Data for all figures in the manuscript (which is Open Access). In the excel .xls files are all the data for each suitable figure in the Open Access paper.

The axes are labelled in these files.

Fig. 2 | Plasmonic activity of the four NR types. Histograms of the dominant coupled mode wavelengths from dark-field spectra of >200 NRs and average spectra from each bin of (a) Au-on-Au, (b) Au-on-Pd, (c) Pd-on-Au, and (d) Pd-on-Pd NRs. Black dotted curves are Gaussian fits of histograms and the centre wavelength (centre) from each fit is noted at the top. (e) Representative dark-field spectrum of each single NR. Normalized SERS spectra of (f) 4-BTP and (g) NC-BPT measured over 5min from each NR under ambient conditions without 2nd reactant, for 100 µW laser. From bottom to top: Au-on-Au (orange), Pd-on-Au (darker orange), Au-on-Pd (brown), Pd-on-Pd (grey), and DFT-simulated spectrum of isolated molecule (dashed).

Fig. 3 | SERS spectra from each NR type in solution of CPBA and K2CO3. (a) Colourmaps of repeated SERS spectra (300 frames @ 1 s integration times). (b) Initial (t = 1 s, blue) and final (t = 5 min, red) SERS spectra from colourmaps in (a). (c) SERS spectra normalized by maximum intensity in solution over 5 min for each NR type. (d) SERS spectra of blue-shaded region in (c). From bottom to top: Au-on-Au (orange), Pd-on-Au (darker orange), Au-on-Pd (brown), and Pd-on-Pd (grey).

Fig. 4 | Progress of SERS peak intensity ratio during Suzuki-Miyaura coupling reaction, comparing NRs to monolayer NP aggregates (MLaggs). (a,b) Dynamics of peak intensity ratio R_21 of 1572 cm-1 NC-BPT mode (ν_2) to 1532 cm-1 mode of 4-BTP (ν_1) for (a) NRs and (b) MLaggs (note multiplied by x5). (c,d) Peak intensity ratio of 2255 cm-1 NC-BPT mode (ν_3) to ν_1 for (c) NRs and (d) MLaggs. (e) Laser-driven catalytic conversion yields at t = 1 s (darker bars) and t = 5 min (for NRs) or t = 30 min (MLaggs) (lighter hatched bars). (f,g) Slow rate constants (k_slow) fitted from (a-d) using two-step kinetics. (h) Schematic molecular alignment in NPoM and MLagg geometries, showing thiols bound to one or both facet surfaces. Labels 1-6 as defined in (a,b).

Suppl. Fig. 2 | Cyclic voltammograms of Au (0 ML Pd) and Au@Pd NPs with different coverages of Pd Suppl. Fig. 6 | Time-series SERS spectra of 4-BPT from individual NRs in ambient conditions Suppl. Fig. 7 | Time-series SERS spectra of NC-BTP from individual NRs in ambient conditions Suppl. Fig. 8 | Laser-power dependent SERS spectra Suppl. Fig. 9 | DFT-calculated vibrational modes Suppl. Fig. 10 | SERS spectra from each NR type in solution of phenylboranic acid (PBA) and K2CO3 Suppl. Fig. 11 | Lorentzian peak fitting results for NRs Suppl. Fig. 12 | Progress of 1550 cm-1 mode intensity during the reaction Suppl. Fig. 14 | Averaged SERS of MLaggs before and after reaction Suppl. Fig. 15 | Time-series SERS spectra colormaps from MLaggs during reaction Suppl. Fig. 16 | Lorentzian peak fitting results for MLaggs Suppl. Fig. 17 | SERS spectra with 785 nm laser excitation Suppl. Fig. 18 | Peak analysis results of Au and Pd MLaggs at different laser powers Suppl. Fig. 20 | DFT-calculated projected density of states (PDOS) of surface atoms Suppl. Fig. 21 | Electrochemical characterization of Au@Pd films