Ion-pairing assemblies of π-extended anion-responsive organoplatinum complexes

ABSTRACT PtII complexes of π-extended dipyrrolyldiketones were synthesized as anion-responsive π-electronic molecules. The dipyrrolyldiketone PtII complexes exhibited red-shifted absorption and photoluminescence properties. In the solid state, [1 + 1]-type anion complexes formed charge-by-charge ion-pairing assemblies when combined with countercations. Detailed theoretical studies of the packing structures revealed favorable interactions between the planar anion complexes and π-electronic cations.


Figure S3
1 H NMR spectrum of 2b in DMSO-d6 at 20 °C. 13C{ 1 H} NMR spectrum was not measured due to the decomposition after prolonged measurement time.

Figure S4
1 H NMR spectrum of 2c in CDCl3 at 20 °C. 13C{ 1 H} NMR spectrum was not measured due to the decomposition after prolonged measurement time.

Figure S5
UV/vis absorption spectra of (a) 2b and (b) 2c in CH2Cl2 (0.02 mM) along with unsubstituted Pt II complex 2a as a reference (gray).

X-ray crystallographic data
Figure S6 Ortep drawings of single-crystal X-ray structure (top and side views) of 1c´ as three independent structures A-C.Thermal ellipsoids are scaled to the 50% probability level.In structure A, disordered structures are represented by black and white bonds for major and minor structures, respectively, in the ratio of 58.2:41.8 for a pyrrole unit.Atom color code: black, blue, red, and green refer to carbon, nitrogen, oxygen, and fluorine, respectively.

Figure S27
Single-crystal X-ray structure of 2c•Cl --TBA + for the EDA calculations (Table S2): (a) top view of structure and (b) side view of shaded part in (a).The labels (c1,2 and a1) correspond to the fragments shown in Table S2.
Table S2 Energies between selected fragments in 2c•Cl --TBA + (Figure S27) estimated by EDA calculation [S5] based on an FMO2-MP2 using mixed basis sets including NOSeC-V-TZP for Au and Pt and NOSeC-V-DZP for the other atoms.

Figure S28
Single-crystal X-ray structure of 2b•Cl --TPPAu + for the EDA calculations (Table S3): (a) top view of structure and (b) side view of shaded part in (a).The labels (c1,2 and a1) correspond to the fragments shown in Table S3.
Table S3 Energies between selected fragments in 2b•Cl --TPPAu + (Figure S28) estimated by EDA calculation [S5] based on an FMO2-MP2 using mixed basis sets including NOSeC-V-TZP for Au and Pt and NOSeC-V-DZP for the other atoms.

Figure S29
Single-crystal X-ray structure of 2c•Cl --TPPAu + for the EDA calculations (Table S4): (a) top view of structure and (b) side view of shaded part in (a).The labels (c1,2 and a1) correspond to the fragments shown in Table S4.
Table S4 Energies between selected fragments in 2c•Cl --TPPAu + (Figure S29) estimated by EDA calculation [S5] based on an FMO2-MP2 using mixed basis sets including NOSeC-V-TZP for Au and Pt and NOSeC-V-DZP for the other atoms.Table S5 Emission quantum yields of 2b,c in non-deoxygenated and deoxygenated CH2Cl2 at 20 °C.

Figure S8
Figure S8Ortep drawings of single-crystal X-ray structure (top and side views) of 2c•Cl --TBA + .Thermal ellipsoids are scaled to the 50% probability level.Disordered structures are represented by black and white bonds for major and minor structures, respectively, in the ratio of 55.6:44.4 for one side of the pyrrole unit with arylethynyl and 60.0:40.0 for the ethyl units.Atom color code: black, blue, red, green, yellow green, and gray refer to carbon, nitrogen, oxygen, fluorine, chlorine, and platinum, respectively.

Figure S9
Figure S9Ortep drawings of single-crystal X-ray structure (top and side views) of 2b•Cl --TPPAu + .Thermal ellipsoids are scaled to the 50% probability level.Atom color code: black, blue, red, yellow green, gray, and orange refer to carbon, nitrogen, oxygen, chlorine, platinum, and gold, respectively.

Figure S10
Figure S10Ortep drawings of single-crystal X-ray structure (top and side views) of 2c•Cl --TPPAu + .Thermal ellipsoids are scaled to the 50% probability level.Atom color code: black, blue, red, green, yellow green, gray, and orange refer to carbon, nitrogen, oxygen, fluorine, chlorine, platinum, and gold, respectively.Solvent molecules are omitted for clarity.

Figure S15
Figure S15Hirshfeld surfaces[2,3]  of 2b•Cl -(independent structures(a,b) and (c,d), wherein (b,d) show different sides of (a,c)) in the crystal structure of 2b•Cl --TBA + mapped over (i) shape-index and (ii) curvedness properties for only surface (left) and surface with a ball-and-stick model of the neighboring TBA + (right).Shape index is a qualitative measure of shape and is sensitive to subtle changes in surface shape, particularly in a flat region by differing by signs representing complementary bumps (blue) and hollows (red), whereas curvedness is a function of the root-mean-square curvature of the surface, and maps of curvedness typically show large regions of green (relatively flat) separated by dark blue edges (large positive curvature).The flat region on the curvedness surface suggested the characteristic mapping pattern for stacking between TBA + and 2b•Cl -.

Figure S16
Figure S16Hirshfeld surfaces[2,3]  of 2c•Cl -((a,b) for different sides) in the crystal structure of 2c•Cl --TBA + mapped over (i) shape-index and (ii) curvedness properties for only surface (left) and surface with a ball-and-stick model of the neighboring TBA + (right).Shape index is a qualitative measure of shape and is sensitive to subtle changes in surface shape, particularly in a flat region by differing by signs representing complementary bumps (blue) and hollows (red), whereas curvedness is a function of the root-mean-square curvature of the surface, and maps of curvedness typically show large regions of green (relatively flat) separated by dark blue edges (large positive curvature).The flat region on the curvedness surface suggested the characteristic mapping pattern for stacking between TBA + and 2c•Cl -.

Figure S17
Figure S17Hirshfeld surfaces[2,3]  of 2b•Cl -((a,b) for different sides) in the crystal structure of 2b•Cl --TPPAu + mapped over (i) shape-index and (ii) curvedness properties for only surface (left) and surface with a ball-and-stick model of the neighboring TPPAu + (right).Shape index is a qualitative measure of shape and is sensitive to subtle changes in surface shape, particularly in a flat region by differing by signs representing complementary bumps (blue) and hollows (red), whereas curvedness is a function of the root-mean-square curvature of the surface, and maps of curvedness typically show large regions of green (relatively flat) separated by dark blue edges (large positive curvature).The flat region on the curvedness surface suggested the characteristic mapping pattern for stacking between TPPAu + and 2b•Cl -.

Figure S18 Figure 20
Figure S18Hirshfeld surfaces[2,3]  of 2c•Cl -((a,b) for different sides) in the crystal structure of 2c•Cl --TPPAu + mapped over (i) shape-index and (ii) curvedness properties for only surface (left) and surface with a ball-and-stick model of the neighboring TPPAu + (right).Shape index is a qualitative measure of shape and is sensitive to subtle changes in surface shape, particularly in a flat region by differing by signs representing complementary bumps (blue) and hollows (red), whereas curvedness is a function of the root-mean-square curvature of the surface, and maps of curvedness typically show large regions of green (relatively flat) separated by dark blue edges (large positive curvature).The flat region on the curvedness surface suggested the characteristic mapping pattern for stacking between TPPAu + and 2c•Cl -.

Figure S22
Figure S22 Molecular orbitals (HOMO and LUMO) of 2c (left) and 2c•Cl -(right) estimated at the PCM-B3LYP level by using 6-31+G(d,p) basis set was used for C, H, N, O, F, and Cl and the LanL2DZ basis set and associated effective core potentials were used for Pt in solution phase (CH2Cl2).[S4]

Figure S25
Figure S25ESP mapping (δ = 0.0004) of (a) Pt II complexes (i) 2b and (ii) 2c and (b) their Cl -complexes calculated at the CAM-B3LYP level by using 6-31+G(d,p) basis set was used for C, H, N, O, F, and Cl and the LanL2DZ basis set and associated effective core potentials were used for Pt in solution phase.[S4]

Figure
Figure S30 UV/vis absorption spectral changes (left) and corresponding titration plots and 1:1 fitting curves (right) of (a) 2b and (b) 2c upon the addition of Cl -as a tetrabutylammonium (TBA) salt in CH2Cl2 (0.02 mM).Due to the observation of slightly decomposed species during titration experiment, the Ka values should be roughly estimated values.

Figure S31 1
Figure S31 1 H NMR spectral changes of 2b (1.0 mM) upon the addition of Cl -(0-1.3equiv) added as a TBA salt in CD2Cl2 at (a) 20 °C and (b) -50 °C.Upon the addition of Cl -, initial signals of pyrrole NH (9.29 and 9.23 ppm) and bridging CH (6.38 ppm) decreased and new signals were emerged in the downfield regions, whose signals were identified as anion-binding pyrrole NH (12.62 ppm) and bridging CH (6.61 ppm) with 1.3 equiv of TBACl at -50 °C.

Figure S33
Figure S33Emission spectra of (a) 2b (lex = 462 nm) and (b) 2c (lex = 460 nm) upon the addition of 3000 equiv of Cl - as a TBA salt in deoxygenated CH2Cl2 (1.9 µM for each) at r.t.Emission peaks at 490 and 487 nm are ascribed to partially decomposed products.

Figure S34
Figure S34 Emission decay profiles of (a) 2b and (b) 2c excited at 403 nm in deoxygenated CH2Cl2 at 20 °C.The emission decay profiles were fitted with the single exponential decay function, providing the emission lifetimes of 17.3 and 8.0 µs for 2b,c, respectively.