Spectroscopic Characterization of Chloride and Pseudohalide Ruthenium (II) Complexes With

Spectroscopic characterization of chloride and pseudohalide ruthenium (II) complexes with 4-(4-nitrobenzyl)pyridine.

Anna M. Maroń, Jan G. Małecki

Supplementary Materials.

Table S1. Hydrogen bonds for [[RuHCl(CO)(pyCHPhNO2)(PPh3)2] (1), [RuH(NCO)(CO)(pyCHPhNO2)(PPh3)2] (2), [RuH(NCS)(CO)(pyCHPhNO2)(PPh3)2] (3). (Å and o).

D-H...A / d(D–H) / d(H...A) / d(D...A) / <(DHA)
(1)
C(6)-H(6)...Cl(1) / 0.93 / 2.60 / 3.281(6) / 130.6
C(51)-H(51)...Cl(2) / 0.93 / 2.54 / 3.231(6) / 131.0
C(74)-H(74)...Cl(2) / 0.93 / 2.65 / 3.474(10) / 147.7
C(100)-H(100)...Cl(3) / 0.93 / 2.66 / 3.302(6) / 126.5
(2)
C(6)-H(6)...N(3) / 0.93 / 2.40 / 3.007(7) / 122.6
C(9)-H(9)...O(4) #1 / 0.93 / 2.34 / 3.228(12) / 158.8
C(21)-H(21)...N(3) / 0.93 / 2.54 / 3.181(7) / 126.5
(3)
C(15)-H(15) ...N(3) / 0.93 / 2.62 / 3.141(4) / 115.7
C(31)-H(31) ...N(1) / 0.93 / 2.60 / 3.421(4) / 147.7
C(39)-H(39) ...N(3) / 0.93 / 2.55 / 3.357(4) / 145.3

Symmetry transformation used to generate equivalent atoms: #1 x,1/2-y,-1/2+z

Table S2. π… interactions in molecular structures of complexes (1) - (3).

angle [o] / distance [Å] / shift distance [Å]
(1)*
centroids: #Cg1: (N1 C6 C5 C4 C3 C2); #Cg2:(C32– C37); #Cg3: (C26- C31)
#Cg1:#Cg2 / 20.690 / 3.843 / 1.516
#Cg1:#Cg3 / 24.661 / 3.861 / 1.569
(2)
centroids: #Cg1: (N1 C2 C3 C4 C5 C6); #Cg2: (C26 - C31); #Cg3: (C44 - C49)
#Cg1:#Cg2 / 16.620 / 3.736 / 1.758
#Cg1:#Cg3 / 18.676 / 3.640 / 1.144
(3)
centroids: #Cg1: (N1 C6 C5 C4 C3 C2);#Cg3: (C38-C43)
#Cg1:#Cg3 / 147.874 / 3.905 / 1.890

* average values

(1)

(2)

(3)

Figure S1. Experimental and calculated powder XRD spectra of complexes (1) – (3)

Figure S2. 2D map of fluorescence of the ligand NO2PhCH2py in methanol:ethanol (1:4) mixture (1∙10-3 mol/L) at 298K. The graph shows only Raman scattering of solvent, any emissions of the ligand are not visible.

Figure S3. Emission decay traces of complexes.

(1) / (2) / (3)

Figure S4. Spin density maps of complexes.