Supporting Information Controlling the formation of two concomitant polymorphs in Hg(II) coordination polymers Francisco Sánchez-Férez a, Xavier Solans-Monforta, Teresa Calvetb, Mercè Font- Bardiac, Josefina Ponsa,*. a Departament de Química, Universitat Autònoma de Barcelona, 08193-Bellaterra, Barcelona, Spain b Departament de Mineralogia, Petrologia i Geologia Aplicada, Universitat de Barcelona, Martí i Franquès s/n, 08028 Barcelona, Spain. c Unitat de Difracció de Raig-X, Centres Científics i Tecnològics de la Universitat de Barcelona (CCiTUB), Universitat de Barcelona, Solé i Sabarís, 1-3, 08028 Barcelona, Spain. *Corresponding Author’s E-mail: Josefina.Pons@uab.es 1 Figures Caption Figure S1. Cooling ramp used in the synthesis of isolated P1A and P1B. 3 Figure S2. SC-XRD (top) and PXRD (bottom) patterns of 2. 3 Figure S3. SC-XRD (top) and PXRD (bottom) patterns of P1B. 4 Figure S4. FTIR-ATR spectrum of P1A and P1B crystals mixture. 4 Figure S5. FTIR-ATR spectrum of isolated P1A crystals. 5 Figure S6. FTIR-ATR spectrum of isolated P1B crystals. 5 Figure S7. FTIR-ATR spectrum of compound 2 synthesized in DMF as solvent. 6 Figure S8. FTIR-ATR spectrum of compound 2 synthesized in milliQ as solvent. 6 Figure S9. FTIR-ATR spectrum of compound 2 synthesized in MeOH as solvent. 7 1 Figure S10. H NMR spectrum of P1A and P1B mixture recorded at 298K in DMSO- d6. 7 1 Figure S11. H NMR spectrum of compound 2 recorded at 298K in DMSO-d6. 8 13 1 Figure S12. C{ H} NMR (top) and DEPT-135 NMR (bottom) spectra of compound 2 recorded at 298K in DMSO-d6. 9 Figure S13. TG-DTA of 2. 10 Figure S14. TG-DTA of P1A. 10 Figure S15. TG-DTA of P1B 11 Figure S16. Hirshfeld surfaces and 2D fingerprint plots of complexes P1A, P1B and 2. 11 Figure S17. Hirshfeld surfaces and 2D fingerprint plots of DMF molecules in complexes P1A and P1B. 12 Figure S18. Model used in the energy partitioning scheme. It includes two dimers of vicinal chains in P1B. 12 Figure S19. Samples of single crystals of (a) 2; (b) P1A and (c) P1B used for the photophysical measurements. 13 Figure S20. Representation of the emission color of P1A, P1B and 2 within the CIE 1931 chromaticity diagram. 13 Tables Caption Table S1. P1A-P1B relative energies per [Hg(Pip)2(4,4’-bipy)]·DMF unit formula in kJ mol-1 as function of the Grimme’s dispersion correction term. A positive value indicates that P1A is more stable than P1B. 14 Table S2. Unit cell measurements of P1A and P1B crystals 14 1,2 Table S3. Geometry distortions analysis using S parameter calculated with SHAPE 15 Table S4. Percentage (%) of Hirshfeld surface implied in each contact for compounds P1A, P1B and 2. 15 2 Furnace conditions Cooling steps 95 95 ºC 45 min 90 °C 10 min 85 82 °C 10 min Temperature (ºC) 74 °C 10 min 75 66 °C 10 min 58 °C 10 min 65 50 °C 10 min 42 ºC 10 min 36 ºC 10 min 55 30 ºC 10 min 45 35 25 0 1 2 3 4 5 6 7 Time (h) Figure S1. Cooling ramp used in the synthesis of isolated P1A and P1B. PXRD patterns Intensity (a.u.) 5 10 15 20 25 30 2q (º) Figure S2. SC-XRD (top) and PXRD (bottom) patterns of 2. 3 Intensity (a.u.) 5 10 15 20 25 30 2q(º) Figure S3. SC-XRD (top) and PXRD (bottom) patterns of P1B. FTIR-ATR and 1H, 13C{1H} and DEPT-135 NMR spectroscopies Figure S4. FTIR-ATR spectrum of P1A and P1B crystals mixture. 4 80 70 Transmittance (%) 60 50 40 30 20 2780 3050 2895 3098 3075 1658 1542 1606 1483 1368 1327 10 1427 1101 1035 805 771 719 680 1248 1229 935 923 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm-1) F Figure S5. FTIR-ATR spectrum of isolated P1A crystals. 80 70 Transmittance (%) 60 50 40 30 2786 3052 2894 3098 3080 1658 1540 1606 1483 1367 1325 1428 1302 1101 1036 805 769 720 680 1453 1251 1230 935 920 20 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm-1) Figure S6. FTIR-ATR spectrum of isolated P1B crystals. 5 Figure S7. FTIR-ATR spectrum of compound 2 synthesized in DMF as solvent. Figure S8. FTIR-ATR spectrum of compound 2 synthesized in milliQ as solvent. 6 Figure S9. FTIR-ATR spectrum of compound 2 synthesized in MeOH as solvent. H4 H5 H6 H1 H8 H9 H2 H3 H7 Figure S10. 1H NMR spectrum of P1A and P1B mixture recorded at 298K in DMSO- d6. 7 H4 H6 H5 H1 H3 H2 Figure S11. 1H NMR spectrum of compound 2 recorded at 298K in DMSO-d6. 8 C9 C10 C7 C4 C8 C3 C6 C5 C11 C1 C2 Figure S12. 13C{1H} NMR (top) and DEPT-135 NMR (bottom) spectra of compound 2 recorded at 298K in DMSO-d6. 9 Thermogravimetric analysis Figure S13. TG-DTA of 2. Figure S14. TG-DTA of P1A. 10 TG /% DTA /(uV/mg) exo 0 100.00 -8.60 -0.1 90.00 109 ºC -0.2 80.00 + -0.3 70.00 199.0 ºC + -0.4 60.00 -0.5 + [1] [1] 50.00 187.1 ºC 50.0 100.0 150.0 200.0 250.0 Temperatura /°C Administrador 2021-05-25 13:27 Main Temperature /C Instrument: NETZSCH STA 409 C/CD File: C:\ngbwin\ta\data5\EXTERN TERESA\Fina Pons\PB1 01.sss Proyecto: Material: Segmentos: 1/1 Identidad: P1B 01 Fichero de Corrección: Crisol: DTA/TG crucible Al2O3 Fecha/Tiempo: 25/05/2021 10:38:22 Temp.Cal./Fichero.Sens: Tcalzero.tcx / Senszero.exx Atmósfera: nitrogeno/80 / ---/--- / ---/--- Figure S15. TG-DTA of P1B Laboratorio: Operador: FACULTAD DE GEOLOGICA Mercedes Rango: Muestra Car./TC: 20/5.0(K/min)/350 DTA(/TG) HIGH RG 2 / S TG Corr./M.Rango: DSC Corr./M.Rango: 000/50 mg 000/500 µV Muestra: P1B 01, 46,800 mg Modo/Tipo de Medid.: DTA-TG / Muestra Hirshfeld Surfaces and 2D fingerprint plot analyses C···C Hg···C All···C C···C Hg···C All···C P1B-Hg1 P1A H···O O···H H···O O···H C···C Hg···C C···Hg C···C Hg···C C···Hg P1B-Hg2 P1B-Hg3 H···O O···H H···O O···H C···C Hg···C C···Hg C···C H···O O···H P1B-Hg4 2 H···O O···H Figure S16. Hirshfeld surfaces and 2D fingerprint plots of complexes P1A, P1B and 2. 11 P1A Cg6-Cg7 DMF DMF H···O O···H H···O O···H DMF DMF H···O O···H Cg5-Cg5 H···O O···H Cg8-Cg8 DMF H···O O···H Figure S17. Hirshfeld surfaces and 2D fingerprint plots of DMF molecules in complexes P1A and P1B. Energy partitioning scheme Figure S18. Model used in the energy partitioning scheme. It includes two dimers of vicinal chains in P1B. 12 Solid-state photoluminescence a) b) c) Figure S19. Samples of single crystals of (a) 2; (b) P1A and (c) P1B used for the CIE photophysical measurements. 1931 520 0,8 540 560 0,6 2 P1A 500 580 y P1B 0,4 600 620 0,2 480 460 0,0 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 x Figure S20. Representation of the emission color of P1A, P1B and 2 within the CIE 1931 chromaticity diagram. 13 Table S1. P1A-P1B relative energies per [Hg(Pip)2(4,4’-bipy)]·DMF unit formula in kJ mol-1 as function of the Grimme’s dispersion correction term. A positive value indicates that P1A is more stable than P1B. Method E PBE 8.9 PBE-D2 -13.4 a PBE-D* -11.9 PBE-D3 -17.4 a PBE-D* stands for a modification of the D2 Grimme’s empirical term 1 Table S2. Unit cell measurements of P1A and P1B crystals P1A (structure elucidation) P1B (structure elucidation) a = 6.0027(7) α = 71.181(4) a = 13.6326(15) α = 105.796(4) b = 13.5859(17) β = 83.249(4) b = 20.267(2) β = 105.114(4) c = 17.769(2) γ = 80.217(4) c = 21.899(2) γ = 100.923(4) P1A (unit cell measurement) P1B (unit cell measurement) a = 6.00 α = 71.06 a = 13.60 α = 105.75 b = 13.60 β = 83.51 b = 20.21 β = 105.12 c = 17.80 γ = 80.67 c = 21.80 γ = 100.94 P1A (unit cell measurement) P1B (unit cell measurement) a = 6.16 α = 70.98 a = 13.69 α = 105.68 b = 13.47 β = 83.12 b = 20.33 β = 105.12 c = 17.69 γ = 80.10 c = 21.98 γ = 100.92 P1A (unit cell measurement) P1B (unit cell measurement) a = 6.00 α = 71.65 a = 13.60 α = 105.77 b = 13.70 β = 83.41 b = 20.31 β = 105.20 c = 17.80 γ = 80.26 c = 21.86 γ = 100.90 14 Table S3. Geometry distortions analysis using S parameter calculated with SHAPE2,3 Compound Geometrya S value TPR-6 13.467 P1A OC-6 23.098 PPY-6 5.748 TPR-6 13.187 P1B (Hg1) OC-6 20.261 PPY-6 7.550 TPR-6 12.787 P1B (Hg2) OC-6 22.941 PPY-6 6.450 TPR-6 11.386 P1B (Hg3) OC-6 20.300 PPY-6 7.466 TPR-6 12.540 P1B (Hg4) OC-6 22.255 PPY-6 5.863 TPR-6 8.452 2 OC-6 16.523 PPY-6 18.028 Closer values have been highlighted in bold. aTPR-6 = Trigonal prismatic; OC-6 = Octahedral; PPY-6 = Pentagonal pyramidal. Table S4. Percentage (%) of Hirshfeld surface implied in each contact for compounds P1A, P1B and 2. Sample Inter-chain contacts DMF C···C Hga H···Ob O···H b H···O O···H P1A 4.1 3.4 17.0 10.3 20.4c 15.2c Hg1 2.7 3.2 16.6 11.4 18.0d 14.3d P1B Hg2 4.1 3.4 16.5 10.7 17.6e 14.2e Hg3 2.7 3.0 16.4 11.4 18.9e 15.0e Hg4 3.8 3.3 16.0 11.0 16.4f 14.3f 2 14.1 0.0 16.4 11.6 - - a Contacts between Hg(II) centers and aromatic rings. b Contacts belonging from C-H···O interactions. dmf molecules interacting with H atoms from cCg1-Cg1; dCg5-Cg5; eCg6-Cg7; or fCg8-Cg8. References (1) Civalleri, B.; Zicovich-Wilson, C. M. .; Valenzano, L.; Ugliengo, P. Analysis of the Compression of Molecular Crystal Structures Using Hirshfeld Surfaces. CrystEngComm 2008, 10, 405–410. (2) Pinsky, M.; Avnir, D. Continuous Symmetry Measures. 5. The Classical Polyhedra. Inorg. Chem. 1998, 37, 5575–5582. (3) Llunell, M.; Casanova, D.; Cirera, J.; Bofill, J. M.; Alemany, P.; Alvarez, S.; Pinsky, M.; Avnir, D. SHAPE Version 2.1. Universitat de Barcelona and The Hebrew University of Jerusalem 2013. 15