Figure S1. ¹H-NMR spectrum of R-2 (399.8 MHz, CD₂Cl₂, 298 K, Me₄Si).

Figure S2 ¹³C-NMR spectrum of R-2 (150.9 MHz, CDCl₃, 298 K, Me₄Si).

Figure S3 Mass spectrum of R-2.

Figure S4 ¹H-NMR spectrum of S-2 (399.8 MHz, CD₂Cl₂, 298 K, Me₄Si).

Figure S5 ¹³C-NMR spectrum of S-2 (150.9 MHz, CDCl₃, 298 K, Me₄Si).

Figure S6 Mass spectrum of S-2.

Figure S7 ¹H-NMR spectrum of R-3 (399.8 MHz, CD₂Cl₂, 298 K, Me₄Si).

Figure S8 ¹³C-NMR spectrum of R-3 (100.5 MHz, CDCl₃, 298 K, Me₄Si).

Figure S9 Mass spectrum of R-3.

Figure S10 Schematic diagram of HTCPL system.

Figure S11 CPL and luminescence spectra for R-2 and S-2 at fw of (A) 0%, (B) 50%, (C) 60%, (D) 65%, (E) 70%, (F) 75%, (G) 80%, (H) 85%, and (I) 90%. The CPL and luminescence spectra for R-2 are the average of three separate measurements. The variation range is defined as $$$ \pm \sigma $$$.

Figure S12 (A) CPL and (B) luminescence spectra for R-3 at fw of 0%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, and 90%.

Figure S13 (A) CPL and (B) luminescence spectra for S-1 at fw of 0%, 70%, 75%, 80%, and 90%.

Table S1 Relationship between fw and luminescence intensity for R-2 and S-2 (645.5 nm), S-1 (650 nm), and R-3 (650 nm).

Table S2 Crystallographic data for (A) R-2 and (B) R-3.

Figure S14 Crystal structure of R-2. (A) CH $$$ \cdots $$$ π interactions in a-axis and a-b directions and (B) in c-axis direction.

Figure S15 Crystal structure of R-3. (A) - (C) CH $$$ \cdots $$$ π interactions and (D) CH $$$ \cdots $$$ O interaction.

Figure S16 CD and absorption spectra of R-2 simulated by TD-DFT calculations together with experimental spectra.

Table S3 Selected TD-DFT calculated excitation energies corresponding to experimental absorption wavelengths and main weights of transitions for R-2.

Figure S17 Kohn-Sham orbitals for R-2 related to excitations listed in Table S3.

Figure S18 CD and absorption spectra of R-3 simulated by TD-DFT calculations together with experimental spectra.

Table S4 Selected TD-DFT calculated excitation energies corresponding to experimental absorption wavelengths and main weights of transitions for R-3.

Figure S19 Kohn-Sham orbitals for R-3 related to excitations listed in Table S4.

Figure S20 CPL and luminescence spectra of (A) R-2 and S-2 and (B) R-3 in powder state.

Table S5 $$$ {g}_{cpl} $$$ values for each complex in powder state. ^a