Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2014 Photochemical reactivity of a lamellar Lanthanum MOF Adonis Michaelides,* a, Maria Aravia, a Michael G. Siskos* a and Stavroula Skoulika* a vskoul@uoi.gr, amihail@uoi.gr, msiskos@cc.uoi.gr Department of Chemistry, University of Ioannina, 45110 Ioannina, Greece
Figure S1. ORTEP drawing of the asymmetric unit of compound 1.
Figure S2. Top: DTG analysis of compound 1. Bottom: DSC analysis of compound 1.
3.5 3.0 2.5 k=5.4x10-2 (s -1 ) 1600-1645 cm -1 987-1035 cm -1 absorbance 2.0 1.5 1.0 0.5 0.0 k=4.3x10-2 (s -1 ) 0 20 40 60 80 time (s) Figure S3. Top: IR spectrum of compound 1as a function of irradiation time. Bottom: Absorbance in two spectral regions as a function of irradiation time with the corresponding calculated reaction constants for compound 1.
90 6.97 6.20 80 7.03 6.14 70 6.98 6.19 60 50 40 30 5.86 20 7.06 6.94 6.63 6.61 6.57 10 0 1.56 0.81 1.56 0.92 5.79 7.02 6.16 6.54 6.23 6.11 5.83 5.77 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 f1 (ppm) 6.2 6.1 6.0 5.9 5.8 5.7 5.6 90 80 70 60 50 2.81 40 30 20 3.81 3.43 3.16 2.85 2.79 10 0 0.05 0.17 0.17 0.95 0.17 0.02 2.67 2.35 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 f1 (ppm) 3.0 2.9 2.8 2.7 2.6 2.5 2.4 Figure S4. 1 H-NMR spectrum of the photoreaction products of 1 (1 h of irradiation) in alkaline D 2 O solution.
(a) (b) (c) (d) (e) Figure S5.(a) Conformations of the hexadiendionc dianion and the photoproducts, in the anionic form, as obtained from DFT calculation.
δ calc =7.15 ppm δ exp = 7.02 ppm δ calc =3.38 ppm δ exp = 2.85 ppm (a) Hb δ calc =6.25 ppm δ exp = 6.14 ppm (c) δ calc =2.65 ppm δ exp = 2.35 ppm (b) δ calc =4.03 ppm δ exp = 3.80 ppm δ calc =5.65 ppm δ exp = 5.70 ppm δ calc =3.38 ppm δ exp = 3.45 ppm δ calc =3.19 ppm δ exp = 3.17 ppm (d) H c H c H d H d δ calc =6.74 ppm δ exp = 6.65 ppm δ calc =5.97ppm δ exp = 5.80 ppm δ calc =2.78ppm δ exp = 2.81 ppm H c H c δ calc =5.88 ppm δ exp = 5.80 ppm H d δ calc =2.57 ppm δ exp = 2.60-2.90 ppm H d δ calc =6.45 ppm δ exp = 6.65 ppm (e) Figure S5(b). Calculated and experimental chemical shifts of the hexadiendionc dianion and all photoproducts( in the anionic form).
Figure S6. From bottom to the top: DSC analysis, TG analysis and DTG analysis of the photoproduct obtained after irradiation of compound 1 for 1 hour.
Figure S7.(a) TG analysis of hydrates 2 (top) and 2r (bottom).
Figure S7. (b) TG analysis of hydrates 3 (top) and 3r (bottom).
Figure S7.(c) TG analysis of hydrates 4.
absorbance 4.0 area 1595-1645 cm area 1025-980 cm -1 3.5 3.0 2.5 2.0 1.5 k=1.6x10-2 k=1.4x10-2 1.0 0 20 40 60 80 100 120 140 160 time (s) Figure S8 (a). Top: IR spectrum of compound 2. Bottom: Absorbance in two spectral regions as a function of irradiation time with the corresponding calculated reaction constants for compound 2.
1.2 0.9 area 1595-1645 cm -1 area 1025-980 cm -1 k=3.2x10-2 k=2.5x10-2 absorbance 0.6 0.3 0 20 40 60 80 100 time (s) Figure S8(b). Top: IR spectrum of compound 2r.. Bottom: Absorbance in two spectral regions as a function of irradiation time with the corresponding calculated reaction constants for compound 2r.
6 area 1595-1645 cm -1 area 1025-980 cm -1 k=7.5x10-3 k=7.3x10-3 absorbance 5 4 3 0 50 100 150 200 250 time (s) Figure S8(c). Top: IR spectrum of compound 3. Bottom: Absorbance in two spectral regions as a function of irradiation time with the corresponding calculated reaction constants for compound 3.
2.5 2.0 area 1595-1645 cm -1 area 1025-980 cm -1 k=2.1x10-2 k=1.6x10-2 absorbance 1.5 1.0 0.5 0 20 40 60 80 100 120 140 160 180 time (s) Figure S8(d). Top: IR spectrum of compound 3r. Bottom: Absorbance in two spectral regions as a function of irradiation time with the corresponding calculated reaction constants for compound 3r.
absorbance 4 3 2 area 1598-1630 cm -1 ) area 1030-987 cm -1 k=16.1x10-2 k=12.2x10-2 1 0 0 10 20 30 40 50 60 time (s) Figure S8(e). Top: IR spectrum of compound 4. Bottom: Absorbance in two spectral regions as a function of irradiation time with the corresponding calculated reaction constants for compound 4.
7.048 7.018 7.005 6.971 6.959 6.929 6.925 6.656 6.634 6.603 6.571 6.466 6.217 6.213 6.183 6.170 6.136 6.124 6.094 6.002 5.830 5.819 5.768 5.758 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 1.0396 0.1296 0.9714 0.1639-0.5 7.00 6.90 6.80 6.70 6.60 6.50 6.40 f1 (ppm) 6.30 6.20 6.10 6.00 5.90 5.80 3.832 3.638 3.357 3.175 3.136 3.021 2.740 2.347 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.0423 0.0861 0.0866 0.0316 0.0167 0.0270-0.5 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 f1 (ppm) 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 Figure S9. 1 H-NMR spectrum of the photoreaction products of 3r (6 h of irradiation) in alkaline D 2 O solution.