Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions

Transcription

1 Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions Zhan Zhang, Dong Sub Kim, Chung-Yon Lin, Huacheng Zhang, Aaron D. Lammer, Vincent M. Lynch, Ilya Popov, Ognjen Š. Miljanić, Eric V. Anslyn * and Jonathan L. Sessler * Department of Chemistry, The University of Texas at Austin, 105 East 24th Street-Stop A5300, Austin, Texas United States Department of Chemistry, University of Houston, Houston, Texas United States Contents 1. Synthetic Experimental.. S1 2. SEM Images...S3 3. Solution Studies....S4 4. X-Ray Experimental..S6 5. Solvent Response.S28 6. Anion Response...S42 7. Measurement of pka S53 8. References...S54 S1

2 1. Synthetic Experimental General. All reagents and solvents were purchased from commercial suppliers and used without further purification. Scanning electron microscopy (SEM) was carried out using a Quanta650 instrument. The samples were prepared on a silicon wafer, which was cleaned using nitric acid prior to use. Microstructures obtained from slow evaporation of P m P n -diacid suspension in CH 2 Cl 2 were examined. UV-vis spectra were measured on a Varian Cary 5000 spectrophotometer. Fluorescence spectra were recorded on a Triax 320 fluorescence spectrometer. X-ray crystallographic analyses were carried out on either an Agilent Technologies SuperNova Dual Source diffractometer or a Rigaku AFC12 diffractometer equipped with a Saturn 724+ CCD or Nonius Kappa CCD, respectively. Preparation of 1:1 P m P n -diacid polymer samples. The free-base form of the macrocycle in question, P 2 P 4 or P 3 P 3, (0.01 mmol) was dissolved in roughly 80 ml CH 2 Cl 2 and 1.2 equivalents of acid were added in solid form. The mixture was then sonicated until all the granules were dissolved. After cooling, more CH 2 Cl 2 was added to obtain a total volume of 100 ml. The resulting solution was ready for use in solvent and anion sensing studies. Preparation of 1:2 P m P n -diacid assembly samples. These ensembles were prepared using the procedure used to obtain the 1:1 P m P n -diacid polymers with the exception that 2.4 molar equivalents of acid were used. S2

3 2. SEM Images Figure S1. P 3 P 3 -BPDSA. Figure S2. P 3 P 3 -TFTPA. Figure S3. P 3 P 3 -OA. Figure S4. P 2 P 4 -ADCA. S3

4 3. Solution Studies 3.1. Job Plots Figure S5. Continuous variation plot for 1:1 mixtures of the indicated P m P n macrocycle and BPDSA. These plots were constructed by plotting the product of the absorption change at 370 nm (P 3 P 3 ) or 451 nm (P 2 P 4 ) and the mole fraction of P m P n vs the mole fraction of P m P n. Figure S6. Continuous variation plot for a 1:2 mixture of P 2 P 4 and oxalic acid. This plot was constructed by plotting the product of the absorption change at 460 nm and the mole fraction of P 2 P 4 vs the mole fraction of P 2 P 4. Note: Classic Job plots (not modified ones) were performed. S4

5 3.2. Isodesmic Titrations (a) (b) (c) Figure S7. (a) Changes in the optical spectrum of P 3 P 3 (100 ml chloroform solution containing 0.3 ml methanol; ambient temperature) observed upon the incremental addition of BPDSA. (b) Plot of molar extinction coefficient as a function of the total concentration of an equimolar mixture of P 3 P 3 and BPDSA. (c) Simulation of the number average aggregate size based on the calculated binding constant, K = M 1. Figure S8. (a) Changes in the optical spectrum of P 2 P 4 (100 ml chloroform solution containing 0.3 ml methanol; ambient temperature) observed upon the incremental addition of BPDSA. (b) Plot of molar extinction coefficient as a function of the total concentration of an equimolar mixture of P 2 P 4 and BPDSA. (c) Simulation of the number average aggregate size based on the calculated binding constant, K = M 1. S5

6 4. X-Ray Experimental 4.1. P 3 P 3 - BPDSA (CCDC: ) Crystals grew as red needles upon the slow diffusion of a methanol solution of BPDSA into a chloroform solution of the P 3 P 3 macrocycle in a NMR tube. The data crystal had approximate dimensions; 0.37 x 0.05 x 0.01 mm. The data were collected on an Agilent Technologies SuperNova Dual Source diffractometer using a -focus Cu K radiation source ( = Å) with collimating mirror monochromators. Data were collected using -scans. The data were collected at 150 K using an Oxford Cryostream low temperature device. Details of crystal data, data collection and structure refinement are listed in Table S1. Data collection, unit cell refinement and data reduction were performed using Agilent Technologies CrysAlisPro V The structure was solved by direct methods using SIR97 2 and refined by fullmatrix least-squares on F 2 with anisotropic displacement parameters for the non-h atoms using SHELXL Structure analysis was aided by use of the programs PLATON98 4 and WinGX. 5 The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5xUeq for methyl hydrogen atoms). One solvent molecule was found to be badly disordered. The contributions to the scattering factors due to this solvent molecule were removed by use of the utility SQUEEZE 6 in PLATON98. PLATON98 was used as incorporated in WinGX 5. The function, w( Fo 2 - Fc 2 ) 2, was minimized, where w = 1/[( (Fo)) 2 + (0.1319*P) 2 + (1.6595*P)] and P = ( Fo Fc 2 )/3. Rw(F 2 ) refined to 0.312, with R(F) equal to and a goodness of fit, S, = Definitions used for calculating R(F), Rw(F 2 ) and the goodness of fit, S, are given below. 7 The data were checked for secondary extinction effects but no correction was necessary. Neutral atom scattering factors and values used to calculate the linear absorption coefficient are from the International Tables for X-ray Crystallography (1992). 8 All figures were generated using SHELXTL/PC. 9 S6

7 Figure S9. Crystal structure of P 3 P 3 -BPDSA. Left: top view; right: packing. For the sake of clarity, hydrogen atoms and solvent molecule(s) are not shown. Table S1. Crystal data for P 3 P 3 -BPDSA. Empirical Formula C 48 H 45 N 6 O 6 Cl 3 S 2 Formula Weight Temperature 150K Wavelength Å Crystal Color, Habit red, needle Crystal Dimensions 0.37 X 0.05 X 0.01 mm Crystal System triclinic Space Group P-1 a/å b/å c/å Lattice Parameters α/deg β/deg /deg V/Å Z Value 4 D calc /g cm F S7

8 No. of Reflections Measured Total: Unique: (R int = 0.111) Data/restraints/parameters 23551/0/1179 R1; wr2 (all data) ; Goodness of Fit Indicator (GOF) 1.65 R1; wr2 (I>2σ(I)) 0.115; S8

9 4.2. P 2 P 4 -TFTPA (CCDC: ) Crystals grew as brown needles by vapor diffusion of hexanes into a chloroform solution (containing trace methanol) of the free base form of the P 2 P 4 macrocycle and excess TFTPA. The data crystal had approximate dimensions: x x mm. The data were collected on a Nonius Kappa CCD diffractometer using a graphite monochromator with MoK radiation ( = Å). A total of 525 frames of data were collected using -scans. The data were collected at 163 K using an Oxford Cryostream low temperature device. Details of crystal data, data collection and structure refinement are listed in Table S2. Data reduction were performed using DENZO-SMN. 10 The structure was solved by direct methods using SIR97 2 and refined by full-matrix least-squares on F 2 with anisotropic displacement parameters for the non- H atoms using SHELXL The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5xUeq for methyl hydrogen atoms). The function, w( Fo 2 - Fc 2 ) 2, was minimized, where w = 1/[( (Fo)) 2 + (0.0415*P) 2 + (0.9360*P)] and P = ( Fo Fc 2 )/3. Rw(F 2 ) refined to 0.191, with R(F) equal to and a goodness of fit, S = Definitions used for calculating R(F), Rw(F 2 ) and the goodness of fit, S, are given below. 7 The data were corrected for secondary extinction effects. The correction takes the form: Fcorr = kfc/[1 + (2.3(2)x10-6 )* Fc 2 3 /(sin2 )] 0.25 where k is the overall scale factor. Neutral atom scattering factors and values used to calculate the linear absorption coefficient are from the International Tables for X-ray Crystallography (1992). 8 All figures were generated using SHELXTL/PC. 9 Figure S10. Crystal structure of P 2 P 4 -TFTPA. Left: top view; right: packing. For the sake of clarity, hydrogen atoms and solvent molecule(s) are not shown. S9

10 Table S2. Crystal data for P 2 P 4 -TFTPA. Empirical Formula C 26 H 27 N 3 O 2 Cl 3 F 2 Formula Weight Temperature 163K Wavelength Å Crystal Color, Habit brown, needle Crystal Dimensions X X mm Crystal System triclinic Space Group P-1 a/å b/å c/å Lattice Parameters α/deg β/deg /deg V/Å Z Value 2 D calc /g cm F No. of Reflections Measured Total: Unique: 5679 (R int = 0.070) Data/restraints/parameters 5679/0/329 R1; wr2 (all data) 0.101; Goodness of Fit Indicator (GOF) 1.04 R1; wr2 (I>2σ(I)) 0.063; S10

11 4.3. P 2 P 4 -OFBPA (CCDC: ) Crystals grew as brown plates by vapor diffusion of hexanes into a chloroform solution (containing trace methanol) of the free base form of the P 2 P 4 macrocycle and excess OFBPA. The data crystal had approximate dimensions: x x mm. The data were collected on a Nonius Kappa CCD diffractometer using a graphite monochromator with MoK radiation ( = Å). A total of 379 frames of data were collected using -scans. The data were collected at 163 K using an Oxford Cryostream low temperature device. Details of crystal data, data collection and structure refinement are listed in Table S3. Data reduction were performed using DENZO-SMN. 10 The structure was solved by direct methods using SIR97 2 and refined by full-matrix least-squares on F 2 with anisotropic displacement parameters for the non- H atoms using SHELXL The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5xUeq for methyl hydrogen atoms). One solvent molecule was found to be badly disordered. The contributions to the scattering factors due to this solvent molecule were removed by use of the utility SQUEEZE 6 in PLATON98 4. PLATON98 was used as incorporated in WinGX 5. The function, w( Fo 2 - Fc 2 ) 2, was minimized, where w = 1/[( (Fo)) 2 + (0.0415*P) 2 + (0.9360*P)] and P = ( Fo Fc 2 )/3. Rw(F 2 ) refined to 0.156, with R(F) equal to and a goodness of fit, S = Definitions used for calculating R(F), Rw(F 2 ) and the goodness of fit, S, are given below. 7 The data were corrected for secondary extinction effects. The correction takes the form: Fcorr = kfc/[1 + (2.3(2)x10-6 )* Fc 2 3 /(sin2 )] 0.25 where k is the overall scale factor. Neutral atom scattering factors and values used to calculate the linear absorption coefficient are from the International Tables for X-ray Crystallography (1992). 8 All figures were generated using SHELXTL/PC. 9 S11

12 Figure S11. Crystal structure of P 2 P 4 -OFBPA. Left: top view; right: packing. For the sake of clarity, hydrogen atoms are not shown. Table S3. Crystal data for P 2 P 4 -OFBPA. Empirical Formula C 28 H 26 N 3 O 2 F 4 Formula Weight Temperature 163K Wavelength Å Crystal Color, Habit brown, plate Crystal Dimensions X X mm Crystal System orthorhombic Space Group Pccn a/å b/å c/å Lattice Parameters α/deg β/deg /deg V/Å Z Value 8 D calc /g cm F No. of Reflections Measured Total: S12

13 Unique: 4705 (R int = 0.106) Data/restraints/parameters 4705/222/338 R1; wr2 (all data) 0.082; Goodness of Fit Indicator (GOF) 1.06 R1; wr2 (I>2σ(I)) 0.057; S13

14 4.4. P 2 P 4 -ADCA (CCDC: ) Crystals grew as brown needles by vapor diffusion of hexanes into a CH 2 Cl 2 solution (containing trace methanol) of the free base form of the P 2 P 4 macrocycle and excess ADCA. The data crystal had approximate dimensions: x x mm. The data were collected on a Nonius Kappa CCD diffractometer using a graphite monochromator with MoK radiation ( = Å). A total of 314 frames of data were collected using -scans. The data were collected at 163 K using an Oxford Cryostream low temperature device. Details of crystal data, data collection and structure refinement are listed in Table S4. Data reduction were performed using DENZO-SMN. 10 The structure was solved by direct methods using SIR97 2 and refined by fullmatrix least-squares on F 2 with anisotropic displacement parameters for the non-h atoms using SHELXL The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5xUeq for methyl hydrogen atoms). The function, w( Fo 2 - Fc 2 ) 2, was minimized, where w = 1/[( (Fo)) 2 + (0.0415*P) 2 + (0.9360*P)] and P = ( Fo Fc 2 )/3. Rw(F 2 ) refined to 0.221, with R(F) equal to and a goodness of fit, S = Definitions used for calculating R(F), Rw(F 2 ) and the goodness of fit, S, are given below. 7 The data were corrected for secondary extinction effects. The correction takes the form: Fcorr = kfc/[1 + (2.3(2)x10-6 )* Fc 2 3 /(sin2 )] 0.25 where k is the overall scale factor. Neutral atom scattering factors and values used to calculate the linear absorption coefficient are from the International Tables for X-ray Crystallography (1992). 8 All figures were generated using SHELXTL/PC. 9 S14

15 Figure S12. Crystal structure of P 2 P 4 -ADCA. Left: top view; right: packing. For the sake of clarity, hydrogen atoms and solvent molecule(s) are not shown. Table S4. Crystal data for P 2 P 4 -ADCA. Empirical Formula C 26 H 26 N 3 O 4 Cl 2 Formula Weight Temperature 163K Wavelength Å Crystal Color, Habit brown, needle Crystal Dimensions X X mm Crystal System monoclinic Space Group P21/n a/å b/å c/å Lattice Parameters α/deg β/deg /deg V/Å Z Value 4 D calc /g cm F S15

16 No. of Reflections Measured Total: Unique: 4681 (R int = 0.105) Data/restraints/parameters 4681/216/332 R1; wr2 (all data) 0.125; Goodness of Fit Indicator (GOF) 1.10 R1; wr2 (I>2σ(I)) 0.080; S16

17 4.5. P 2 P 4 -OA (CCDC: ) Crystals grew as brown prisms by vapor diffusion of hexanes into a chloroform solution (containing trace methanol) of the free base form of the P 2 P 4 macrocycle and excess oxalic acid. The data crystal had approximate dimensions: x x 0.06 mm. The data were collected on a Nonius Kappa CCD diffractometer using a graphite monochromator with MoK radiation ( = Å). A total of 1453 frames of data were collected using -scans. The data were collected at 163 K using an Oxford Cryostream low temperature device. Details of crystal data, data collection and structure refinement are listed in Table S5. Data reduction were performed using DENZO-SMN. 10 The structure was solved by direct methods using SIR97 2 and refined by full-matrix least-squares on F 2 with anisotropic displacement parameters for the non-h atoms using SHELXL The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5xUeq for methyl hydrogen atoms). The function, w( Fo 2 - Fc 2 ) 2, was minimized, where w = 1/[( (Fo)) 2 + (0.0415*P) 2 + (0.9360*P)] and P = ( Fo Fc 2 )/3. Rw(F 2 ) refined to 0.239, with R(F) equal to and a goodness of fit, S = Definitions used for calculating R(F), Rw(F 2 ) and the goodness of fit, S, are given below. 7 The data were corrected for secondary extinction effects. The correction takes the form: Fcorr = kfc/[1 + (2.3(2)x10-6 )* Fc 2 3 /(sin2 )] 0.25 where k is the overall scale factor. Neutral atom scattering factors and values used to calculate the linear absorption coefficient are from the International Tables for X-ray Crystallography (1992). 8 All figures were generated using SHELXTL/PC. 9 Figure S13. Crystal structure of P 2 P 4 -OA. Left: top view; right: packing. For the sake of clarity, hydrogen atoms and solvent molecule(s) are not shown. S17

18 Table S5. Crystal data for P 2 P 4 -OA. Empirical Formula C 48 H 56 N 6 O 8 Cl 6 Formula Weight Temperature 163K Wavelength Å Crystal Color, Habit brown, prism Crystal Dimensions X X 0.06 mm Crystal System triclinic Space Group P-1 a/å b/å c/å Lattice Parameters α/deg β/deg /deg V/Å Z Value 2 D calc /g cm F No. of Reflections Measured Total: Unique: 8939 (R int = 0.067) Data/restraints/parameters 8939/0/623 R1; wr2 (all data) 0.124; Goodness of Fit Indicator (GOF) 1.02 R1; wr2 (I>2σ(I)) 0.079; S18

19 4.6. P 3 P 3 -TFTPA (CCDC: ) Crystals grew as red plates by vapor diffusion of hexanes into a chloroform solution (containing trace methanol) of the free base form of the P 3 P 3 macrocycle and excess TFTPA. The data crystal had approximate dimensions: x x mm. The data were collected on a Nonius Kappa CCD diffractometer using a graphite monochromator with MoK radiation ( = Å). A total of 1064 frames of data were collected using -scans. The data were collected at 163 K using an Oxford Cryostream low temperature device. Details of crystal data, data collection and structure refinement are listed in Table S6. Data reduction were performed using DENZO-SMN. 10 The structure was solved by direct methods using SIR97 2 and refined by full-matrix least-squares on F 2 with anisotropic displacement parameters for the non- H atoms using SHELXL The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5xUeq for methyl hydrogen atoms). One solvent molecule was found to be badly disordered. The contributions to the scattering factors due to this solvent molecule were removed by use of the utility SQUEEZE 6 in PLATON98. 4 PLATON98 was used as incorporated in WinGX. 5 The function, w( Fo 2 - Fc 2 ) 2, was minimized, where w = 1/[( (Fo)) 2 + (0.0415*P) 2 + (0.9360*P)] and P = ( Fo Fc 2 )/3. Rw(F 2 ) refined to 0.245, with R(F) equal to and a goodness of fit, S = Definitions used for calculating R(F), Rw(F 2 ) and the goodness of fit, S, are given below. 7 The data were corrected for secondary extinction effects. The correction takes the form: Fcorr = kfc/[1 + (2.3(2)x10-6 )* Fc 2 3 /(sin2 )] 0.25 where k is the overall scale factor. Neutral atom scattering factors and values used to calculate the linear absorption coefficient are from the International Tables for X-ray Crystallography (1992). 8 All figures were generated using SHELXTL/PC. 9 S19

20 Figure S14. Crystal structure of P 3 P 3 -TFTPA. Left: top view; right: packing. For the sake of clarity, hydrogen atoms are not shown. Table S6. Crystal data for P 3 P 3 -TFTPA. Empirical Formula C 51 H 36 N 6 O 8 F 8 Formula Weight Temperature 163K Wavelength Å Crystal Color, Habit red, plate Crystal Dimensions X X mm Crystal System monoclinic Space Group P21/c a/å b/å c/å Lattice Parameters α/deg β/deg /deg V/Å Z Value 4 D calc /g cm S20

21 F No. of Reflections Measured Total: Unique: 8694 (R int = 0.140) Data/restraints/parameters 8694/0/662 R1; wr2 (all data) 0.163; Goodness of Fit Indicator (GOF) 1.02 R1; wr2 (I>2σ(I)) 0.088; S21

22 4.7. P 3 P 3 -ADCA (CCDC: ) Crystals grew as red plates by vapor diffusion of hexanes into a chloroform solution (containing trace THF) of the free base form of the P 3 P 3 macrocycle and excess ADCA. The data crystal had approximate dimensions: x x mm. The data were collected on a Nonius Kappa CCD diffractometer using a graphite monochromator with MoK radiation ( = Å). A total of 598 frames of data were collected using -scans. The data were collected at 163 K using an Oxford Cryostream low temperature device. Details of crystal data, data collection and structure refinement are listed in Table S7. Data reduction were performed using DENZO-SMN. 10 The structure was solved by direct methods using SIR97 2 and refined by fullmatrix least-squares on F 2 with anisotropic displacement parameters for the non-h atoms using SHELXL The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5xUeq for methyl hydrogen atoms). One solvent molecule was found to be badly disordered. The contributions to the scattering factors due to this solvent molecule were removed by use of the utility SQUEEZE 6 in PLATON98. 4 PLATON98 was used as incorporated in WinGX. 5 The function, w( Fo 2 - Fc 2 ) 2, was minimized, where w = 1/[( (Fo)) 2 + (0.0415*P) 2 + (0.9360*P)] and P = ( Fo Fc 2 )/3. Rw(F 2 ) refined to 0.192, with R(F) equal to and a goodness of fit, S = Definitions used for calculating R(F), Rw(F 2 ) and the goodness of fit, S, are given below. 7 The data were corrected for secondary extinction effects. The correction takes the form: Fcorr = kfc/[1 + (2.3(2)x10-6 )* Fc 2 3 /(sin2 )] 0.25 where k is the overall scale factor. Neutral atom scattering factors and values used to calculate the linear absorption coefficient are from the International Tables for X-ray Crystallography (1992). 8 All figures were generated using SHELXTL/PC. 9 S22

23 Figure 15. Crystal structure of P 3 P 3 -ADCA. Left: top view; right: 2D packing. For the sake of clarity, hydrogen atoms are not shown. Table S7. Crystal data for P 3 P 3 -ADCA. Empirical Formula C 45 H 36 N 6 O 11 Formula Weight Temperature 163K Wavelength Å Crystal Color, Habit red, plate Crystal Dimensions X X mm Crystal System triclinic Space Group P-1 a/å b/å c/å Lattice Parameters α/deg β/deg /deg V/Å Z Value 2 D calc /g cm F S23

24 No. of Reflections Measured Total: Unique: 7910 (R int = 0.156) Data/restraints/parameters 7910/372/563 R1; wr2 (all data) 0.129; Goodness of Fit Indicator (GOF) 0.97 R1; wr2 (I>2σ(I)) 0.073; S24

25 4.8. P 3 P 3 -OA (CCDC: ) Single crystals grew as red plates by vapor diffusion of hexanes into a CH 2 Cl 2 solution (containing trace methanol) of the free base form of the P 3 P 3 macrocycle and excess oxalic acid. The data crystal had approximate dimensions: 0.64 x 0.21 x 0.08 mm. The data were collected on a Rigaku AFC12 diffractometer with a Saturn 724+ CCD using a graphite monochromator with MoK radiation ( = Å). The data were collected at 100 K using a Rigaku XStream low temperature device. Details of crystal data are listed in Table S8. Data reduction were performed using the Rigaku Americas Corporation s Crystal Clear version The structure was solved by direct methods using SIR97 2 and refined by full-matrix least-squares on F 2 with anisotropic displacement parameters for the non-h atoms using SHELXL Structure analysis was aided by use of WinGX. 5 The hydrogen atoms on carbon were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5xUeq for methyl hydrogen atoms). One solvent molecule was found to be badly disordered. The contributions to the scattering factors due to this solvent molecule were removed by use of the utility SQUEEZE 6 in PLATON98. 4 PLATON98 was used as incorporated in WinGX. 5 The function, w( Fo 2 - Fc 2 ) 2, was minimized, where w = 1/[( (Fo)) 2 + (0.0528*P) 2 + (0.685*P)] and P = ( Fo Fc 2 )/3. Rw(F 2 ) refined to 0.139, with R(F) equal to and a goodness of fit, S, = Definitions used for calculating R(F), Rw(F 2 ) and the goodness of fit, S, are given below. 7 The data were checked for secondary extinction effects but no correction was necessary. Neutral atom scattering factors and values used to calculate the linear absorption coefficient are from the International Tables for X-ray Crystallography (1992). 8 All figures were generated using SHELXTL/PC. 9 S25

26 Figure S16. Crystal structure of P 3 P 3 -OA. Left: top view; right: packing. For the sake of clarity, hydrogen atoms are not shown. Table S8. Crystal data for P 3 P 3 -OA. Empirical Formula C 41 H 40 N 6 O 12 Formula Weight Temperature 100K Wavelength Å Crystal Color, Habit red, plate Crystal Dimensions 0.64 X 0.21 X 0.08 mm Crystal System Triclinic Space Group P-1 a/å b/å c/å Lattice Parameters α/deg β/deg /deg V/Å Z Value 2 D calc /g cm S26

27 F No. of Reflections Measured Total: Unique: 9191 (R int = 0.046) Data/restraints/parameters 9191/354/540 R1; wr2 (all data) 0.064; Goodness of Fit Indicator (GOF) 0.95 R1; wr2 (I>2σ(I)) 0.048; S27

28 5. Solvent Response Solvent response tests. A 5 ml solution/suspension of an assembly sample prepared as above was transferred to a 15 ml vial, followed by addition of 0.5 ml of the test solvent in question. The samples were shaken and the pictures were taken. A smaller sample (0.4 ml) was taken and diluted to 4 ml in a UV cell. The UV-Vis and fluorescence spectra were then recorded using the diluted sample. For the UV-Vis studies, the letters UT were printed on a white background to aid in visualization and to facilitate distinction between samples that were turbid and fully dissolved. Note: All the assemblies, as judged by the naked eye, produced a similar response towards benzene and toluene; methanol and ethanol. Benzene and ethanol were not included in the pictures for the sake of brevity. However, they were included in the spectral measurement studies. Solvent mixture discrimination studies. Using 96-well plates, acetonitrile, chloroform, benzene, or toluene (100 μl) were mixed with diethyl ether, THF, ethyl acetate, acetone, methanol, ethanol, DMF, or DMSO (10 μl) to make a total of 32 wells each containing a different solvent mixture. The assembly solution (100 μl in CH 2 Cl 2 ) was pipetted into each well. The fluorescence was then recorded on a well plate reader ( nm, 20 nm increments). S28

29 Table S9. Results of solvent response studies. Note: the underlined solvents are those that give rise to a unique response. Visible change Fluorescence change P 2 P 4 -BPDSA DMSO diethyl ether, THF, MeOH, acetone P 3 P 3 -BPDSA THF, MeOH, DMF, DMSO THF, MeOH, DMF, DMSO P 2 P 4 -TFTPA THF, MeOH, DMF, DMSO MeOH P 3 P 3 -TFTPA diethyl ether, THF, ethyl acetate, acetone, MeOH, DMF, DMSO MeOH P 2 P 4 -OFBPA THF, MeOH, DMF, DMSO diethyl ether, THF, ethyl acetate, acetone, MeOH, DMF, DMSO P 3 P 3 -OFBPA diethyl ether, THF, ethyl acetate, Acetone, MeOH, DMF, DMSO MeOH P 2 P 4 -OA diethyl ether, THF, acetone, MeOH, DMF, DMSO diethyl ether, THF, ethyl acetate, acetone, MeOH, DMF, DMSO P 3 P 3 -OA diethyl ether, THF, ethyl acetate, acetone, MeOH, MeCN, DMF, DMSO diethyl ether, THF, ethyl acetate, acetone, MeOH, MeCN, DMF, DMSO P 2 P 4 -ADCA eiethyl ether, THF, acetone, MeOH, DMF, DMSO diethyl ether, THF, acetone, MeOH, DMF, DMSO P 3 P 3 -ADCA diethyl ether, THF, ethyl acetate, acetone, MeOH, MeCN, DMF, DMSO diethyl ether, THF, ethyl acetate, acetone, MeOH S29

30 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) Control (5) DMF (6) DMSO (7) Ethyl Acetate (8) Ethanol (9) Diethyl Ether (10) Methanol (11) THF (12) Toluene (13) Wavelength (nm) Figure S17. Response of P 2 P 4 -BPDSA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S30

31 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) Control (5) DMF (6) DMSO (7) Ethyl Acetate (8) Ethanol (9) Diethyl Ether (10) Methanol (11) THF (12) Toluene (13) Wavelength (nm) Figure S18. Response of P 2 P 4 -TFTPA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S31

32 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) DMF (5) DMSO (6) Ethyl Acetate (7) Ethanol (8) Diethyl Ether (9) Methanol (10) THF (11) Toluene (12) Wavelength (nm) Figure S19. Response of P 2 P 4 -OFBPA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S32

33 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) Control (5) DMF (6) DMSO (7) Ethyl Acetate (8) Ethanol (9) Diethyl Ether (10) Methanol (11) THF (12) Toluene (13) Wavelength (nm) Figure S20. Response of P 2 P 4 -OA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S33

34 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) Control (5) DMF (6) DMSO (7) Ethyl Acetate (8) Diethyl Ether (9) Ethanol (10) Methanol (11) THF (12) Toluene (13) Wavelength (nm) Figure S21. Response of P 2 P 4 -ADCA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S34

35 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) Control (5) DMF (6) DMSO (7) Ethyl Acetate (8) Ethanol (9) Diethyl Ether (10) Methanol (11) THF (12) Toluene (13) Wavelength (nm) Figure S22. Response of P 3 P 3 -BPDSA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S35

36 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) Control (5) DMF (6) DMSO (7) Ethyl Acetate (8) Ethanol (9) Diethyl Ether (10) Methanol (11) THF (12) Toluene (13) Wavelength (nm) Figure S23. Response of P 3 P 3 -TFTPA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S36

37 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) Control (5) DMF (6) DMSO (7) Ethyl Acetate (8) Ethanol (9) Diethyl Ether (10) Methanol (11) THF (12) Toluene (13) Wavelength (nm) Figure S24. Response of P 3 P 3 -OFBPA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S37

38 Intensity Acetone (1) Acetonitril (2) Benzene (3) Chloroform (4) Control (5) DMF (6) DMSO (7) Ethyl Acetate (8) Ethanol (9) Diethyl Ether (10) Methanol (11) THF (12) Toluene (13) Wavelength (nm) Figure S25. Response of P 3 P 3 -OA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S38

39 Intensity Acetone (1) Acetonitril (2) DMF (3) DMSO (4) Ethyl Acetate (5) Diethyl Ether (6) Ethanol (7) Methanol (8) THF (9) Wavelength (nm) Figure S26. Response of P 3 P 3 -ADCA (in CH 2 Cl 2 ) towards solvents. Upper left: color change upon addition of a solvent (in the order of CH 2 Cl 2, chloroform, toluene, diethyl ether, THF, ethyl acetate, acetone, methanol, acetonitrile, DMF and DMSO); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S39

40 F3 (18.02 %) F3 (18.02 %) F2 (22.51 %) Observations (axes F1 and F2: %) F1 (46.08 %) A1 A3 A5 A7 C1 C3 C5 C7 E1 E3 E5 E7 G1 G3 G5 G7 A2 A4 A6 A8 C2 C4 C6 C8 E2 E4 E6 E8 G2 G4 G6 G8 Observations (axes F2 and F3: %) F2 (22.51 %) A1 A3 A5 A7 C1 C3 C5 C7 E1 E3 E5 E7 G1 G3 G5 A2 A4 A6 A8 C2 C4 C6 C8 E2 E4 E6 E8 G2 G4 G6 Observations (axes F4 and F3: %) F4 (4.75 %) A1 A3 A5 A7 C1 C3 C5 C7 E1 E3 E5 E7 G1 G3 G5 A2 A4 A6 A8 C2 C4 C6 C8 E2 E4 E6 E8 G2 G4 G6 Figure S27. Differentiation of 32 different solvent mixtures with P 3 P 3 -BPDSA, P 2 P 4 - BPDSA, P 2 P 4 -ACA, and P 3 P 3 -TFTPA. Discrimination experiments were conducted on a 96- well plate with the response being recorded using a BioTek Cytation3 plate reader. Using the Gen5 program, the fluorescence emission ( nm, 20 nm increments, 451 nm excitation) for each assembly was recorded. Each assembly (1.0 mm in CH 2 Cl 2, 100 μl) was subjected to S40

41 32 different solvent mixtures, each composed of two solvents: either acetonitrile, chloroform, benzene, or toluene (100 μl) mixed with diethyl ether, THF, ethyl acetate, acetone, methanol, ethanol, DMF, or DMSO (10 μl). The three figures shown here are included so as to illustrate the four dimensionality of the processed data feature space. S41

42 6. Anion Response Anion response tests. A 5 ml solution/suspension of an assembly sample prepared as above was transferred to a 15 ml vial. This was followed by the addition of an excess of the organic anion in solid salt form. The samples were shaken and the pictures were taken. A 0.4 ml aliquot was taken and diluted to 4 ml in a UV cell. The UV-Vis and fluorescence spectra were then recorded using the diluted sample. Note: The organic anion salts used in these tests were TBA fluoride, TBA chloride, TBA bromide, TBA iodide, TBA nitrate, TMA sulfate and TBA monobasic phosphate, where TBA = tetrabutylammonium and TMA = tetramethylammonium. Table S10. Results of anion response studies. Note: the underlined solvents are those that give rise to a unique response. Visible change P 2 P 4 -BPDSA F -, Cl -, Br - (1 h), NO (1 h), H 2 PO 4 P 3 P 3 -BPDSA F -, Cl -, Br -, NO - - 3, H 2 PO 4 P 2 P 4 -TFTPA F -, Cl - -, H 2 PO 4 P 3 P 3 -TFTPA F - -, H 2 PO 4 P 2 P 4 -OFBPA F -, Cl - -, H 2 PO 4 P 3 P 3 -OFBPA F -, Cl - -, H 2 PO 4 P 2 P 4 -OA F - -, H 2 PO 4 P 3 P 3 -OA F -, NO - - 3, H 2 PO 4 P 2 P 4 -ADCA F -, Cl - -, H 2 PO 4 P 3 P 3 -ADCA F -, Cl - -, H 2 PO 4 Fluorescence change F -, Cl -, Br -, NO - 3, SO , H 2 PO 4 Cl -, Br - F -, Cl F -, Cl -, Br - (1 h), SO (1 h), H 2 PO F - -, H 2 PO F -, Cl - -, H 2 PO S42

43 Intensity Br Cl Control F H 2 PO 4 I NO 3 SO Wavelength (nm) Figure S28. Response of P 2 P 4 -BPDSA (in CH 2 Cl 2 ) towards anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); middle-left: corresponding color change after 1 h; middle-right: corresponding fluorescence change after 1 h; lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S43

44 Intensity Br Cl Control F H 2 PO 4 I NO 3 SO Wavelength (nm) Figure S29. Response of P 2 P 4 -TFTPA (in CH 2 Cl 2 ) to anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S44

45 Intensity Br Cl Control F H 2 PO 4 I NO 3 SO Wavelength (nm) Figure S30. Response of P 2 P 4 -OA (in CH 2 Cl 2 ) towards anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S45

46 Intensity Br Cl Control F H 2 PO 4 I NO 3 SO Wavelength (nm) Figure S31. Response of P 2 P 4 -OFBPA (in CH 2 Cl 2 ) towards anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); middle left: corresponding color change after 1 h; middle right: corresponding fluorescence change after 1 h; lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S46

47 Intensity Br Cl F I NO 3 H 2 PO 4 SO Wavelength (nm) Figure S32. Response of P 2 P 4 -ADCA (in CH 2 Cl 2 ) to anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S47

48 Intensity Br Cl Control F H 2 PO 4 I NO 3 SO Wavelength (nm) Figure S33. Response of P 3 P 3 -BPDSA (in CH 2 Cl 2 ) to anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S48

49 Intensity Br Cl Control F H 2 PO 4 I NO 3 SO Wavelength (nm) Figure S34. Response of P 3 P 3 -TFTPA (in CH 2 Cl 2 ) to anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S49

50 Intensity Br Cl Control F I NO 3 H 2 PO 4 SO Wavelength (nm) Figure S35. Response of P 3 P 3 -OFBPA (in CH 2 Cl 2 ) to anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S50

51 Intensity Br Cl Control F H 2 PO 4 I NO 3 SO Wavelength (nm) Figure S36. Response of P 3 P 3 -OA (in CH 2 Cl 2 ) towards anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate and monobasic phosphate); upper right: corresponding fluorescence change (excited at 365 nm); lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S51

52 Intensity Br Cl Control F I NO 3 H 2 PO 4 SO Wavelength (nm) Figure S37. Response of P 3 P 3 -ADCA (in CH 2 Cl 2 ) to anions. Upper left: color change upon addition of an anion (in the order of control, fluoride, chloride, bromide, iodide, nitrate, sulfate lower left: UV-Vis spectra of diluted samples; lower right: corresponding fluorescence spectra. S52

53 7. Measurement of pka 2 ph values were measured with Mettler Toledo SevenEasy probe. A solution of tetrafluoroteraphthalic acid (TFTPA) (52 mg in 10 ml H 2 O) was titrated with 0.25 M NaOH at 0.1 ml aliquots. pka 2 was calculated from the 2 nd derivative of the titration curve. pka 2 = 2.0. A solution of 4,4'-biphenyldisulfonic acid (BPDSA) (72 mg in 10 ml H 2 O) was titrated with 0.25 M NaOH at 0.1 ml aliquots. pka 2 was calculated from the 2 nd derivative of the titration curve. pka 2 = 1.7. S53

54 8. References 1. CrysAlisPro. Agilent Technologies (2013). Agilent Technologies UK Ltd., Oxford, UK, SuperNova CCD System, CrysAlicPro Software System, SIR97. Altomare A., Burla M. C., Camalli M.; Cascarano G. L.; Giacovazzo C.; Guagliardi A.; Moliterni A. G. G.; Polidori G.; Spagna, R. J. Appl. Cryst. 1999, 32, SHELXL Sheldrick, G. M. Acta Cryst. 2008, A64, Spek, A. L. (1998). PLATON, A Multipurpose Crystallographic Tool. Utrecht University, The Netherlands. 5. WinGX Farrugia, L. J. J. Appl. Cryst. 1999, 32, SQUEEZE. Sluis, P. v. d.; Spek, A. L. Acta Cryst. 1990, A46, Rw(F 2 ) = { w( Fo 2 - Fc 2 ) 2 / w( Fo ) 4 } 1/2 where w is the weight given each reflection. R(F) = ( Fo - Fc )/ Fo } for reflections with Fo > 4( (Fo)). S = [ w( Fo 2 - Fc 2 ) 2 /(n - p)] 1/2, where n is the number of reflections and p is the number of refined parameters. 8. International Tables for X-ray Crystallography 1992, C, Tables and , A. J. C. Wilson, editor, Boston: Kluwer Academic Press. 9. Sheldrick, G. M. (1994). SHELXTL/PC (Version 5.03). Siemens Analytical X- ray Instruments, Inc., Madison, Wisconsin, USA. 10. DENZO-SMN (1997). Otwinowski, Z.; Minor, W. Methods in Enzymology, 276: Macromolecular Crystallography, part A, , C. W. Carter, Jr. and R. M. Sweets, Editors, Academic Press. 11. CrystalClear 1.40 (2008). Rigaku Americas Corportion, The Woodlands, TX. S54