SUPPLEMENTARY INFORMATION

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1 SUPPLEMENTARY INFORMATION 1) de Mello method for the calculation of the absolute quantum efficiency of a compound pg. 2 2) XRD analysis of a sample of cuprorivaite pg.36

2 1) de Mello method for the calculation of the absolute quantum efficiency of a compound DE MELLO s method for integrating spheres. The emission spectra described in Fig. SI1 are recorded, and corrected for the response of the sensor, The integrals of the spectra are calculated and used in the equation in Fig.SI1 to calculate the absolute emission quantum yield. EXCITATION LIGHT RANGE EMISSION LIGHT RANGE A B B2 C2 Φ emsmpl Abs % C2 = Abs = 1 C B ( 1 Abs% ) % A B2 C Fig. SI1 Description of the method for the determination of the absolute emission quantum yield proposed by De Mello et al. J. C. De Mello, H. F. Wittmann and R. H. Friend, Advanced Materials, 1997, 9, 230.

3 Φ emsmpl C2 = Abs ( 1 Abs% ) % A B2 Abs % = 1 C B Fig. SI2 Example of the determination of the emission quantum yield of a sample of quinine sulphate using the De Mello s method. This experiment was undertaken in our lab in order to verify the confidence of the technique.

4 Raw data of the emission spectra recorded to calculate the emission quantum yield of the Cuprorivaite are listed below (left column = nm ; right column = emission intensity). The name of the spectrum refers to the experimental conditions described in Fig. SI1. A E E E E E E E E E E E E E E E E6

5 E E E E E E E E E E E E E E E E E E E

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36 2) XRD analysis of a sample of cuprorivaite X-ray powder diffraction data have been used to detect the crystalline phases contained in the sample. X-ray powder diffraction data were collected in theta-theta reflection geometry with the CuKα radiation on a PANalytical X PERT PRO diffractometer, PW3050 goniometer equipped with an X'Celerator detector. The LFF tube operated at 40KV, 40mA. Data were collected using a step size of and a count time of 10s per step. The data were analysed using a PANAlytical X'PERT HighScore V.2.2b program. The position of the experimental 2theta peaks was determined using the minimum 2nd derivative method; the processed data were then used in the search and match procedure implemented in the program, which makes use of the ICDD PDF2 database (see Table 2). The final result of this investigation determined the presence of cuprorivaite. Scan Parameters Dataset Name: File name: Comment: Operator: Raw Data Origin: Scan Axis: Start Position [ 2Th.]: End Position [ 2Th.]: Step Size [ 2Th.]: Scan Step Time [s]: Scan Type: Continuous PSD Mode: Scanning PSD Length [ 2Th.]: 2.12 Offset [ 2Th.]: Divergence Slit Type: Fixed Divergence Slit Size [ ]: Specimen Length [mm]: Measurement Temperature [ C]: Anode Material: Cu K-Alpha1 [Å]: K-Alpha2 [Å]: K-Beta [Å]: K-A2 / K-A1 Ratio: Generator Settings: 40 ma, 40 kv bludegitto D:\riccardo\documenti\x\aldo\bludegitto.xrdml Configuration=BRACKET, Owner=User-1, Creation date=1/9/ :11:56 PM Goniometer=PW3050/60 (Theta/Theta); Minimum step size 2Theta:0.001; Minimum step size Omega:0.001 Sample stage=pw3071/xx Bracket Diffractometer system=xpert-pro Measurement program=ric, Owner=User-1, Creation date=1/16/ :35:32 AM bracket labin XRD measurement (*.XRDML) Gonio

37 Diffractometer Type: Diffractometer Number: 0 Goniometer Radius [mm]: Dist. Focus-Diverg. Slit [mm]: Incident Beam Monochromator: No Spinning: No Counts bludegitto Position [ 2Theta] (Copper (Cu)) Fig. SI3 X-ray powder diffraction pattern of Egyptian blue

38 Table 1: Phase matching results Ref.Code Score Compound Name Displ.[ 2Th] Scale Fac. Chem. Formula Calcium Copper Silicate Ca Cu ( Si4 O10) Document History Insert Measurement: - File name = "bludegitto.xrdml" Default properties: - Measurement step axis = "None" - Internal wavelengths used from anode material: Copper (Cu) - Original K-Alpha1 wavelength = " " - Used K-Alpha1 wavelength = " " - Original K-Alpha2 wavelength = " " - Used K-Alpha2 wavelength = " " - Original K-Beta wavelength = " " - Used K-Beta wavelength = " " - Incident beam monochromator = "No" - Dist. focus to div. slit = " " - Irradiated length = " " - Spinner used = "No" - Receiving slit size = " " - Step axis value = " " - Offset = " " - Sample length = " " Interpolate Step Size: - Step Size = "Derived" Determine Background: - Correction method = "Automatic" - Bending factor = "0" - Use smoothed input data = "Yes" - Granularity = "21" - Add to net scan = "Nothing" Search Peaks: - Minimum significance = "1.00" - Minimum tip width = "0.05" - Maximum tip width = "3.00" - Peak base width = "5.00" - Method = "Minimum 2nd derivative" Search & Match: - Data source = "Peak list" - Restriction = "None" - Scoring schema = "Multi phase" - Auto residue = "Yes" - Match intensity = "Yes" - Demote unmatched strong = "Yes" - Allow pattern shift = "Yes" - Two theta shift = "0" - Identify = "No"

39 Table 2: Peak position, intensity and phase matching for the pattern shown in Fig. SI3. No. Pos. [ 2Th.] d-spacing [Å] Rel. Int. [%] Area [cts* 2Th.] Height [cts] Matched by

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41 Counts bludegitto calcium copper silicate Position [ 2Theta] (Copper (Cu)) Selected Pattern: Calcium Copper Silicate Residue + Peak List Fig. SI4: Comparison between the experimental peaks (blue) and those relative to the matched calcium copper silicate phase (red, PDF number: ). The experimental pattern is also shown (black).

42 Counts bludegitto calcium copper silicate Position [ 2Theta] (Copper (Cu)) Selected Pattern: Calcium Copper Silicate Residue + Peak List Fig. SI5: Enlargement of Fig. SI4 in the theta range

43 Counts bludegitto calcium copper silicate Position [ 2Theta] (Copper (Cu)) Selected Pattern: Calcium Copper Silicate Residue + Peak List Fig. SI6: Enlargement of Fig. SI4 in the theta range.

44 Details of Calcium Copper Silicate, Ref. Code Name and formula Reference code: ICSD name: Calcium Copper Silicate Empirical formula: CaCuO 10 Si 4 Chemical formula: CaCu ( Si 4 O 10 ) Crystallographic parameters Crystal system: Tetragonal Space group: P4/ncc Space group number: 130 a (Å): b (Å): c (Å): Alpha ( ): Beta ( ): Gamma ( ): Calculated density (g/cm^3): 3.10 Measured density (g/cm^3): 3.06 Volume of cell (10^6 pm^3): Z: 4.00 RIR: 1.21 Subfiles and Quality Subfiles: Quality: Inorganic Corrosion Modelled additional pattern Calculated (C) Comments Additional pattern: See PDF See PDF ICSD collection code: References Primary reference: Calculated from ICSD using POWD-12++, (1997) Structure: Pabst, A., Acta Crystallogr., 12, 733, (1959) Peak list No. h k l d [A] 2Theta[deg] I [%]

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