ELECTRONIC SUPPLEMENTARY INFORMATION (ESI)

Transcription

1 ELECTRONIC SUPPLEMENTARY INFORMATION (ESI) Formation in aqueous solution of non-oxido V IV complex with VN 6 coordination. Potentiometric, ESI-MS, spectroscopic and computational characterization Elzbieta Lodyga-Chruscinska, a Agnieszka Szebesczyk, b Daniele Sanna, c Kaspar Hegetschweiler, d Giovanni Micera e and Eugenio Garribba e,* a b c d e Institute of General Food Chemistry, Technical University of Lodz, ul. Stefanowskiego 4/10, PL , Lodz, Poland Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie St., PL-50383, Wrocław, Poland Istituto CNR di Chimica Biomolecolare, Trav. La Crucca 3, I Sassari, Italy Fachrichtung Chemie, Universität des Saarlandes, Postfach , D Saarbrücken, Germany Dipartimento di Chimica e Farmacia, and Centro Interdisciplinare per lo Sviluppo della Ricerca Biotecnologica e per lo Studio della Biodiversità della Sardegna, Università di Sassari, Via Vienna 2, I Sassari, Italy. garribba@uniss.it; Fax: ; Tel:

2 EPR theory background The 51 V HFC tensor A has three contributions: the isotropic Fermi contact (A FC ), the anisotropic or dipolar hyperfine interaction (A D ), and the second-order term that arises from spin-orbit (SO) coupling (A SO ): 1 FC D SO A A 1 A A (1) where 1 is the unit tensor; A FC and the components D A and SO A of the tensors A D and A SO are given by the following equations: FC 4π 1 α β A = gegnβeβn S z ρn (2) α β r δ 3r r e N e N z k, l k 5 l kl, r D 1 A = g g β β S P Φ Φ 2 (3) α β Pkl, SOC e N e N k l (4) kl, I SO 1 A = g g β β Φ h Φ 2S g e and g N are the g-factors of the free electron and the nucleus, e and N the electron and nuclear magnetons, the nucleus, S z the expectation value of the electronic spin on the z axis, α β kl, α β ρ N the spin density at P the spin density matrix, r the distance between the unpaired electron and the nucleus, and SOC h the spatial part of an effective one-electron spin-orbit operator. 1 The tensor A D is always traceless: their sum being zero: D A x, D A y and D A z are the elements of the diagonilized tensor, D D D x y z 0 A + A A (5) be: The values of the 51 V anisotropic hyperfine coupling constants along the x, y and z axes result to FC D SO x x x A A + A A (6) FC D SO y y y A A + A A (7) 2

3 FC D SO z z z A A + A A (8) From eqs. (5)-(8), the value of A iso is: 1 FC 1 SO SO SO FC PC Aiso Ax Ay Az A Ax Ay Az A A (9) SO SO SO The term x y z 3 A A A is named isotropic pseudocontact, APC. 1 Gaussian neglects the second-order SO effects and eqs. (6)-(9) become: FC D x + x (10) A A A y FC D y A A + A (11) z FC D z A A + A (12) A iso FC A (13) 3

4 Table S1 Main calculated and experimental electronic transitions calculated for [VO(taci)(H 2 O) 2 ] 2+, [VO(tmca)(H 2 O) 2 ] 2+, [V(taci) 2 ] 4+ and [V(tmcaH 2 ) 2 ] till 300 nm. Main transition Character (%) a f 10 5 b exptl exptl a,c / [VO(taci)(H 2 O) 2 ] 2+ H( ) L( ) d xy d xz (66.3) / 15 H( ) L+1( ) d xy d yz (79.6) / 5 H( ) L+3( ) d xy d x 2 y 2 (61.8) / 10 H( ) L+6( ) d xy d z 2 (53.6) / 190 [VO(tmca)(H 2 O) 2 ] 2+ d H-1( ) L( ) d xy d xz (75.9) H-1( ) L+1( ) d xy d yz (77.2) /20 H-1( ) L+2( ) d xy d x 2 y 2 (82.4) / 30 [V(taci) 2 ] 4+ H( ) L( ) d xy d yz (87.2) H( ) L+1( ) d xy d xz (87.3) H-3( ) L( ) / H-1( ) L+1( ) O lp d yz (35.1)/ O lp d xz (29.1) H-2( ) L+1( ) O lp d xz (62.8) / 1190 H-1( ) L( ) O lp d xy (49.3) H-1( ) L( ) O lp d xy (36.8) H-8( ) L( ) O lp d yz (35.4) / 1790 [V(tmcaH 2 ) 2 ] H( ) L( ) d xy d yz (95.0) H( ) L+1( ) d xy d xz (90.2) H-1( ) L( ) N lp d yz (52.6) H-2( ) L( ) N lp d yz (70.8) / 935 H-1( ) L+1( ) N lp d xz (60.7) H( ) L( ) N lp d yz (60.3) / 1335 e H( ) L+2( ) N lp d xz (72.8) H-1( ) L+1( ) N lp d xy (55.1) H-1( ) L+2( ) N lp d xz (42.0) H( ) L+2( ) N lp d xz (32.7) / 7100 a values measured in nm. b Oscillator strength. c values measured in M 1 cm 1. d d xy d z 2 predicted at nm. e Shoulder of a more intense absorption. 4

5 Fig. S1 Experimental electronic absorption spectrum of [VOLH 1 ] +, recorded on the V IV O 2+ /tmca (L) system with a total V IV O 2+ concentration of M, L/V IV O = 15, ph 7.05 (in black). The spectra calculated by DFT methods for the two possible species [VO(tmca)(OH)(H 2 O)] + and [VO(tmcaH 1 )(H 2 O) 2 ] + are shown in red and blue, respectively. 5

6 Fig. S2 ESI positive ion mass spectrum recorded on the V IV O 2+ /tmca (L) system in a mixture MeOH/H 2 O 1:1 v/v with a total L concentration of M, L/V IV O = 15, ph In the inset the region between m/z 573 and 580. The peaks at m/z and were assigned to the ions {2tmca + Na + } and {2tmca + NaCl + Na + }, that at m/z of to {[V(tmcaH 2 ) 2 ] + Na + + 2H 2 O + MeOH}. 6

7 Fig. S3 ESI positive ion mass spectrum recorded on the V IV O 2+ /tmca (L) system in a mixture MeOH/H 2 O 1:1 v/v with a total L concentration of M, L/V IV O = 15, ph The peaks at m/z and were assigned to the ions {2tmca + Na + } and {2tmca + NaCl + Na + }. 7

8 Fig. S4 ESI negative ion mass spectrum recorded on the V IV O 2+ /tmca (L) system in a mixture MeOH/H 2 O 1:1 v/v with a total L concentration of M, L/V IV O = 15, ph The peaks at m/z and were assigned to the ions {[V(tmcaH 2 ) 2 ] + NaCl + OH } and {[V(tmcaH 2 ) 2 ] + NaCl + 2H 2 O + SO 2 4 }, those at m/z and to {[VO(OH) 3 ] + 5NaCl + Cl + OH + SO 2 4 } and {[VO(OH) 3 ] + 6NaCl + Cl + OH + SO 2 4 }. 8

9 Fig. S5 Molecular orbitals for [VO(taci)(H 2 O) 2 ] 2+ : (a) H( ), V-d xy, (b) L( ), V-d xz, (c) L+1( ), V- d yz, (d) L+3( ), V-d x 2 y 2 and (e) L+6( ), V-d z 2. 9

10 Fig. S6 Molecular orbitals for [VO(tmca)(H 2 O) 2 ] 2+ : (a) H-1( ), V-d xy, (b) L( ), V-d xz, (c) L+1( ), V-d yz and (d) L+2( ), V-d x 2 y 2. 10

11 Fig. S7 Molecular orbitals for [V(taci) 2 ] 4+ : (a) H-8( ), taci-o lp, (b) H-3( ), taci-o lp, (c) H-2( ), taci-o lp, (d) H-1( ), taci-o lp, (e) H( ), V-d xy, (f) L( ), V-d yz, (g) L+1( ), V-d xz, (h) H-1( ),taci-o lp and (i) L( ), V-d xy. The superscript lp indicates an electron lone pair. 11

12 Fig. S8 Molecular orbitals for [V(tmcaH 2 ) 2 ]: (a) H-2( ), tmca-n lp, (b) H-1( ), tmca-n lp, (c) H( ), V-d xy, (d) L( ), V-d yz, (e) L+1( ), V-d xz, (f) H-1( ), tmca-n lp, (g) H( ), tmca-n lp, (h) L( ), V-d yz, (h) L+1( ), V-d xy, and (i) (h) L+2( ), V-d xz. The superscript lp indicates an electron lone pair. 12

13 Fig. S9 Spin density contour of (a) [V(taci) 2 ] 4+, (b) [V(tdci) 2 ] 4+, (c) [V(inoH 3 ) 2 ] 2 and (d) [V(tmcaH 2 ) 2 ]. The three Cartesian axes are also represented. 13

14 (i) (ii) (iii) (iv) H 2 N H 2 N HO OH HO H 2 N OH NH 2 HO OH H 2 N NH 2 Scheme S1 Possible coordination modes of a papa ligand. 14

15 H 2 N H 3 CO H 2 N H 2 N H 3 CO OCH 3 OCH 3 NH 2 H 3 CO OCH 3 H 2 N NH 2 Scheme S2 The two chair conformations of tmca. 15

16 References 1. F. Neese, ORCA - An Ab Initio, DFT and Semiempirical Program Package, Version 2.9, Max-Planck-Institute for Bioinorganic Chemistry, Mülheim a. d. Ruhr, Germany,