All the chemicals and reagents were purchased from commercial sources and used as received without further purification. The final products were subjected to vacuum sublimation to further improve purity before PL and EL properties investigations. 1 H and C NMR spectra were measured on Bruker AV 500 spectrometer or Bruker AV 400 spectrometer in CDCl3, CD2Cl2 or C2D6SO at room temperature. High resolution mass spectra (HRMS) were recorded on a GCT premier CAB048 mass spectrometer operating in MALDI-TOF mode. Thermogravimetric analysis (TGA) was carried on a TA TGA Q5000 under dry nitrogen at a heating rate of 20 °C min -1 . Thermal transition was investigated by a TA DSC Q1000 under dry nitrogen at a heating rate of 10 °C min -1 . Single crystals of CBP-1, CCO-1, CCO-2 and CCO-3 are cultured in dichloromethane/n-hexane, chloroform/n-hexane, deuterated chloroform and chloroform/ethanol, respectively. Single crystal X-ray diffraction intensity data were collected at 173 K on a Bruker-Nonices Smart Apex CCD diffractometer with graphite monochromated MoKα radiation. Processing of the intensity data was carried out using the SAINT and SADABS routines, and the structure and refinement were conducted using the SHELTL suite of X-ray programs (version 6.10). UV-vis absorption spectra were measured on a Shimadzu UV-2600 spectrophotometer (f ≈ 4.33 × 10 -9 ε ⋅ Δv 1/2 ; ε is absorption intensity; Δv 1/2 is wavenumber at half absorption strength). PL spectra were recorded on a Horiba Fluoromax-4 spectrofluorometer. PL quantum yields were measured using a Hamamatsu absolute PL quantum yield spectrometer C11347 Quantaurus_QY. Transient PL decay spectra were measured using Quantaurus-Tau fluorescence lifetime measurement system (C11367-03, Hamamatsu Photonics Co., Japan). The transient absorption spectra were recorded by a commercial TA system (Transpec-NS, CIS) equipped with a nanosecond pulse laser (Opolette 355 LD, 7 ns, 20 Hz) as the pump source and a broadband laser-driven light source (EQ99X LDLS) as the probe source. The detector output was fed to a digital oscilloscope (PicoScope 5000), which acquired the waveform and stored it for eventual data processing. The pump wavelength was 355 nm, and the measurement was carried out at room temperature. The angular-dependent spectra were measured with an ARM angle-resolved spectroscopy system (IdeaOptics Instruments). Cyclic voltammograms were measured in a solution of tetra-n-butylammonium hexafluorophosphate (nBu4NPF6, 0.1 M) in dichloromethane (anodic) and dimethylformamide (cathodic) at a scan rate of 50 mV s -1 , using a platinum wire as the auxiliary electrode, a glass carbon disk as the working electrode and Ag/Ag + as the reference electrode, standardized for the redox couple ferricenium/ferrocene (Fc/Fc + ) (HOMO = -[Eonset ox + 4.8] eV, and LUMO = -[Eonset re + 4.8] eV). Eonset ox and Eonset re represent the onset oxidation and reduction potentials relative to Fc/Fc + , respectively.