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Metal cyanide clusterfullerenes (CYCFs) are formed via the encapsulation of a single metal atom and a cyanide unit inside fullerene cages, endowing them with excellent properties in various applications. In this work, we report the synthesis, isolation, and characterizations of the first cases of thulium (Tm)-based CYCFs with the popular C82 carbon cages. The structural elucidation of the two TmCN@C82 isomers was achieved via diverse analytical techniques, including mass spectrometry, Vis-NIR spectroscopy, single-crystal X-ray crystallography, and cyclic voltammetry. The crystallographic analyses unambiguously confirmed the molecular structures of the two TmCN@C82 isomers as TmCN@Cs(6)-C82 and TmCN@C2v(9)-C82. Both TmCN clusters adopt a well-established triangular configuration, with the Tm ion located on the symmetrical plane of the carbon cages. The electronic structures of both TmCN@C82 isomers adopt a Tm3+(CN)−@(C82)2− configuration, exhibiting characteristic spectral and electrochemical properties reminiscent of divalent endohedral metallofullerenes (EMFs). Intriguingly, unlike the divalent Tm2+ ion observed in the mono-metallofullerenes Tm@C2n, a higher oxidation state of Tm3+ is identified in the monometallic TmCN cluster due to bonding with the cyanide anion. This result provides valuable insight into the essential role of the non-metallic endo-units in governing the oxidation state of the metal ion and the electronic behaviors of EMFs. [ABSTRACT FROM AUTHOR]

Flexible photodetectors (PDs) are attracting more attention due to their promising applications in wearable optoelectronic devices, bendable imaging sensors, and implantable optoelectronics. For the easy‐processable technology of massively fabricating PDs, instead of the expensive and complex high‐vacuum technique, the well‐matched work function of their active materials is essential. Herein, all‐sprayed‐processable and large‐area PDs are demonstrated on common paper based on two‐dimensional (2D) CsPbBr3 nanosheets and conductive Ti3C2Tx (MXene). Ascribed to the superior conductivity of MXene, high crystallinity of 2D CsPbBr3, and their well‐matched work function, the as‐prepared PDs exhibit an outstanding on/off current ratio up to 2.3 × 103 and a remarkable photoresponse as fast as 18 ms. Specifically, the detectivity (D*) of 6.4 × 108 Jones and responsivity (R) of 44.9 mA W−1 under a bias of 10 V are achieved. Besides, after bending 1500 cycles, the as‐prepared PDs can still maintain the excellent flexibility and stability. Based on this, a superior‐quality and large‐area 1665 pixel sensor in 72 cm2 (≈24 units cm−2) is developed, and it can clearly transmit the image of "0" to realize the photocommunication function. This work provides a low‐cost method of massively producing the flexible large‐area PDs for wearable optoelectronic devices and expanded photocommunication. The on‐paper flexible photodetectors based on 2D perovskite nanosheets and Ti3C2Tx (MXene) as the active materials and electrode materials by all‐spraying method are demonstrated. The low‐cost photodetectors have high stability, flexibility, photoelectric performance, and can effectively realize the optical communication function of image sensing by large‐area arrays. This technique can be potentially expanded to other optoelectronic devices. [ABSTRACT FROM AUTHOR]

Metal-nitrogen double bonds have been commonly reported for conventional metal complexes, but the coexistence of both transition metal-nitrogen and lanthanide-nitrogen double bonds bridged by nitrogen within one compound has never been reported. Herein, by encapsulating a ternary transition metal-lanthanide heteronuclear dimetallic nitride into a C 84 fullerene cage, transition metal-nitrogen and lanthanide-nitrogen double bonds are costabilized simultaneously within the as-formed clusterfullerene TiCeN@C 1 (12)-C 84 , which is a representative heteronuclear dimetallic nitride clusterfullerene. Its molecular structure was unambiguously determined by single-crystal X-ray diffraction, revealing a slightly bent μ 2 -bridged nitride cluster with short Ti-N (1.761 Å) and Ce-N (2.109 Å) bond lengths, which are comparable to the corresponding Ti=N and Ce=N double bonds of reported metal complexes and consistent with the theoretically predicted values, confirming their coexistence within TiCeN@C 1 (12)-C 84 . Density functional theory (DFT) calculations unveil three-center two-electron (3 c -2 e ) bonds delocalized over the entire TiCeN cluster, which are responsible for costabilization of Ti=N and Ce=N double bonds. An electronic configuration of Ti 4+ Ce 3+ N 3- @C 84 4- is proposed featuring an intramolecular four-electron transfer, drastically different from the analogous actinide dimetallic nitride clusterfullerene (U 2 ) 9+ N 3- @C 80 6- and trimetallic nitride clusterfullerene (Sc 2 ) 6+ Ti 3+ N 3- @C 80 6- , indicating the peculiarity of 4-fold negatively charged fullerene cage in stabilizing the heteronuclear dimetallic nitride cluster., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Co-published by University of Science and Technology of China and American Chemical Society.)