Inspired by the enhanced photoluminescence of Au nanoclusters (AuNCs)with arigid shell, the formation of rigid host-guest assemblies on AuNC surfaces was employed to screen novel electrochemiluminophores with 6-aza-2thiothymine(ATT)-protected AuNCs (ATT-AuNCs) and larginine (ARG) as models for the first time.T he rigid hostguest assemblies formed between ARG and ATTont he ATT-AuNC surface enabled aqueous-soluble ARG/ATT-AuNCs with ad ramatically enhanced electrochemiluminescence (ECL) compared to ATT-AuNCs.T his includes one cathodic ECL process (À1.30 V) and three anodic ECL processes (+ 0.78, 0.90, and 1.05 V) in as o-called half-scan experiment without aco-reactant, as well as a70-fold enhanced oxidativereduction ECL at + 0.78 Vw ith tri-n-propylamine as ac oreactant. Importantly,t he ECL of the ARG/ATT-AuNCs is highly monochromatic with an emission maximum around 532 nm and afull width at half-maximum of 36 nm, whichisof great interest for color-selective ECL assays.

Tunable optics and electronics of II-VI nanocrystals (NCs) is mainly achieved by using the traditional size-dependent strategy. Herein, we show that the triggering energy (potential), intensity, and even reductive-oxidation electrochemiluminescence (ECL) spectra of highly passivated CdTe/CdS NCs of the same size can be adjusted by simply decorating the NCs with counterions, which proves that surface chemistry can bring about varied electrostatic interactions between the surface vacancies and electrochemically injected carriers for adjustable electrochemical redox induced radiative charge transfer. Potential-resolved ECL demonstrates that increasing the surface sulfur vacancies and decreasing the surface cadmium vacancies can clearly enhance the ECL intensity and lower ECL triggering energy. All the traditional accumulated ECL spectra of CdTe/CdS NCs with various surface vacancies are close to the photoluminescence spectrum of monodisperse NCs without surface treatment, indicating the ECL spectra are mainly dominated by the CdTe core, whereas the slightly redshifted ECL spectrum of CdTe/CdS NCs with excessive cadmium vacancies indicates that the electrostatic repulsion between surface cadmium vacancies and electrons partially consumes the energy of the electrochemically injected electrons. Interestingly, spooling ECL spectra of CdTe/CdS NCs with varied surface vacancies are slightly blueshifted with negatively scanned potential, indicating electrons can be injected into conduction band of higher energy levels in a potential modulated way.

Tunable charge transfer in and out of nanocrystals (NCs) is crucial to their profound light-emitting applications. Herein a convenient strategy toward tunable electron-injection channels of NCs was achieved by partially coating highly passivated CdTe NCs with unperfected ZnSe shell. Potential-and spectrum-resolved electrochemiluminescence (ECL) characterizations proved that radiative charge recombination for ECL of the heterostructured ZnSe@CdTe NCs only occurred within CdTe core, whereas configurational ions in ECL solution could electrostatically or chemically change the surface states of both the ZnSe shell and the uncoated CdTe core, resulting in tunable electron-injection channels for ECL of ZnSe@CdTe NCs. S 2− anion postponed the electron-injection channel for ECL of ZnSe@CdTe NCs from −1.44 to −1.58 V, Zn 2+ cation presented two electron-injection channels for ECL at −1.53 and −1.22 V, respectively, whereas Cd 2+ cation enabled three electron-injection channels for ECL at −1.53, −1.18, and −0.95 V, respectively. The "valve"-like role of configurational ions on the electron-injection channels of ZnSe@CdTe NCs is promising to design novel electrochemiluminophores.

Inspired by the enhanced photoluminescence of Au nanoclusters (AuNCs) with a rigid shell, the formation of rigid host–guest assemblies on AuNC surfaces was employed to screen novel electrochemiluminophores with 6‐aza‐2‐thiothymine(ATT)‐protected AuNCs (ATT‐AuNCs) and l‐arginine (ARG) as models for the first time. The rigid host–guest assemblies formed between ARG and ATT on the ATT‐AuNC surface enabled aqueous‐soluble ARG/ATT‐AuNCs with a dramatically enhanced electrochemiluminescence (ECL) compared to ATT‐AuNCs. This includes one cathodic ECL process (−1.30 V) and three anodic ECL processes (+0.78, 0.90, and 1.05 V) in a so‐called half‐scan experiment without a co‐reactant, as well as a 70‐fold enhanced oxidative‐reduction ECL at +0.78 V with tri‐n‐propylamine as a co‐reactant. Importantly, the ECL of the ARG/ATT‐AuNCs is highly monochromatic with an emission maximum around 532 nm and a full width at half‐maximum of 36 nm, which is of great interest for color‐selective ECL assays.