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A sumanene derivative functionalized with triphenylbenzene units was found to exhibit aggregation-induced emission enhancement (AIEE). A disaggregation process after the addition of caesium cations (Cs+) was observed. This feature was employed for the design of the first sumanene-containing disaggregation-based fluorescent probe for specific, efficient and fast Cs+ recognition.The phosphine-borane iPr2P(o-C6H4)BFXyl2 (Fxyl = 3,5-(F3C)2C6H3) was found to react with gold(i) alkynyl and vinyl complexes via an original 1,1-phosphaboration