π-extended diketopyrrolopyrrole-porphyrin arrays: one- and two-photon photophysical investigations and theoretical studies

Figure S5: Absorption spectra of the four compounds in (a) DMSO and (b) H2O + 1% DMSO. 10 Figure S6: Normalized corrected room temperature emission spectra of the four compounds in (a) DMSO and (b) H2O + 1% DMSO. 11 Figure S7: (a) Absorption spectra of (DPP)4-ZnP in DCM (full line) and DCM + 1% pyridine (dashed line) and (b) emission spectra of isoabsorbing solutions of (DPP)4-ZnP 6.3 × 10-7 M in the same solvents, excitation at 655 nm. 12 Figure S8: Normalized corrected fluorescence spectra of the four compounds at 77 K in DCM:MeOH (1:1). 12 Figure S9: Arbitrarily scaled luminescence spectra of the four compounds at 77 K in DCM:MeOH:EtI (1:1:2). 13 Table S1: Fluorescence and phosphorescence data at 77 K in DCM:MeOH (1:1) and DCM:MeOH:EtI (1:1:2), respectively. 13 Table S2: Triplet excited-state spectral features and lifetimes in air-free DMSO solutions. 14


Supporting Information
General information and experimental procedures 4 Figure S1: Synthesis of (DPP) 4
18 Scheme S1: Labels of the important bond lengths.
19 Figure S12: DFT optimized structure of m-ZnP in the electronic ground state, as compared to the X-ray structure of ZnP (the DMSO coordinated to the Zn metal centre is not shown, for the complete structure see Fig. S16). H atoms are hidden for the sake of clarity.  Table S6: TD-DFT transition energies (in eV) and absorption wavelengths (in nm) of m-ZnP, m-DPP-ZnP, m-(DPP) 2 -ZnP and m-(DPP) 4 -ZnP calculated in DCM and associated oscillator strengths (only the values > 0.05 are reported here). 26 Table S7: TD-DFT absorption wavelengths (λ, in nm) and associated main one-electron excitations (> 20%) corresponding to the most intense OP 1 A u transitions (f > 0.5) depicted in the theoretical spectra of Fig. 6 for m-ZnP and m-DPP-ZnP 28 Table S8: TD-DFT absorption wavelengths (λ, in nm) and associated main one-electron excitations (> 20%) corresponding to the most intense OP 1 A u transitions (f > 0.5) depicted in the theoretical spectra of 32 Table S9: Crystal data and structure refinement for ZnP. 33

General information and experimental procedures
All chemicals were of the best commercially available grade and used without further purification. Tetrahydrofuran was dried using a dry solvent station GT S100. Column chromatographies were carried out on silica (Fluka 60, 70-230 mesh). NMR spectra were recorded at the ambient probe temperature using Bruker AVANCE 500 spectrometers.
Chemical shifts are quoted as parts per million (ppm) relative to the residual peak of solvent and coupling constants (J) are quoted in Hertz (Hz). X-Ray diffraction data collection was carried out on a Bruker APEX II DUO Kappa-CCD diffractometer equipped with an Oxford Cryosystem liquid N 2 device, using Cu-Kα radiation (λ = 1,54178 Å). Compounds (TIPS) 4 -ZnP [1] and DPP-Br [2] were prepared according to the literature. Figure S1. Synthesis of (DPP) 4 -ZnP.

Synthesis of (DPP) 4 -ZnP
To a degassed solution of (TIPS) 4 Table S2. Triplet excited-state spectral features and lifetimes in air-free DMSO solutions.
S 0 T n on the geometry of the a 1 A g or a 1 A electronic ground state S 0 T n on the geometry of the lowest T 1 (a 3 A u or a 3 A) excited state T 1 T n on the geometry of the lowest T 1 (a 3 A u or a 3 A) excited state m-ZnP      Table S7. TD-DFT absorption wavelengths (λ, in nm) and associated main one-electron excitations (> 20%) corresponding to the most intense OP 1 A u transitions (f > 0.5) depicted in the theoretical spectra of Fig. 6 for m-ZnP and m-DPP-ZnP.  Table S8. TD-DFT absorption wavelengths (λ, in nm) and associated main oneelectron excitations (> 20%) corresponding to the most intense OP 1 A u transitions (f > 0.5) depicted in the theoretical spectra of Fig. 6 for m-(DPP) 2 -ZnP and m-(DPP) 4 -ZnP.
30 Transition λ f m-(DPP) 2 Table S5). Crystallographic data X-ray crystal structure determination. The crystal-detector distance was 40 mm. The cell parameters were determined (APEX2 software) [3] from reflections taken from three sets of 20 frames, each at 10s exposure. The structure was solved by Direct methods using the program SHELXS-97. [4] The refinement and all further calculations were carried out using SHELXL-2013. [5] The H-atoms were included in calculated positions and treated as riding atoms using SHELXL default parameters. The non-H atoms were refined anisotropically, using weighted full-matrix least-squares on F2. A semi-empirical absorption correction was applied using SADABS in APEX2. [6] CCDC 1451986 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Figure S16. Representation of the crystal packing of ZnP. Hydrogens are omitted for clarity. One DMSO molecule is linked to each zinc metal centre.