1：Experimental Design and Method Selection:

The study involved synthesizing poly(imino ether sulfone) (PIES) via nucleophilic substitution polycondensation, utilizing its temperature-dependent fluorescence for Tg detection and imaging. Theoretical models include free volume theory and density functional theory (DFT) for mechanism investigation.

2：Sample Selection and Data Sources:

PIES was synthesized from 4,4'-dihydroxydiphenylamine and 4,4'-difluorodiphenyl sulfone. Films were prepared by casting from NMP solution. Data from FT-IR, NMR, TGA, DSC, stress-strain tests, UV-vis, and fluorescence spectroscopy were used.

3：List of Experimental Equipment and Materials:

Equipment includes Nicolet 6700 FTIR spectrometer, Bruker AMX600 NMR spectrometer, Vario EL III elemental analyzer, Setaram TG-92 TGA, DSC instrument, WDW-100 universal testing machine, SHIMADZU UV-3150 spectrophotometer, PerkinElmer LS-55 fluorescence spectrometer, Wyatt DAWN HELEOS GPC. Materials include 4,4'-difluorodiphenyl sulfone, Pd2(dba)3, BINAP, K2CO3, NMP, DMF, DMSO-d6, and others from commercial sources.

4：Experimental Procedures and Operational Workflow:

Synthesis involved heating reactants in NMP with K2CO3 at 140°C for 3h and 180°C for 6h under nitrogen. Films were cast on glass, evaporated at 60-90°C, washed, and dried. Characterization included spectral measurements, thermal analysis, mechanical testing, and variable-temperature NMR.

5：Data Analysis Methods:

Data were analyzed using standard techniques for spectroscopy, thermal properties, mechanical properties, and computational DFT calculations for conformational changes.