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In situchemistry of solid silver pyrazolates with ethylene gas, depending on the pyrazolyl ring substituents, stops at a trinuclear complex or leads to complete structure re-organizations producing dinuclear complexes as evident from PXRD data. 

Described herein is the synthesis and photophysics of two tetranuclear copper complexes, {[3,5-(Pr i ) 2 ,4-(Br)Pz]Cu} 4 and {[3-(CF 3 ),5-(Bu t )Pz]Cu} 4 tailor-designed by manipulating the pyrazolyl ring substituents. Unlike their trinuclear analogues, the luminescence of the tetranuclear species is molecular (not supramolecular) in nature with extremely high solid-state quantum yields of ∼80% at room temperature. 

Abstract Non‐porous small molecule adsorbents such as {[3,5‐(CF₃)₂Pz]Cu}₃(where Pz=pyrazolate) are an emerging class of materials that display attractive features for ethene−ethane separation. This work examines the chemistry of fluorinated copper(I) pyrazolates {[3,5‐(CF₃)₂Pz]Cu}₃and {[4‐Br‐3,5‐(CF₃)₂Pz]Cu}₃with much larger 1‐butene in both solution and solid state, and reports the isolation of rare 1‐butene complexes of copper(I), {[3,5‐(CF₃)₂Pz]Cu(H₂C=CHC₂H₅)}₂and {[4‐Br‐3,5‐(CF₃)₂Pz]Cu(H₂C=CHC₂H₅)}₂and their structural, spectroscopic, and computational data. The copper−butene adduct formation in solution involves olefin‐induced structural transformation of trinuclear copper(I) pyrazolates to dinuclear mixed‐ligand systems. Remarkably, larger 1‐butene is able to penetrate the dense solid material and to coordinate with copper(I) ions at high molar occupancy. A comparison to analogous ethene and propene complexes of copper(I) is also provided.