Supporting Information Amide-driven secondary building unit structural transformations between Zn(II) coordination polymers Daniel Ejarque a, Teresa Calvet b, Mercè Font-Bardia c, and Josefina Pons a,* 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 E-mail: josefina.pons@uab.es S1 EXPERIMENTAL SECTION Materials and general details Zinc(II) acetate dihydrate (Zn(OAc)2·2H2O), α-acetamidocinnamic acid (HACA), 4,4’-bipyridine (4.4’-bipy) ligands, and anhydrous ethanol (EtOH), chloroform (CHCl3), diethyl ether (Et2O) and methanol (MeOH) as solvents were purchased from Sigma- Aldrich. The water used for the obtention of 3 was MilliQ. Deuterated dimethylsulfoxide (DMSO-d6) was used for the NMR experiments and was purchased from Eurisotop. All of them were used without further purification. The reactions and manipulations for the obtention of 1 and 2 were carried out at room temperature (RT), while those for the obtention of 1C, 3 and 4C were done in a Digiheat-TFT furnace (JP Selecta) using sealed vials under autogenous pressure using a cooling ramp from 50ºC to 25ºC (1C), or a constant temperature of 70 ºC (3), or 30 ºC (4C). Compound 4 was obtained after air exposure of 4C. Powder X-ray diffraction (PXRD) patterns were measured with a Siemens D5000 apparatus with 40 kW and 45 mA using CuKα radiation with λ = 1.5406 Å. All of them were recorded from 2Ɵ = 5º to 30º with a step scan of 0.02º counting one second at each step. Elemental analyses (C, H, N) were carried on a Thermo Scientific Flash 2000 CHNS Analyzer. Simultaneous thermogravimetric (TG)/differential thermal analysis (DTA) determinations for 1 and 4 were performed using 57.6 mg (1) and 53.5 mg (4) in a Netzsch STA 409 instrument, with an aluminum oxide powder crucible and an oxide powder as a standard (Al2O3, PerkinElmer 0419-0197), and heating at 5 °C·min−1 from 25 to 350 °C, under nitrogen atmosphere with a flow rate of 80 mL·min−1. HR-ESI-MS measurements were recorded after dissolving the corresponding complexes in MeOH in a MicroTOF-Q instrument equipped with an electrospray ionization source (ESI) in positive mode. Na+ ions come from the MeOH solvent which contains <50 ppb. Conditions were those used in routine experiments. The nebulizer pressure was 1.5 bar, the desolvation temperature was 180 ºC, dry gas at 6 L·min-1, the capillary counter- electrode voltage was 5 kV, and the quadrupole ion energy, 5.0 eV. FTIR-ATR spectra were recorded on a Perkin Elmer spectrometer, equipped with an attenuated total reflectance (ATR) accessory model MKII Golden Gate with diamond window in the range 4000–500 cm−1. 1H, 13 C{1H} and DEPT-135 NMR spectra were recorded on a Bruker Ascend 300 MHz spectrometer in DMSO-d6 solutions at RT. All the chemical shifts (δ) are given in ppm relative to TMS as internal standard. Solid-state photoluminescence measurements were recorded using a Varian Cary Eclipse S2 Fluorescence spectrophotometer between 350 and 600 nm. CIE 1931 chromaticity diagram was generated using Origin Pro 2019b software. Characterization of compounds 1-4 {[Zn(ACA)2(4,4’-bipy)]·EtOH}n (1). Yield: 262 mg (85.1%) (based on Zn). Elemental analysis calc(%). for C34H34ZnN4O7 (676.05): C 60.40; H 5.07; N 8.29; found: C 60.28; H 5.15; N 8.17. HR-MS (ESI+, MeOH): m/z (%) = 157.0768 (100%) (calc. for [4,4’-bipy + H+] = 157.0760); 228.0630 (100%) (calc. for [HACA + Na]+ = 228.0631); 473.0697 (100%) (calc. for [Zn(ACA)2 + H]+ = 473.0686); 495.0492 (100%) (calc. for [Zn(ACA)2 + Na]+ = 495.0505); 740.0591 (79%) (calc. for [Zn2(ACA)3]+ = 740.0559); 967.1126 (74%) (calc. for [Zn2(ACA)4 + Na]+ = 967.1118); 504.0268 (40%) (calc. for [Zn3(ACA)4]2+ = 504.0253). FTIR-ATR (wavenumber, cm-1): 3455-3378(br) [ν(O-H)], 3237(w) [ν(N-H)], 3163-3023(br) [ν(C-H)ar] + [ν(C-H)alk], 2980-2946(br) [ν(C-H)al], 1661(w) [ν(C=O)], 1642(sh), 1608(s) [νas(COO)], 1519(m) [ν(C=C/C=N)], 1491(m) [ν(C=C/C=N)], 1447(w), 1417(m), 1372(s) [νs(COO)], 1340(s) [δ(C=C/C=N)], 1283(m), 1222(w), 1216(sh), 1182(w), 1144(w), 1072(w) [δip(C-H)], 1045(w), 1032(w), 1017(w) [δip(C-H)], 985(w), 927(w), 891(w), 850(w), 813(w), 775(w), 769(w), 744(w), 731(w), 692(s) [δoop(C-H)], 640(m) [δoop(C-H)], 601(sh), 592(m), 571(m), 554(w), 525(m). 1H NMR (300 MHz; DMSO-d6; Me4Si; 298 K): δ = 9.20 [2H, s, NHACA], 8.73 [4H, dd, 3J = 4.6 Hz, 4J = 1.6 Hz, o-H4,4’-bipy], 7.85 [4H, dd, 3J = 4.5 Hz, 4J = 1.7 Hz, m-H4,4’-bipy], 7.50 [4H, d, 3J = 7.2 Hz, o-HACA], 7.35 [4H, t, 3J = 7.3 Hz, m-HACA], 7.29 [2H, d, 3J = 7.1 Hz, p-HACA], 7.24 [2H, s, NH-C-CHACA], 1.95 [6H, s, CO-CH3,ACA]. 13C{1H} NMR (75 MHz; DMSO-d6; Me4Si; 298 K): δ = 170.6 [NH-COACA], 168.7 [COOACA], 150.7 [o-C4,4’-bipy], 144.7 [N-CH-CH-C4,4’-bipy], 135.1 [O2C-CACA], 129.7 [HN-C-CH-CACA], 129.4 [o-CACA], 129.3 [p-CACA], 128.5 [m-CACA], 128.4 [NH-C-CHACA], 121.6 [m-C4,4’-bipy], 23.1 [CO- CH3,ACA]. DEPT-135 NMR (75 MHz; DMSO-d6; Me4Si, 298 K): δ = 150.7 [o-C4,4’-bipy], 129.4 [o-CACA], 129.3 [p-CACA], 128.5 [m-CACA], 128.4 [NH-C-CHACA], 121.6 [m-C4,4’- bipy], 23.1 [CO-CH3,ACA]. {[Zn(ACA)2(4,4’-bipy)]·2MeOH}n (2). Yield: 11.6 mg (56.5%) (based on Zn). Elemental analysis calc(%). for C34H36ZnN4O8 (694.06): C 58.84; H 5.23; N 8.07; found: C 58.58; H 4.98; N 7.92. HR-MS (ESI+, MeOH): m/z (%) = 157.0768 (100%) (calc. for [4,4’-bipy + H]+ = 157.0760); 228.0630 (100%) (calc. for [HACA + Na]+ = 228.0631); 473.0697 (100%) (calc. for [Zn(ACA)2 + H]+ = 473.0686); 495.0492 (100%) (calc. for [Zn(ACA)2 + Na]+ = 495.0505); 740.0591 (79%) (calc. for [Zn2(ACA)3]+ = 740.0559); S3 967.1126 (74%) (calc. for [Zn2(ACA)4 + Na]+ = 967.1118); 504.0268 (40%) (calc. for [Zn3(ACA)4]2+ = 504.0253). FTIR-ATR (wavenumber, cm-1): 3646(w) [ν(O-H)], 3403(w), 3248(w) [ν(N-H)], 3171-3025(br) [ν(C-H)ar] + [ν(C-H)alk], 2999-2812(br) [ν(C- H)al], 1668(w) [ν(C=O)], 1643(w), 1613(sh), 1593(s) [νas(COO)], 1515(m) [ν(C=C/C=N)], 1491(m) [ν(C=C/C=N)], 1447(w), 1422(m), 1385(s) [νs(COO)], 1370(s), 1355(s) [δ(C=C/C=N)], 1328(br), 1275(m), 1269(w), 1223(w), 1208(w), 1187(w), 1149(w), 1070(w) [δip(C-H)], 1032(w) [δip(C-H)], 1017(w) [δip(C-H)], 1003(w), 987(w) [δip(C-H)], 924(w), 896(w), 851(w), 818(m), 772(m), 750(m), 727(w), 688(s) [δoop(C- H)], 641(m) [δoop(C-H)], 629(sh), 594(m), 556(m), 523(m). 1H NMR (300 MHz; DMSO- d6; Me4Si; 298 K): δ = 9.17 [2H, s, NHACA], 8.72 [4H, dd, 3J = 4.5 Hz, 4J = 1.7 Hz, o- H4,4’-bipy], 7.83 [4H, dd, 3J = 4.5 Hz, 4J = 1.7 Hz, m-H4,4’-bipy], 7.49 [4H, d, 3J = 7.4 Hz, o- HACA], 7.34 [4H, t, 3J = 7.3 Hz, p-HACA], 7.28 [2H, d, 3J = 7.2 Hz, m-HACA], 7.23 [2H, s, NH-C-CHACA], 4.18 [2H, q, 3J = 5.1 Hz, OHMeOH], 3.16 [6H, d, 3J = 5.1 Hz, CH3,MeOH], 1.95 [6H, s, CO-CH3,ACA]. 13C{1H} NMR (75 MHz; DMSO-d6; Me4Si; 298 K): δ = 170.3 [NH-COACA], 168.5 [COOACA], 150.7 [o-C4,4’-bipy], 144.6 [N-CH-CH-C4,4’-bipy], 135.2 [O2C-CACA], 129.8 [HN-C-CH-CACA], 129.4 [o-CACA], 128.8 [p-CACA], 128.4 [m-CACA], 128.2 [NH-C-CHACA], 121.5 [m-C4,4’-bipy], 48.7 [CH3OH], 23.1 [CO-CH3,ACA]. DEPT- 135 NMR (75 MHz; DMSO-d6; Me4Si, 298 K): δ = 150.7 [o-C4,4’-bipy], 129.4 [o-CACA], 128.9 [p-CACA], 128.4 [m-CACA], 128.2 [NH-C-CHACA], 121.5 [m-C4,4’-bipy], 48.7 [CH3OH], 23.1 [CO-CH3,ACA]. {[Zn2(μ-ACA)2(ACA)2(4,4’-bipy)]·2H2O}n (3). Yield: 9.3 mg (55.2%) (based on Zn). Elemental analysis calc(%). for C54H52Zn2N6O14 (1139.80): C 56.90; H 4.60; N 7.37; found: C 56.74; H 4.48; N 7.20. HR-MS (ESI+, MeOH): m/z (%) = 157.0768 (100%) (calc. for [4,4’-bipy + H]+ = 157.0760); 228.0630 (100%) (calc. for [HACA + Na]+ = 228.0631); 473.0697 (100%) (calc. for [Zn(ACA)2 + H]+ = 473.0686); 495.0492 (100%) (calc. for [Zn(ACA)2 + Na]+ = 495.0505); 740.0591 (79%) (calc. for [Zn2(ACA)3]+ = 740.0559); 967.1126 (74%) (calc. for [Zn2(ACA)4 + Na]+ = 967.1118); 504.0268 (40%) (calc. for [Zn3(ACA)4]2+ = 504.0253). FTIR-ATR (wavenumber, cm-1): 3581(w) [ν(O- H)], 3496(w) [ν(O-H)], 3212(w) [ν(N-H)], 3154-3007(br) [ν(C-H)]ar + [ν(C-H)]alk, 2944- 2802(br) [ν(C-H)]al, 1632(m) [ν(C=O)], 1613(w), 1585(m) [νas(COO)], 1523(s) [νas(COO)], 1493(m) [ν(C=C/C=N)], 1449(w), 1410(s) [νs(COO)], 1363(s) [δ(C=C/C=N)], 1339(sh), 1285(s), 1216(m), 1150(w), 1138(w), 1068(w) [δip(C-H)], 1041(w), 1013(w) [δip(C-H)], 985(w) [δip(C-H)], 927(w), 900(w), 850(w), 826(m), S4 780(m), 767(m), 750(m), 729(w), 692(s) [δoop(C-H)], 642(m) [δoop(C-H)], 609(m), 591(w), 570(s), 526(m). 1H NMR (300 MHz; DMSO-d6; Me4Si; 298 K): δ = 9.17 [4H, s, NHACA], 8.73 [4H, dd, 3J = 4.5 Hz, 4J = 1.7 Hz, o-H4,4’-bipy], 7.84 [4H, dd, 3J = 4.5 Hz, 4J = 1.7 Hz, m-H4,4’-bipy], 7.50 [8H, d, 3J = 7.3 Hz, o-HACA], 7.35 [8H, t, 3J = 7.4 Hz, m- HACA], 7.29 [4H, d, 3J = 7.1 Hz, p-HACA], 7.24 [2H, s, NH-C-CHACA], 1.95 [6H, s, CO- CH3,ACA]. 13C{1H} NMR (75 MHz; DMSO-d6; Me4Si; 298 K): δ = 170.5 [NH-COACA], 168.4 [COOACA], 150.6 [o-C4,4’-bipy], 144.5 [N-CH-CH-C4,4’-bipy], 135.1 [O2C-CACA], 129.7 [HN-C-CH-CACA], 129.3 [o-CACA], 129.0 [p-CACA], 128.3 [m-CACA], 128.2 [NH- C-CHACA], 121.4 [m-C4,4’-bipy], 23.0 [CO-CH3,ACA]. DEPT-135 NMR (75 MHz; DMSO- d6; Me4Si, 298 K): δ = 150.6 [o-C4,4’-bipy], 129.3 [o-CACA], 129.0 [p-CACA], 128.3 [m- CACA], 128.2 [NH-C-CHACA], 121.4 [m-C4,4’-bipy], 23.0 [CO-CH3,ACA]. {[Zn3(μ-ACA)6(4,4’-bipy)]·0.75CHCl3}n (4). 9.7 mg (59.0%) (based on Zn). Elemental analysis calc(%). for C76.75H68.75Zn3N8O18Cl2.25 (1667.10): C 55.29; H 4.17; N 6.72; found: C 55.63; H 4.21; N 6.79. HR-MS (ESI+, MeOH): m/z (%) = 157.0768 (100%) (calc. for [4,4’-bipy + H]+ = 157.0760); 228.0630 (100%) (calc. for [HACA + Na]+ = 228.0631); 473.0697 (100%) (calc. for [Zn(ACA)2 + H]+ = 473.0686); 495.0492 (100%) (calc. for [Zn(ACA)2 + Na]+ = 495.0505); 740.0591 (79%) (calc. for [Zn2(ACA)3]+ = 740.0559); 967.1126 (74%) (calc. for [Zn2(ACA)4 + Na]+ = 967.1118); 504.0268 (40%) (calc. for [Zn3(ACA)4]2+ = 504.0253). FTIR-ATR (wavenumber, cm-1): 3242(w) [ν(N-H)], 3163-3025(br) [ν(C-H)ar] + [ν(C-H)alk], 2956-2853(br) [ν(C-H)al], 1677(w), 1660(w), 1646(w) [ν(C=O)], 1589(s), 1573(s) [νas(COO)], 1532(m) [ν(C=C/C=N)], 1492(w) [ν(C=C/C=N)], 1446(w), 1389(s) [νs(COO)], 1365(s) [δ(C=C/C=N)], 1351(sh), 1278(m), 1226(w), 1210(w), 1184(w), 1158(w), 1123(w), 1080(w) [δip(C-H)], 1030(sh), 1018(w) [δip(C-H)], 980(w) [δip(C-H)], 962(w), 927(w), 847(w), 810(w), 790(w), 763(s), 751(m), 731(w), 688(s) [δoop(C-H)], 673(sh), 643(w) [δoop(C-H)], 619(w), 604(m), 592(s), 575(s), 524(m). 1H NMR (300 MHz; DMSO-d6; Me4Si; 298 K): δ = 9.20 [6H, s, NHACA], 8.73 [4H, dd, 3J = 4.5 Hz, 4J = 1.7 Hz, o-H4,4’- bipy], 7.84 [4H, dd, 3J = 4.5 Hz, 4J = 1.7 Hz, m-H4,4’-bipy], 7.50 [12H, d, 3J = 7.1 Hz, o- HACA], 7.36 [12H, t, 3J = 7.3 Hz, o-HACA], 7.29 [2H, d, 3J = 6.9 Hz, m-HACA], 7.23 [2H, s, NH-C-CHACA], 1.95 [6H, s, CO-CH3,ACA]. 13C{1H} NMR (75 MHz; DMSO-d6; Me4Si; 298 K): δ = 170.5 [NH-COACA], 168.6 [COOACA], 150.7 [o-C4,4’-bipy], 144.6 [N-CH-CH- C4,4’-bipy], 135.1 [O2C-CACA], 129.7 [HN-C-CH-CACA], 129.4 [o-CACA], 129.1 [p-CACA], 128.5 [m-CACA], 128.3 [NH-C-CHACA], 121.5 [m-C4,4’-bipy], 23.1 [CO-CH3,ACA]. DEPT- S5 135 NMR (75 MHz; DMSO-d6; Me4Si, 298 K): δ = 150.7 [o-C4,4’-bipy], 129.4 [o-CACA], 129.2 [p-CACA], 128.5 [m-CACA], 128.3 [NH-C-CHACA], 121.5 [m-C4,4’-bipy], 23.1 [CO- CH3,ACA]. X-ray crystallographic refinement data The X-ray intensity data were measured on a D8 Venture system equipped with a multilayer monochromator and a Mo microfocus (λ = 0.71073 Å). For 1C, the integration of the data using a triclinic unit cell yielded a total of 11749 reflections to a maximum θ angle of 31.38º (0.68 Å resolution), of which 11749 were independent (average redundancy 1.000, completeness = 96.0%, Rint = 5.87%, Rsig = 0.38%) and 10950 (93.20%) were greater than 2σ(|F|2). The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.6903 and 0.7461. For 2, the integration of the data using a monoclinic unit cell yielded a total of 25688 reflections to a maximum θ angle of 30.61 (0.70 Å resolution), of which 5003 were independent (average redundancy 5.135, completeness = 99.7%, Rint = 11.50%, Rsig = 9.84%) and 3044 (60.84%) were greater than 2σ(|F|2). The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.6646 and 0.7461. For 3, the integration of the data using a monoclinic unit cell yielded a total of 52017 reflections to a maximum θ angle of 30.59° (0.70 Å resolution), of which 7846 were independent (average redundancy 6.630, completeness = 98.3%, Rint = 2.72%, Rsig = 1.70%) and 7481 (95.35%) were greater than 2σ(|F|2). The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.6688 and 0.7461. For 4C, the integration of the data using a triclinic unit cell yielded a total of 70704 reflections to a maximum θ angle of 26.49° (0.80 Å resolution), of which 11166 were independent (average redundancy 6.332, completeness = 99.2%, Rint = 16.53%, Rsig = 10.86%) and 7193 (64.42%) were greater than 2σ(|F|2). The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.6774 and 0.7454. The structures were solved and refined using a SHELXTL Software Package (version-2018/3)1. For 1C, the final anisotropic full-matrix least-squares refinement on |F|2 with 461 variables converged at R1 = 4.03%, for the observed data and wR2 = 9.98% for all data. For 2, the final anisotropic full-matrix least-squares refinement on |F|2 with 216 variables converged at R1 = 5.70%, for the observed data and wR2 = 13.63% for all data. For 3, the final anisotropic full-matrix least-squares refinement on |F|2 with 351 variables converged at R1 = 3.47%, for the observed data and wR2 = 9.15% for all data. S6 For 4C, the final anisotropic full-matrix least-squares refinement on |F|2 with 630 variables converged at R1 = 7.34%, for the observed data and wR2 = 14.69% for all data. For 1C, 2, 3 and 4C the final cell constants and volume are based upon refinement of the XYZ-centroids of reflections above 20 σ(I). Data were corrected for absorption effects using the Multi-Scan method (SADABS). Molecular graphics were generated using Mercury 4.3.1 software2, using the POV-Ray image package3. The color codes for all of the molecular graphics are as follows: dark blue (Zn), red (O), light blue (N), light green (Cl), gray (C), and white (H). All the accessible void volumes have been calculated with Mercury 4.3.1 software2 using a probe radius of 1.2 Å4. The evaluation of the geometry distortion of Zn(II) cores in 1C, 2, 3 and 4C has been done using version 2.1 of SHAPE software from the corresponding .cif files5. Obtention of single crystals of 1C Figure S1. Cooling ramp used for the obtention of single crystals of compound {[Zn(ACA)2(4,4’-bipy)] 2.5EtOH}n (1C). S7 PXRD patterns Single crystal 1C Powder 1 Figure S2. XRD patterns from the single crystal collected data at 100K of {[Zn(ACA)2(4,4’-bipy)]·2.5EtOH}n (1C) and powder XRD pattern at 298K of compound {[Zn(ACA)2(4,4’-bipy)]·EtOH}n (1). Single crystal 2 Powder 2 Figure S3. XRD patterns from the single crystal collected data at 100K and powder XRD pattern at 298K of compound {[Zn(ACA)2(4,4’-bipy)]·2MeOH}n (2). S8 Single crystal 3 Powder 3 Figure S4. XRD patterns from the single crystal collected data at 100K and powder XRD pattern at 298K of compound {[Zn2(μ-ACA)2(ACA)2(4,4’-bipy)]·2H2O}n (3). Single crystal 4C Powder 4 Figure S5. XRD patterns from the single crystal collected data at 100K of {[Zn3(μ- ACA)6(4,4’-bipy)]·8CHCl3}n (4C) and powder XRD pattern at 298K of compound {[Zn3(μ-ACA)6(4,4’-bipy)]·0.75CHCl3}n (4). S9 Thermogravimetric analysis DTA /(uV/mg) TG /% ↓ exo 100.00 0 4.88 % -0.1 90.00 -0.2 232 ºC -0.3 80.00 -0.4 70.00 -0.5 -0.6 60.00 -0.7 50.00 [1] [1] -0.8 50.0 100.0 150.0 200.0 250.0 300.0 Temperature /°C Figure S6. TG-DTA of compound {[Zn(ACA)2(4,4’-bipy)]·EtOH}n (1). TG /% DTA /(uV/mg) ↓ exo 100.00 0 95.00 -0.1 90.00 -0.2 244 ºC 85.00 -0.3 80.00 -0.4 75.00 -0.5 -0.6 70.00 -0.7 65.00 -0.8 60.00 [1] 50.0 100.0 150.0 200.0 250.0 300.0 Temperature /°C Figure S7. TG-DTA of compound {[Zn3(μ-ACA)6(4,4’-bipy)]·0.75CHCl3}n (4). S10 HR-ESI-MS a) b) Intens. [%] Intens. [%] 100 473.0697 Experimental 100 495.0492 Experimental 84 84 67 475.0661 67 497.0472 50 477.0670 50 34 34 496.0485 499.0476 474.0708 476.0673 498.0475 17 478.0681 17 479.2392 500.0475 501.0477 0 0 100 473.0686 Theoretical 100 495.0505 Theoretical 75 75 475.0660 497.0480 50 477.0649 50 499.0468 474.0718 476.0681 496.0537 498.0500 25 25 478.0678 500.0497 479.0677 501.0496 0 0 473 474 475 476 477 478 479 m/z 495 496 497 498 499 500 501 m/z c) d) Intens. [%] Intens. [%] 100 742.0576 744.0556 Experimental 100 971.1113 Experimental 969.1117 84 84 740.0591 967.1126 67 67 743.0581 970.1136 50 50 972.1108 745.0563 746.0523 973.1065 741.0608 968.1157 34 34 974.1079 17 747.0556 17 975.1059 748.0526 976.1015 977.0955 749.0564 0 0 100 742.0535 744.0520 Theoretical 100 971.1083 Theoretical 969.1097 740.0559 75 75 967.1118 970.1117 972.1102973.1071 50 743.0556 746.0504 50 745.0540 968.1150 741.0591 974.1083 25 747.0520 25 975.1061 748.0494 749.0516 976.1078 977.1079 0 0 740 742 744 746 748 750 m/z 968 970 972 974 976 m/z e) Intens. [%] 506.0253 Experimental 100 84 507.0241 505.0253 67 506.5255 50 508.0235 505.5268 507.5251 504.0268 34 508.5243 504.5283 509.0222 17 509.5226 510.0225 510.5251 0 100 506.0233 Theoretical 507.0224 75 505.0241 506.5242 508.0218 50 505.5252 507.5231 504.0253 508.5224 25 504.5269 509.0212 509.5217 510.0207 510.5215 0 504 505 506 507 508 509 510 m/z Figure S8. In detail views of the HR-ESI-MS fragments of 1-4: (a) [Zn(ACA)2+H]+. (b) [Zn(ACA)2+Na]+. (c) [Zn2(ACA)3]+. (d) [Zn2(ACA)4 + Na]+. (e) [Zn3(ACA)4]2+. S11 FTIR-ATR, 1H, 13C{1H} and DEPT-135 NMR spectroscopies Figure S9. FTIR-ATR spectrum of compound {[Zn(ACA)2(4,4’-bipy)]·EtOH}n (1). Figure S10. FTIR-ATR spectrum of compound {[Zn(ACA)2(4,4’-bipy)]·2MeOH}n (2). S12 Figure S11. FTIR-ATR spectrum of compound {[Zn2(μ-ACA)2(ACA)2(4,4’- bipy)]·2H2O}n (3). Figure S12. FTIR-ATR spectrum of compound {[Zn3(μ-ACA)6(4,4’-bipy)]·0.75CHCl3}n (4). S13 H8 H6 H3 H2 H5 H4 H7 H1 Figure S13. 1H NMR spectrum of compound {[Zn(ACA)2(4,4’-bipy)]·EtOH}n (1). H2 H4 H5 H8 H10 H3 H7 H3 H2 H5 H4 H6 H9 H1 Figure S14. 1H NMR spectrum of compound {[Zn(ACA)2(4,4’-bipy)]·2MeOH}n (2). S14 H8 H6 H3 H7 H2 H5 H4 H1 Figure S15. 1H NMR spectrum of compound {[Zn2(μ-ACA)2(ACA)2(4,4’-bipy)]·2H2O}n (3). H3 H2 H6 H5 H8 H4 H1 H7 Figure S16. 1H NMR spectrum of compound {[Zn3(μ-ACA)6(4,4’-bipy)]·0.75CHCl3}n (4). S15 a) C10 C11 C6 C5 C4 C7 C3 C12 C9 C2 C8 C1 b) C10 C11 C6 C5 C7 C3 C9 Figure S17. (a) 13C{1H} and (b) DEPT-135 NMR spectra of compound {[Zn(ACA)2(4,4’- bipy)]·EtOH}n (1). S16 a) C11 C10 C6 C5 C C4 C7 3 C12 C13 C9 C8 C1 C2 b) C11 C10 C5 C6 C7 C3 C9 C13 Figure S18. (a) 13C{1H} and (b) DEPT-135 NMR spectra of compound {[Zn(ACA)2(4,4’- bipy)]·2MeOH}n (2). S17 a) C6 C11 C5 C10 C4 C7 C3 C9 C12 C2 C1 C8 b) CCC111111 CCC101010 CC1111 CCC C 66666 CC CC C 55555 CC3 3 CCCC 7777 CCC333 CCC 9 99 Figure S19. (a) 13C{1H} and (b) DEPT-135 NMR spectra of compound {[Zn2(μ- ACA)2(ACA)2(4,4’-bipy)]·2H2O}n (3). S18 a) C5 C5 CC66 CC1111 C10 C C77 C33 CC44 C C9 C2 C1 C8 C12 b) C6 C5 C11 C3 C7 C9 C10 Figure S20. (a) 13C{1H} and (b) DEPT-135 NMR spectra of compound {[Zn3(μ- ACA)6(4,4’-bipy)]·0.75CHCl3}n (4). S19 Geometric Evaluation Table S1. Geometry distortion analysis of the Zn(II) cores from 1C, 2, 3 and 4C using S parameter calculated with SHAPE5,6. Compound Label Geometrya S value 1C Zn(1) T-4 0.946 SS-4 5.501 vTBPY-4 1.808 2 Zn(1) T-4 0.630 SS-4 8.302 vTBPY-4 2.962 3 Zn(1) PP-5 30.204 vOC-5 4.508 TBPY-5 4.308 SPY-5 2.525 JTBPY-5 6.230 4C Zn(1) T-4 0.843 SS-4 6.764 vTBPY-4 1.265 Zn(2) OC-6 0.245 TPR-6 16.152 Closer values have been highlighted in bold. a T-4 = Tetrahedron; SS-4 = Seesaw or sawhorse; vTBPY-4 = Axially vacant trigonal bipyramid; PP-5 = Pentagon; vOC-5 = Vacant octahedron; TBPY-5 = Trigonal bipyramid; SPY-5 = Square pyramid; JTBPY-5 = Johnson trigonal bipyramid; OC-6 = Octahedron; TPR- 6 = Trigonal prism. Photoluminescence data Figure S21. CIE 1931 chromaticity diagram for 1-4. S20 References (1) Sheldrick, G. M. A Short History of SHELX. Acta Cryst. Sect. A 2008, 64, 112–122. https://doi.org/10.1107/S0108767307043930. (2) MacRae, C. F.; Sovago, I.; Cottrell, S. J.; Galek, P. T. A.; McCabe, P.; Pidcock, E.; Platings, M.; Shields, G. P.; Stevens, J. S.; Towler, M.; Wood, P. A. Mercury 4.0: From Visualization to Analysis, Design and Prediction. J. Appl. Cryst. 2020, 53, 226–235. https://doi.org/10.1107/S1600576719014092. (3) Persistence of Vision Pty. Ltd. Persistence of Vision (TM) Raytracer; Persistence of Vision Pty. Ltd.: Williamstown, Australia, 2004. (4) Spek, A. L. Single-Crystal Structure Validation with the Program PLATON. J. Appl. Cryst. 2003, 36, 7–13. https://doi.org/10.1107/S0021889802022112. (5) Llunell, M.; Casanova, D.; Cirera, J.; Alemany, P.; Alvarez, S. SHAPE. Program for the Stereochemical Analysis of Molecular Fragments by Means of Continuous Shape Measures and Associated Tools. Universitat de Barcelona, Barcelona 2013. (6) Pinsky, M.; Avnir, D. Continuous Symmetry Measures. 5. The Classical Polyhedra. Inorg. Chem. 1998, 37, 5575–5582. https://doi.org/10.1021/ic9804925. S21