1：Experimental Design and Method Selection:

The study involved synthesizing complexes via salt metathesis reactions, characterizing them using X-ray crystallography, variable temperature NMR spectroscopy, absorption and emission spectroscopy, TD-DFT calculations, and cyclic voltammetry to understand their structural, dynamic, optical, and electrochemical properties.

2：Sample Selection and Data Sources:

The ligand precursor HMePMPMe was synthesized from acetylacetone and 2-(aminomethyl)pyridine. Complexes were prepared by reacting deprotonated ligand with MCl4 (M = Zr, Hf). Data were collected from NMR, UV-vis, emission spectra, and computational models.

3：List of Experimental Equipment and Materials:

Equipment includes NMR spectrometers (Agilent 400 MHz, JOEL 400 MHz, Varian INOVA 600 MHz), UV-vis spectrophotometer (Shimadzu UV-1800), spectrofluorophotometer (Shimadzu RF-5301 PC), Fluorolog-3 Spectrofluorometer (Horiba Jobin Yvon), electrochemical workstation (Gamry Interface 1000), and X-ray diffractometer (Bruker AXS D8 Venture). Materials include THF, n-BuLi, ZrCl4, HfCl4, deuterated solvents, and tetrabutylammonium hexafluorophosphate.

4：Experimental Procedures and Operational Workflow:

Synthesis involved deprotonation of HMePMPMe with n-BuLi, followed by reaction with MCl4, purification, and crystallization. Characterization included NMR at various temperatures, absorption and emission measurements, electrochemical studies, and X-ray crystallography. Computational studies used DFT and TD-DFT with ORCA software.

5：Data Analysis Methods:

Data were analyzed using software like gNMR for NMR line shape analysis, DAS v6.1 for lifetime fitting, and SHELXL for crystallographic refinement. Statistical methods included Eyring analysis for activation parameters.