the previously observed symmetry in 1 (see ESI Section 1.3). Two sets of naphthyridine resonances are observed, one at δ = 8.14 and 7.02 ppm ( 3 J H,H = 7.7 Hz), and another further upfield at δ = 6.55 and 6.06 ppm ( 3 J H,H = 9.1 Hz). Additionally, two singlets are observed at δ = 8.40 and 6.79 ppm, which we attribute to the protons attached to the pendant methine carbons. Combined, these observations are consistent with two distinct binding pockets in 2. One pocket retains its aromaticity, as evidenced by the more downfield set of naphthyridine protons and the singlet at δ = 8.40 ppm, which is consistent with the aldimine character of the methine proton.