Supporting Information

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1 Supporting Information Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism Quentin Benito, a Xavier F. Le Goff, b Gregory Nocton, b Alexandre Fargues, c Alain Garcia, c Aurélie Berhault, d,e Samia Kahlal, d,e Jean-Yves Saillard, d,e Charlotte Martineau, f Julien Trébosc, g Thierry Gacoin, a Jean-Pierre Boilot a and Sandrine Perruchas a * a Laboratoire de Physique de la Matière Condensée (PMC), CNRS - Ecole Polytechnique, Palaiseau Cedex, France. Fax: (+33) (0) ; Phone: (+33) (0) sandrine.perruchas@polytechnique.edu b Laboratoire de Chimie Moléculaire, CNRS - Ecole Polytechnique, Palaiseau Cedex, France. c Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB) - CNRS, 87 Avenue du Docteur A. Schweitzer, Pessac Cedex, France. d UMR-CNRS, 6226 Institut des Sciences Chimiques de Rennes, Université de Rennes 1, Rennes Cedex, France. e Université Européenne de Bretagne, 5 bd. Laënnec, Rennes, France. f Tectospin, Institut Lavoisier de Versailles (ILV), UMR CNRS 8180, Université de Versailles St-Quentin en Yvelines (UVSQ), 45, avenue des Etats-Unis, Versailles Cedex, France. g Université Lille - Science et Technologies, F Lille, France; CNRS UMR 8181, Unité de Catalyse et de Chimie du Solide - UCCS; ENSCL, F Villeneuve d Ascq, France. S1

2 View along the a axis of the crystal structure of 3. View along the a axis of the crystal structure of 1. View along c axis of the crystal structure of 2. Figure S1. Crystal structures of clusters 1-3. S2

3 Table S1. Crystal Data and Structure Refinement for 1-3 at 150 K. Compound [Cu 4 I 4 (PPh 3 ) 4 ] 2.5 C 7 H 8 [Cu 6 I 6 (PPh 2 (CH 2 ) 3 PPh 2 ) 3 ] 2 CH 2 Cl 2 [Cu 4 I 4 (PPh 3 ) 4 ] CH 2 Cl 2 Label (3) 2.5C 7 H 8 (1) 2CH 2 Cl 2 (2) CH 2 Cl 2 Chemical formula C72 H60 Cu4 I4 P4, 2.5(C7H8) C81 H78 Cu6 I6 P6, 2(CH2Cl2) C72 H60 Cu4 I4 P4, CH2Cl2 fw Crystal system Monoclinic Monoclinic Monoclinic Space group P2 1 /c P2 1 /c C2/c a, Å (1) (1) (1) b, Å (1) (1) (1) c, Å (1) (1) (1) α, deg β, deg (1) (1) (1) γ, deg V, Å (9) (8) (7) Z calc, g/cm μ, mm Reflections collected Independent reflections R int Reflections I > 2 (I) Parameters GOF on F R a b 1 /wr 2 (I > 2 (I)) / / / R a 1 /wr b 2 (all) / / / a R 1 = [Σ abs(abs(f O ) abs(fc))]/ [Σ abs(f O )]. b wr 2 = [Σ(w(F 2 O -F 2 c ) 2 )/ Σ[w(F 2 O ) 2 ] 0.5. S3

4 [Cu 6 I 6 (PPh 2 (CH 2 ) 3 PPh 2 ) 3 ] (1) [Cu 4 I 4 (PPh 3 ) 4 ] (2) calculated experimental Intensity (a. u.) calculated experimental Intensity (a. u.) ( ) ( ) [Cu 4 I 4 (PPh 3 ) 4 ] (3) calculated experimental Intensity (a. u.) ( ) Figure S2. Powder X-Ray diffraction diagrams and corresponding calculated ones for 1, 2 and 3 clusters. S4

5 Table S2. Calculated and experimental data of [Cu 4 I 4 (PPh 3 ) 4 ] (2) for different solvents. CHAIR [Cu 4I 4(PPh 3) 4] (X-ray) [Cu 4 I 4 (PPh 3 ) 4 ] C i vacuum [Cu 4 I 4 (PPh 3 ) 4 ] C i toluene [Cu 4 I 4 (PPh 3 ) 4 ] C i chloroform [Cu 4 I 4 (PPh 3 ) 4 ] C i dichloromethane [Cu 4 I 4 (PPh 3 ) 4 ] C i acetonitrile E (a. u.) HOMO-LUMO gap (ev) Cu(1)-Cu(2) (Å) Cu(1)-Cu(1) (Å) Cu(1)-I(1) (Å) Cu(1)-I(2) (Å) Cu(1)-I(2) (Å) Cu(2)-I(1) (Å) Cu(2)-I(2) (Å) Cu(1)-P(1) (Å) Cu(2)-P(2) (Å) C-P (Å) range mean C-C (Å) range mean [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] I(1)-Cu(1)-I(2) ( ) I(2)-Cu(1)-I(2) ( ) P(1)-Cu(1)-I(1) ( ) P(1)-Cu(1)-I(2) ( ) P(2)-Cu(2)-I(1) ( ) P(2)-Cu(2)-I(2) ( ) I(1)-Cu(2)-I(2) ( ) [ ] Table S3. Calculated and experimental data of [Cu 4 I 4 (PPh 3 ) 4 ] (3) for different solvents. CUBANE [Cu [Cu 4 I 4 (PPh 3 ) 4 ] [Cu 4 I 4 (PPh 3 ) 4 ] [Cu 4 I 4 (PPh 3 ) 4 ] [Cu 4 I 4 (PPh 3 ) 4 ] [Cu 4 I 4 (PPh 3 ) 4 ] 4I 4(PPh 3) 4] T T T T T (X-ray) vacuum toluene chloroform dichloromethane acetonitrile E (a. u.) HOMO-LUMO gap (ev) Cu-Cu (Å) [ ] Cu-I (Å) [ ] Cu-P (Å) [ ] C-P (Å) C-C (Å) range mean - [ ] [ ] [ ] [ ] Cu-I-Cu ( ) [ ] Table S4. Dielectric constants of the solvents considered in the calculations. vacuum toluene chloroform dichloromethane acetonitrile ε (C.V -1.m -1 ) S5

6 Figure S3. 13 C CPMAS NMR spectra of 1-3. Figure S4. 1 H MAS NMR spectra of Counts [Cu 6 I 6 (PPh 2 (CH 2 ) 3 PPh 2 ) 3 ] em = 610 nm T = 290 K 1 = 0.7 s 2 = 3.2 s Counts [Cu 4 I 4 (PPh 3 ) 4 ] em = 535 nm T = 290 K = 4.2 s Time (ns) Time (ns) Figure S5. Emission lifetime curves and corresponding fits for 1 and 3 for the LE band at 290 K (λ ex = 300 nm). All first points after the excitation (in red) are not considered for the fitting. S6

7 Figure S6. MO diagram of [Cu 4 I 4 (PPh 3 ) 4 ] cubane (3) in T symmetry with the localization of each MO given (%) in the following order: Cu/I/P/phenyl, from ,8 Cu4I4 cubane Cu4I4 chair Cu6I6 0,6 Abs 0,4 0, Wavelength (nm) Figure S7. UV-vis. absorption spectra of clusters 1-3 in dichloromethane. S7

8 Table S5. Spin density in the triplet state of [Cu 4 I 4 (PPh 3 ) 4 ] chair (2). Cu(2) 0.06 Cu(1)' 0.20 I(1)' 0.06 I(2)' 0.06 P(11) 0.40 C(79) 0.33 C(80) 0.14 C(82) 0.09 C(84) 0.54 C(86) 0.12 C(88) 0.27 Table S6. Comparative distance values in the singlet and triplet states of [Cu 4 I 4 (PPh 3 ) 4 ] chair (2). Distances (Å) C i (S=0) C 1 (S=1) Cu(1)-Cu(2) Cu(1)-Cu(1) Cu(1)-I(1) Cu(1)-I(2) Cu(1)-I(2) Cu(2)-I(1) Cu(2)-I(2) Cu(1)-P(1) Cu(2)-P(2) Cu(1) -P(1) Cu(2) -P(2) Cu(2)-C(82) Cu(2)-C(80) Table S7. Selected bonds lengths (Å) and angles ( ) of the [Cu 4 I 4 (PPh 3 ) 4 ] cubane polymorphs 3 and 3P. Compound [Cu 4 I 4 (PPh 3 ) 4 ] (3) [Cu 4 I 4 (PPh 3 ) 4 ] (3P) 150 K 300 K 150 K 300 K Cu-Cu 2.768(1) 2.863(1) 2.880(1) 2.900(1) 2.964(1) 3.030(1) 2.853(1) 2.977(1) 2.985(1) 2.997(1) 3.082(1) 3.088(1) 2.776(1) 2.820(1) 2.834(1) 2.834(1) 3.038(1) 3.100(1) 2.840(1) 2.868(1) 2.897(1) 2.928(1) 3.108(1) 3.166(1) mean 2.901(1) 2.997(1) 2.901(1) 2.968(1) Cu-I (6) (6) (6) (6) (6) (6) (6) (6) (6) (6) (6) (6) (8) (9) (10) (9) (9) (9) (9) (10) (9) (9) (9) (9) (4) (5) (4) (5) (4) (4) (5) (5) (4) (4) (4) (4) (8) (9) (8) (9) (9) (9) (9) (9) (9) (9) (8) (9) mean (6) (10) (5) (9) S8

9 Cu-P 2.254(1) 2.255(1) 2.256(1) 2.263(1) 2.251(2) 2.255(2) 2.251(2) 2.262(2) 2.253(1) 2.254(1) 2.255(1) 2.258(1) 2.253(2) 2.258(2) 2.252(2) 2.261(2) mean 2.257(1) 2.255(2) 2.255(1) 2.256(2) I-Cu-I (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (2) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (2) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) mean (2) (3) (2) (3) Reference This work This work 1 2 Table S8. Photoluminescence data at different temperatures of the [Cu 4 I 4 (PPh 3 ) 4 ] cubane polymorphs 3 and 3P. compound T (K) max em (nm) [ ex (nm)] Reference [Cu 4 I 4 (PPh 3 ) 4 ] (3) [Cu 4 I 4 (PPh 3 ) 4 ] (3P) [300] This work [300] 425 [300] [300] [300] [300] 415 [300] [300] S9

10 Intensity (a.u) 3 ex = 300 nm 8K 25K 50K 75K 100K 125K 150K 175K 200K 225K 250K 290K Intensity (a. u.) 3P ex = 300 nm 8K 25K 50K 80K 100K 120K 160K 180K 200K 220K 260K 290K Wavelength (nm) Wavelength (nm) Figure S8. Temperature dependant emission spectra of [Cu 4 I 4 (PPh 3 ) 4 ] polymorphs 3 and 3P 1. Figure S9. Photos of powder of cluster 3 and the monoclinic polymorph 3P, under UV irradiation at 312 nm (UV lamp), at room temperature (295 K) and in liquid nitrogen (77 K). S10

11 P V Cu 4 (A 3 ) Temperature (K) Figure S10. Temperature dependence of Cu 4 tetrahedra volume of 3 and its polymorph 3P 2. S11

12 Table S9. Theoretical Gaussian EFG calculations of 1 using PBE1PBE/Def2TZVP. The calculations were performed on both crystallographic limit forms Exp A and Exp. B. In italic are given the experimental C Q values of the copper sites. The signs of C Q cannot be determined from a 1D NMR spectrum, therefore only the absolute values are reported. 1 Exp. A V 11 (a.u.) V 22 (a.u.) V 33 (a.u.) C Q ( 63 Cu)(MHz) C Q ( 65 Cu)(MHz) Q Q = (V 11 -V 22 )/V 33 Cu Cu Cu Cu Cu Cu I I I I I I P P P P P P Exp. B V 11 (a.u.) V 22 (a.u.) V 33 (a.u.) C Q ( 63 Cu)(MHz) C Q ( 65 Cu)(MHz) Q Q = (V 11 -V 22 )/V 33 Cu Cu Cu Cu Cu Cu I I I I I I P P P P P P S12

13 Table S10. Theoretical Gaussian calculations of the shielding tensors using PBE1PBE/Def2TZVP. The calculations were performed on both crystallographic limit forms Exp. A and Exp. B. 1 Exp. A iso = ( )/ 3 = (Span) Cu Cu Cu Cu Cu Cu I I I I I I P P P P P P Exp. B iso = ( )/ 3 = (Span) Cu Cu Cu Cu Cu Cu I I I I I I P P P P P P k = 3( iso - 22 )/ (Skew) k = 3( iso - 22 )/ (Skew) Table S11. Euler angles relating EFG and shielding principal axis systems. They are given for both crystallographic limit forms Exp. A and Exp. B. ( ) ( ) ( ) 1 Exp. A Cu Cu Cu Cu S13

14 Cu Cu I I I I I I Exp. B Cu Cu Cu Cu Cu Cu I I I I I I Figure S11. Experimental 63 Cu WURST-QCPMG NMR spectrum of 1 (exp.). The results of the DFT calculations for both structural models are shown (DFT-1 and DFT-2), along with the best fit, obtained starting from the calculated values and adjusting the C Q values. S14

15 Figure S12. Experimental (Exp.) and deconvoluted (Rec.) 31 P MAS NMR spectrum of 3. The deconvolution was performed with three patterns 1, 2 and 3 of respective relative intensity 1:2:1, in agreement with the four P sites of same intensity in the crystal structure. The chemical shifts are -22.4, and ppm, respectively. The 31 P- 65 Cu J-coupling constants are 1690, 1635 and 1620 Hz, respectively. According to the crystal structure, the RDDs are 1202, 1209, 1211 and 1207 Hz for P1, P2, P3 and P4, respectively. The lines cannot be assigned to the corresponding crystallographic, therefore J cannot be determined. References (1) S. Perruchas, C. Tard, X. F. Le Goff, A. Fargues, A. Garcia, S. Kahlal, J.-Y. Saillard, T. Gacoin, J.-P. Boilot, Inorg. Chem., 2011, 50, (2) H. Kitagawa, Y. Ozawa, K. Toriumi, Chem. Commun. 2010, 46, S15