Supplementary Information Chemical Partition of the Radiative Decay Rate of Luminescence of Europium Complexes

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1 Supplementary Information Chemical Partition of the Radiative Decay Rate of Luminescence of Europium Complexes Nathalia B. D. Lima [a], José Diogo L. Dutra [a,b], Simone M. C. Gonçalves [a], Ricardo O. Freire [b], and Alfredo M. Simas [a] * [a] Departamento de Química Fundamental, CCEN, UFPE, Recife, PE, Brazil. [b] Pople Computational Chemistry Laboratory, Departamento de Química, CCET, UFS, São Cristóvão, SE, Brazil. * Corresponding author: simas@ufpe.br Tel

2 List of Tables Table S1. Fitted Q, D, and C values for all complexes studied, with electronic densities and electrophilic superdelocalizabilities 1, together with calculated and erimental values for the complexes of the general formula Eu(β-diketonate) 3(TPPO) 2 with the RM1 model (except where otherwise indicated), where β-diketonate stands for the ionic ligands TTA, BTFA, and DBM Table S2. Fitted Q, D, and C values for all complexes studied, with electronic densities and electrophilic superdelocalizabilities 1, together with calculated and erimental values for the complexes of the general formula Eu(β-diketonate) 3(L) 2 with the RM1 model (except where otherwise indicated), where β-diketonate stands for the ionic ligands TTA, BTFA, and DBM; and L stands for the non-ionic ligands TPPO, DBSO, and PTSO Table S3. Fitted Q, D, and C values for all complexes studied, with electronic densities and electrophilic superdelocalizabilities 1, together with calculated and erimental values for the complexes of the general formula Eu(β-diketonate) 3(L,L ) with the RM1 model (except where otherwise indicated), where β-diketonate stands for the ionic ligands TTA, BTFA, and DBM; and L and L stand for the non-ionic ligands TPPO, DBSO, and PTSO Table S4. Radiative decay rates A rad and Arad, as well as the ionic and non-ionic partitions of ionic A rad : A rad and A non ionic rad. A rad corresponds to the transitions from 5 D 0 to 7 F 2, 7 F 4, and 7 F 6, and is therefore always smaller thana rad which, in addition, also includes the transitions to 7 F 0, 7 F 1, 7 F 3, and 7 ionic F 5. The A rad partition comprises the terms for each of the three identical - diketonates, ordered into maximum (Max), medium (Med) and minimum (Min) values. The A non ionic rad partition comprises the terms for each of the two identical non-ionic ligands, ordered into maximum (Max), and minimum (Min) values. Geometries were optimized and the chemical partitions were calculated with the RM1 model (except where otherwise indicated) Table S5. Radiative decay rates A rad and Arad, as well as the ionic and non-ionic partitions ionic of A rad : A rad and A non ionic rad. A rad corresponds to the transitions from 5 D 0 to 7 F 2, 7 F 4, and 7 F 6, and is therefore always smaller than A rad which, in addition, also includes the transitions to 7 F 0, 7 F 1, 7 F 3, and 7 ionic F 5. The A rad partition comprises the terms for each of the three identical - diketonates, ordered into maximum (Max), medium (Med) and minimum (Min) values. The non ionic A rad partition comprises the terms for each of the two identical non-ionic ligands, ordered into maximum (Max), and minimum (Min) values. Geometries were optimized and the chemical partitions were calculated with the RM1 model (except where otherwise indicated) Table S6. Radiative decay rates A rad and Arad, as well as the ionic and non-ionic partitions of ionic A rad : A rad and A non ionic rad. A rad corresponds to the transitions from 5 D 0 to 7 F 2, 7 F 4, and 7 F 6, and is therefore always smaller than A rad which, in addition, also includes the transitions to 7 F 0, 7 F 1, 7 F 3, and 7 ionic F 5. The A rad partition comprises the terms for each of the three identical - diketonates, ordered into maximum (Max), medium (Med) and minimum (Min) values. The non ionic A rad partition is comprised of terms corresponding to each of the non-ionic ligands, as 2

3 indicated. Geometries were optimized and the chemical partitions were calculated with the RM1 model (except where otherwise indicated) Table S7. Spherical coordinates of all atoms belonging to the coordination polyhedron of the complexes of general formula Eu(BTFA) 3(L) 2 and Eu(BTFA) 3(L,L ), optimized with the RM1 model (except where otherwise indicated), where L and L stand for the non-ionic ligands TPPO, DBSO, and PTSO Table S8. Spherical coordinates of all atoms belonging to the coordination polyhedron of the complexes of general formula Eu(TTA) 3(L) 2 and Eu(TTA) 3(L,L ) optimized with the RM1 model, where L and L stand for the non-ionic ligands TPPO, DBSO, and PTSO Table S9. Spherical coordinates of all atoms belonging to the coordination polyhedron of the complexes of general formula Eu(DBM) 3(L) 2 and Eu(DBM) 3(L,L ) optimized with the RM1 model (except where otherwise indicated), where β-diketonate stands for the ionic ligands DBM; and L and L stand for the non-ionic ligands TPPO, DBSO, and PTSO

4 Table S1. Fitted Q, D, and C values for all complexes studied, with electronic densities and electrophilic superdelocalizabilities 1, together with calculated and erimental values for the complexes of the general formula Eu(β-diketonate)3(TPPO)2 with the RM1 model (except where otherwise indicated), where β-diketonate stands for the ionic ligands TTA, BTFA, and DBM. Complex Q D C D/C calc Ω 2 Ω 2 calc Ω 4 calc Ω 6 Eu(TTA) 3(TPPO) 2,Non-Adj Eu(TTA) 3(TPPO) 2,Adj Eu(BTFA) 3(TPPO) 2,Non-Adj Eu(BTFA) 3(TPPO) 2,Adj Eu(DBM) 3(TPPO) (a) 2,Non-Adj Eu(DBM) 3(TPPO) 2,Adj Units are: Q (au -1 ); D (au -1 Å3 ); C (Å 3 ); D/C (au -1 ); (10-20 cm 2 ). (a) Geometry was optimized and the chemical partition was calculated with Sparkle/PM3. Ω 4 4

5 Table S2. Fitted Q, D, and C values for all complexes studied, with electronic densities and electrophilic superdelocalizabilities 1, together with calculated and erimental values for the complexes of the general formula Eu(β-diketonate)3(L)2 with the RM1 model (except where otherwise indicated), where β-diketonate stands for the ionic ligands TTA, BTFA, and DBM; and L stands for the non-ionic ligands TPPO, DBSO, and PTSO. Complex Q D C D/C calc Ω 2 Ω 2 calc Ω 4 calc Ω 6 Eu(TTA) 3(DBSO) 2,Non-Adj Eu(TTA) 3(PTSO) 2,Non-Adj Eu(TTA) 3(TPPO) 2,Non-Adj Eu(BTFA) 3(DBSO) 2,Non-Adj Eu(BTFA) 3(PTSO) 2,Non-Adj Eu(BTFA) 3(TPPO) 2,Non-Adj Eu(DBM) 3(DBSO) 2,Non-Adj Eu(DBM) 3(PTSO) 2,Non-Adj Eu(DBM) 3(TPPO) (a) 2,Non-Adj Units are: Q (au -1 ); D (au -1 Å3 ); C (Å 3 ); D/C (au -1 ); (10-20 cm 2 ). (a) Geometry was optimized and the chemical partition was calculated with Sparkle/PM3. Ω 4 5

6 Table S3. Fitted Q, D, and C values for all complexes studied, with electronic densities and electrophilic superdelocalizabilities 1, together with calculated and erimental values for the complexes of the general formula Eu(β-diketonate)3(L,L ) with the RM1 model (except where otherwise indicated), where β-diketonate stands for the ionic ligands TTA, BTFA, and DBM; and L and L stand for the non-ionic ligands TPPO, DBSO, and PTSO. Complex Q D C D/C calc Ω 2 Ω 2 calc Ω 4 calc Ω 6 Eu(TTA) 3(DBSO,TPPO) Non-Adj Eu(TTA) 3(PTSO,TPPO) Non-Adj Eu(TTA) 3(DBSO,PTSO) Non-Adj Eu(BTFA) 3(DBSO,TPPO) Non-Adj (a) Eu(BTFA) 3(PTSO,TPPO) Non-Adj Eu(BTFA) 3(DBSO,PTSO) Non-Adj Eu(DBM) 3(DBSO,TPPO) Non-Adj Eu(DBM) 3(PTSO,TPPO) Non-Adj Eu(DBM) 3(DBSO,PTSO) Non-Adj Units are: Q (au -1 ); D (au -1 Å3 ); C (Å 3 ); D/C (au -1 ); (10-20 cm 2 ). (a) Geometry was optimized and the chemical partition was calculated with Sparkle/RM1. Ω 4 6

7 Complex Table S4. Radiative decay rates A rad and A rad, as well as the ionic and non-ionic ionic partitions of A rad : A rad and A non ionic rad. A rad corresponds to the transitions from 5 D0 to 7 F2, 7 F4, and 7 F6, and is therefore always smaller than A rad which, in addition, also includes the transitions to 7 F0, 7 F1, 7 F3, and 7 ionic F5. The A rad partition comprises the terms for each of the three identical -diketonates, ordered into maximum (Max), medium (Med) and minimum (Min) values. The A non ionic rad partition comprises the terms for each of the two identical non-ionic ligands, ordered into maximum (Max), and minimum (Min) values. Geometries were optimized and the chemical partitions were calculated with the RM1 model (except where otherwise indicated). A rad (s -1 ) A rad (s -1 ) Eu(TTA) 3(TPPO) 2,Non-Adj Eu(TTA) 3(TPPO) 2,Adj Eu(BTFA) 3(TPPO) 2,Non-Adj Eu(BTFA) 3(TPPO) 2,Adj ionic A rad (s -1 ) A rad (s -1 ) Max Med Min Max Min (42%) (34%) (8%) (12%) (4%) (23%) (19%) (7%) (26%) (24%) (30%) (27%) (23%) (20%) (0%) (33%) (11%) (8%) (45%) (4%) Eu(DBM) 3(TPPO) (a) 2,Non-Adj (23%) (23%) (20%) (22%) (13%) Eu(DBM) 3(TPPO) 2,Adj (31%) (22%) (18%) (25%) (4%) (a) Geometry was optimized and the chemical partition was calculated with Sparkle/PM3. 7

8 Table S5. Radiative decay rates A rad and A rad, as well as the ionic and non-ionic ionic partitions of A rad : A rad and A non ionic rad. A rad corresponds to the transitions from 5 D0 to 7 F2, 7 F4, and 7 F6, and is therefore always smaller than A rad which, in addition, also includes the transitions to 7 F0, 7 F1, 7 F3, and 7 ionic F5. The A rad partition comprises the terms for each of the three identical -diketonates, ordered into maximum (Max), medium (Med) and minimum (Min) values. The A non ionic rad partition comprises the terms for each of the two identical non-ionic ligands, ordered into maximum (Max), and minimum (Min) values. Geometries were optimized and the chemical partitions were calculated with the RM1 model (except where otherwise indicated). Complex Eu(TTA) 3(DBSO) 2,Non-Adj Eu(TTA) 3(PTSO) 2,Non-Adj Eu(TTA) 3(TPPO) 2,Non-Adj Eu(BTFA) 3(DBSO) 2,Non-Adj Eu(BTFA) 3(PTSO) 2,Non-Adj Eu(BTFA) 3(TPPO) 2,Non-Adj Eu(DBM) 3(DBSO) 2,Non-Adj A rad (s -1 ) A rad (s -1 ) ionic A rad (s -1 ) A rad (s -1 ) Max Med Min Max Min (65%) (17%) (8%) (9%) (2%) (71%) (15%) (12%) (1%) (0%) (42%) (34%) (8%) (12%) (4%) (52%) (21%) (9%) (14%) (3%) (36%) (20%) (4%) (38%) (2%) (30%) (27%) (23%) (20%) (0%) (52%) (19%) (17%) (7%) (5%) Eu(DBM) 3(PTSO) 2,Non-Adj (38%) (32%) (23%) (4%) (3%) Eu(DBM) 3(TPPO) (a) 2,Non-Adj (23%) (23%) (20%) (22%) (13%) (a) Geometry was optimized and the chemical partition was calculated with Sparkle/PM3. 8

9 Table S6. Radiative decay rates A rad and A rad, as well as the ionic and non-ionic ionic partitions of A rad : A rad and A non ionic rad. A rad corresponds to the transitions from 5 D0 to 7 F2, 7 F4, and 7 F6, and is therefore always smaller than A rad which, in addition, also includes the transitions to 7 F0, 7 F1, 7 F3, and 7 ionic F5. The A rad partition comprises the terms for each of the three identical -diketonates, ordered into maximum (Max), medium (Med) and minimum (Min) values. The A non ionic rad partition is comprised of terms corresponding to each of the non-ionic ligands, as indicated. Geometries were optimized and the chemical partitions were calculated with the RM1 model (except where otherwise indicated). Complex A rad (s -1 ) A rad (s -1 ) ionic A rad (s -1 ) A non ionic rad (s -1 ) Max Min Med DBSO PTSO TPPO Eu(TTA) 3(DBSO,TPPO) Non-Adj (44%) (30%) (10%) (3%) Eu(TTA) 3(PTSO,TPPO) Non-Adj (21%) (13%) (11%) (52%) Eu(TTA) 3(DBSO,PTSO) Non-Adj (39%) (18%) (6%) (36%) (1%) Eu(BTFA) 3(DBSO,TPPO) Non-Adj (a) (23%) (12%) (12%) (44%) Eu(BTFA) 3(PTSO,TPPO) Non-Adj (44%) (39%) (6%) (5%) Eu(BTFA) 3(DBSO,PTSO) Non-Adj (11%) (9%) (2%) (27%) (51%) Eu(DBM) 3(DBSO,PTSO) Non-Adj (55%) (22%) (16%) (6%) Eu(DBM) 3(PTSO,TPPO) Non-Adj (52%) (20%) (6%) (7%) Eu(DBM) 3(DBSO,PTSO) Non-Adj (49%) (16%) (14%) (7%) (15%) (a) Geometry was optimized and the chemical partition was calculated with Sparkle/RM (10%) 28 (3%) (10%) 54 (5%) (1%) 79 (15%)

10 Table S7. Spherical coordinates of all atoms belonging to the coordination polyhedron of the complexes of general formula Eu(BTFA)3(L)2 and Eu(BTFA)3(L,L ), optimized with the RM1 model (except where otherwise indicated), where L and L stand for the nonionic ligands TPPO, DBSO, and PTSO. Complex R (Å) θ ( ) φ ( ) Eu(BTFA) 3(DBSO) 2,Adj O (DBSO1) O (DBSO2) O (BTFA2) O (BTFA2) O (BTFA1) O (BTFA1) O (BTFA3) O (BTFA3) Eu(BTFA) 3(DBSO) 2,Non-Adj O (BTFA3) O (BTFA1) O (DBSO1) O (DBSO2) O (BTFA2) O (BTFA2) O (BTFA3) O (BTFA1) Eu(BTFA) 3(DBSO,PTSO) Adj O (DBSO) O (PTSO) O (BTFA3) O (BTFA3) O (BTFA2) O (BTFA2) O (BTFA1) O (BTFA1) Eu(BTFA) 3(DBSO,PTSO) Non-Adj O (PTSO) O (DBSO) O (BTFA3) O (BTFA3) O (BTFA1) O (BTFA1) O (BTFA2) O (BTFA2) Eu(BTFA) 3(DBSO,TPPO) Adj O (TPPO)

11 O (BTFA2) O (BTFA2) O (BTFA1) O (BTFA1) O (BTFA3) O (BTFA3) O (DBSO) Eu(BTFA) 3(DBSO,TPPO) (a) Non-Adj O (BTFA3) O (BTFA3) O (BTFA2) O (BTFA2) O (DBSO) O (TPPO) O (BTFA1) O (BTFA1) Eu(BTFA) 3(PTSO) 2,Adj O (PTSO1) O (BTFA1) O (BTFA1) O (BTFA2) O (BTFA2) O (BTFA3) O (BTFA3) O (PTSO2) Eu(BTFA) 3(PTSO) 2,Non-Adj O (BTFA2) O (BTFA2) O (PTSO1) O (BTFA3) O (BTFA3) O (PTSO2) O (BTFA1) O (BTFA1) Eu(BTFA) 3(PTSO,TPPO) Adj O (BTFA1) O (BTFA1) O (BTFA3) O (BTFA3) O (BTFA2) O (BTFA2) O (TPPO) O (PTSO) Eu(BTFA) 3(PTSO,TPPO) Non-Adj 11

12 O (BTFA1) O (BTFA2) O (TPPO) O (BTFA3) O (BTFA3) O (PTSO) O (BTFA1) O (BTFA2) Eu(BTFA) 3(TPPO) 2,Adj O (BTFA1) O (TPPO1) O (TPPO2) O (BTFA2) O (BTFA2) O (BTFA3) O (BTFA3) O (BTFA1) Eu(BTFA) 3(TPPO) 2,Non-Adj O (BTFA1) O (TPPO1) O (BTFA2) O (TPPO2) O (BTFA1) O (BTFA3) O (BTFA2) O (BTFA3) (a) Geometry optimized with Sparkle/RM1. 12

13 Table S8. Spherical coordinates of all atoms belonging to the coordination polyhedron of the complexes of general formula Eu(TTA)3(L)2 and Eu(TTA)3(L,L ) optimized with the RM1 model, where L and L stand for the non-ionic ligands TPPO, DBSO, and PTSO. Complex R (Å) θ ( ) φ ( ) Eu(TTA) 3(DBSO) 2,Adj O (DBSO1) O (TTA1) O (TTA1) O (TTA3) O (TTA2) O (TTA2) O (TTA3) O (DBSO2) Eu(TTA) 3(DBSO) 2,Non-Adj O (TTA1) O (TTA1) O (DBSO1) O (TTA2) O (TTA2) O (DBSO2) O (TTA3) O (TTA3) Eu(TTA) 3(DBSO,PTSO) Adj O (PTSO) O (DBSO) O (TTA2) O (TTA2) O (TTA1) O (TTA1) O (TTA3) O (TTA3) Eu(TTA) 3(DBSO,PTSO) Non-Adj O (DBSO) O (TTA1) O (PTSO) O (TTA3) O (TTA3) O (TTA2) O (TTA2) O (TTA1) Eu(TTA) 3(DBSO,TPPO) Adj O (TTA3) O (TTA3) O (DBSO)

14 O (TPPO) O (TTA2) O (TTA2) O (TTA1) O (TTA1) Eu(TTA) 3(DBSO,TPPO) Non-Adj O (TTA2) O (TTA2) O (DBSO) O (TPPO) O (TTA3) O (TTA3) O (TTA1) O (TTA1) Eu(TTA) 3(PTSO) 2,Adj O (PTSO1) O (TTA3) O (TTA3) O (TTA2) O (TTA2) O (PTSO2) O (TTA1) O (TTA1) Eu(TTA) 3(PTSO) 2,Non-Adj O (PTSO1) O (PTSO2) O (TTA2) O (TTA2) O (TTA1) O (TTA1) O (TTA3) O (TTA3) Eu(TTA) 3(PTSO,TPPO) Adj O (TPPO) O (TTA1) O (TTA1) O (TTA2) O (TTA2) O (PTSO) O (TTA3) O (TTA3) Eu(TTA) 3(PTSO,TPPO) Non-Adj O (PTSO) O (TTA1)

15 O (TPPO) O (TTA2) O (TTA2) O (TTA3) O (TTA3) O (TTA1) Eu(TTA) 3(TPPO) 2,Adj O (TTA2) O (TTA2) O (TTA3) O (TTA3) O (TPPO1) O (TTA1) O (TTA1) O (TPPO2) Eu(TTA) 3(TPPO) 2,Non-Adj O (TTA1) O (TPPO1) O (TTA2) O (TTA2) O (TPPO2) O (TTA3) O (TTA3) O (TTA1)

16 Table S9. Spherical coordinates of all atoms belonging to the coordination polyhedron of the complexes of general formula Eu(DBM)3(L)2 and Eu(DBM)3(L,L ) optimized with the RM1 model (except where otherwise indicated), where β-diketonate stands for the ionic ligands DBM; and L and L stand for the non-ionic ligands TPPO, DBSO, and PTSO. Complex R (Å) θ ( ) φ ( ) Eu(DBM) 3(DBSO) 2,Adj O (DBSO1) O (DBSO2) O (DBM1) O (DBM1) O (DBM2) O (DBM2) O (DBM3) O (DBM3) Eu(DBM) 3(DBSO) 2,Non-Adj O (DBM1) O (DBM1) O (DBM2) O (DBM2) O (DBSO1) O (DBM3) O (DBM3) O (DBSO2) Eu(DBM) 3(DBSO,PTSO) Adj O (DBM1) O (DBM1) O (DBM2) O (DBM2) O (PTSO) O (DBSO) O (DBM3) O (DBM3) Eu(DBM) 3(DBSO,PTSO) Non-Adj O (DBSO) O (DBM1) O (DBM1) O (DBM2) O (DBM2) O (PTSO) O (DBM3) O (DBM3) Eu(DBM) 3(DBSO,TPPO) Adj O (DBSO)

17 O (TPPO) O (DBM1) O (DBM2) O (DBM2) O (DBM3) O (DBM3) O (DBM1) Eu(DBM) 3(DBSO,TPPO) Non-Adj O (DBSO) O (TPPO) O (DBM1) O (DBM1) O (DBM2) O (DBM2) O (DBM3) O (DBM3) Eu(DBM) 3(PTSO) 2,Adj O (DBM1) O (PTSO1) O (PTSO2) O (DBM2) O (DBM2) O (DBM3) O (DBM3) O (DBM1) Eu(DBM) 3(PTSO) 2,Non-Adj O (DBM1) O (DBM1) O (DBM2) O (DBM2) O (PTSO1) O (DBM3) O (DBM3) O (PTSO2) Eu(DBM)3(PTSO,TPPO) Adj O (PTSO) O (TPPO) O (DBM1) O (DBM3) O (DBM3) O (DBM2) O (DBM2) O (DBM1) Eu(DBM) 3(PTSO,TPPO) Non-Adj 17

18 O (DBM1) O (PTSO) O (DBM2) O (DBM2) O (TPPO) O (DBM3) O (DBM1) O (DBM3) Eu(DBM) 3(TPPO) (a) 2,Adj O (DBM1) O (TPPO1) O (DBM2) O (TPPO2) O (DBM2) O (DBM3) O (DBM3) O (DBM1) Eu(DBM) 3(TPPO) 2,Non-Adj O (TPPO1) O (TPPO2) O (DBM1) O (DBM3) O (DBM2) O (DBM1) O (DBM2) O (DBM3) (a) Geometry optimized with Sparkle/PM3. Reference 1. Dutra, J.D.L., Lima, N.B.D., Freire, R.O. & Simas, A.M. Europium Luminescence: Electronic Densities and Superdelocalizabilities for a Unique Adjustment of Theoretical Intensity Parameters. Sci. Rep. 5, (2015). 18