This document summarizes the synthesis and characterization of an anilido-imine zinc complex (2a) and its ability to catalyze photoinduced atom transfer radical addition reactions. Key findings include: 1) Complex 2a was synthesized and its structure was confirmed via single crystal X-ray diffraction. 2) Absorption and emission spectroscopy showed 2a has strong absorption in the visible region and emits in the green region. 3) Quantum yield experiments demonstrated 2a has good photoluminescence properties. 4) Time-correlated single photon counting measurements revealed 2a has multi-exponential decay lifetimes of milliseconds, indicating it may be suitable for catalysis.

1. Synthesis, Spectroscopic Characterization of
an Anilido-Imine
Zinc Complex and its Mechanistic
Insight into Photoinduced ATRA
KIRTI SINGH
PH16008
Inorg. Chem. Front., 2021,8, 2078-2087

2. 2(a)
Synthesis of Ligand and metal complex
2(b)
2(c)
ORTEP representation of the single crystal of 2a, 2b with ellipsoid set at 50% probability and hydrogen atoms omitted for
clarity. Optimised geometry for 2c

3. Absorbance AND emission PROFILE
Figure: (a)Comparison of normalised absorption intensities of ligand 1a, 1b and1c , (b) normalised absorption intensities of
zinc complexes 2a, 2b and 2c , (c) normalised emission intensities of ligands 1a, 1band 1c and (d) normalised emission
intensity of zinc complexes 2a, 2b and2c

4. Quantum yield experiments
Absorbance of 2a Emission intensity of 2a
Plot of integrated emission intensity for optical density less than 0.10 vs optical density for 2a with reference to Ru(bipy)2+

5. Tcspc measurements
S.No Sample τ1 τ2 τ3 Condition
1 2a 3.3 6.7 13.4+ 2 DCM/ degassed
2 2b 2.6 5.4 10.2 DCM/ degassed
3 2c 2.7 5.5 11.0 DCM/ degassed
4 2a 0.8 3.5 12.9 Q2
5 2a 0.5 2.4 9.6 Q3
6 2a 0.6 2.6 9.7 Q4
Decay profile and tri-exponential fit of zinc complexes to yield lifetimes under the below metioned conditions.

6. Molecular orbital diagram
 Figure 4: Qualitative MO diagram for 2a showing selected MOs and their TD-DFT states. Arrows symbolises single-electron
excitations with major contribution to absorption band with 203 as HOMO and 204 as LUMO.

7. Catalysis: substrate scope

8. Proposed mechanistic cycle

9. Radical trapping/ TEMPO QUENCHING

10. FLUORENCE QUENCHING EXPERIMENT
Stern Volmer plot for reductive quenching using different concentration of DIPEA in DCM at RT

11. intermittent illumination experiment and
kinetics
Light-on light-off” inter-luminent experiment
Rate of reaction

12. CV and excited state ENERGY
Figure (a) CV of 50 mM of 2ain THF. SCE was taken asreference; glassy carbon as working and Pt as counter electrode
(b) Normalized absorption and emission spectra of 2a in DCM, with E00 is the energy at their intersection point
 E00 from the intersection point of absorption and emission spectra, is
calculated using E*
ox = Eox – Eoo and E*
red = Ered + E00.
 E00 = 3.01 eV (411nm), E*
red = +2.03 volt and E*
ox = -1.81 volt.