The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules29194608/s1, Figure S1. IR spectra of compounds 1f,g and complexes 2f,g. Figure S2. 1H NMR and 13C{1H] NMR spectra of compounds 1f–g. Figure S3. Optimized structures of compounds 1f–g and ligands NHCβ−Me and NHCGlyGly. Figure S4. Optimized structures of complexes: (a) [Ag(NHCβ−Me)2]3−; (b) [Ag(NHCGlyGly)2]3−; and (c) Na3[Ag(NHCβ−Me)2], 2g. Two views of each complex are shown. Figure S5. Comparison of the calculated and experimental 1H and 13C NMR spectra for 2f. Figure S6. Comparison of the calculated and experimental 1H and 13C NMR spectra for 2g. Table S1. Comparison of experimental selected structural parameters of complexes 2c and 2g with the calculated parameters for the anions [Ag(NHCR)2]3− of these complexes. Table S2. Selected structural data of 1f, 2c and 2g. Bond distances (Å) and angles (°). Table S3. Specific rotations [α]D for complexes 2. Figure S7. Crystal packing views of complex 1f. Figure S8. Crystal packing views of complex 2c. Figure S9. Crystal packing views of complex 2g viewed along b axis. Table S4. Optimized structures of complexes [Ni(CO)3(NHCR)]2− and their calculated properties. Figure S10. Correlation between calculated TEP values (νCO) of the NHCR carbenes and the MO energy of the σ lone pair orbitals. Table S5. Percent buried volume, %Vbur, of NHCR ligands. Figure S11. Selected steric maps from optimized [Ag(NHCR)2]3− complexes viewed along the Ag-Ccarbene vector. Figure S12. 1H DOSY NMR spectra of 2b–c. Figure S13. Band selective constant time 1H-13C HMBC NMR spectra (resolution enhanced by NUS) of 2c. Figure S14. Correlation between calculated σ(109Ag) and experimental δ(109Ag) chemical shifts for selected NHC silver complexes. Table S6. Calculated σ(109Ag) and experimental δ(109Ag) data for selected NHC silver complexes. Table S7. Antimicrobial activities of complexes 2 evaluated by MIC and MBC (μg/mL). Figure S15. Qualitative hemolysis test of complex 2a and several control chemicals (AgNO3, H2O2, sodium dodecyl sulfate, SDS and NaOH) for comparison. Table S8. Crystal data and structure refinement for 1f. Table S9. Crystal data and structure refinement for 2c. Table S10. Crystal data and structure refinement for 2g. Table S11. Coordinates and optimized structures of NHC-silver complexes used for the correlation between calculated and experimental 109Ag NMR chemical shifts. Table S12. Coordinates of complexes [Ni(CO)3(NHCR)]2− used for the determination of the Tolman Electronic Parameter (TEP). Table S13. Coordinates of the optimized structures., The antimicrobial properties of a series of anionic bis(carbene) silver complexes Na-3[Ag(NHC (R))(2)] were investigated (2a-2g and 2c ', where NHC (R) is a 2,2 '-(imidazol-2-ylidene)dicarboxylate-type N-heterocyclic carbene). The complexes were synthesized by the interaction of imidazolium dicarboxylate compounds with silver oxide in the presence of aqueous sodium hydroxide. Complexes 2f,g were characterized analytically and spectroscopically, and the ligand precursor 1f and complexes 2c and 2g were structurally identified by X-ray diffraction methods. The anions of 2c and 2g, [Ag(NHC (R))(2)](3-), showed a typical linear disposition of C-carbene-Ag-C-carbene atoms and an uncommonly eclipsed conformation of carbene ligands. The antimicrobial properties of complexes 2a-g, which contains chiral (2b-2e and 2c ') and non-chiral derivatives (2a,f,g), were evaluated against Gram-negative bacteria, Escherichia coli and Pseudomonas aeruginosa, and a Gram-positive bacterium, Staphylococcus aureus. From the observed values of the minimal inhibitory concentration and minimal bactericidal concentration, complexes 2a and 2b showed the best antimicrobial activity against all strains. An interesting chirality-antimicrobial relationship was found, and eutomer 2c ' showed better activity than its enantiomer 2c against the three bacteria. Furthermore, these complexes were investigated experimentally and theoretically by Ag-109 nuclear magnetic resonance, and the electronic and steric characteristics of the dianionic carbene ligands were also examined., C.J.C. thanks a research contract from PAIDI 2020, supported by the European Social Fund and the Junta de Andalucía. The authors thank Centro de Investigaciones, Tecnología e Innovación (CITIUS) of the University of Sevilla for providing several research services and to Centro de Servicios de Informática y Redes de Comunicaciones (CSIRC), Universidad de Granada, for providing the computing time., This research was funded by Ministerio de Ciencia e Innovación, PGC2018-093443-B-I00, University of Sevilla, grant number VIPPIT-2021-I.5 (VI Plan Propio de Investigación y Transferencia), and Bruker, Bruker-University of Sevilla award., Peer reviewed