Is a High Photoluminescence Quantum Yield Good Enough for OLEDs? Can Luminescence Rigidochromism Be Manifest in the Solid State? an Optoelectronic Device Screening Case Study for Diphosphine/Pyrazolate Copper(I) Complexes

摘要

This paper provides a 4thmanifestation of a new tradition bywhich the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry. (For the 1st, 2nd and 3rd manifestations, see: a) Otten, B. M.; Melancon, K. M.; Omary, M. A. "All That Glitters is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d~(10) Metal Centers-A Tribute to Al Cotton on the 10th Anniversary of His Passing," Comments Inorg. Chem. 2018, 38, 1-35; b) Yaseen, W. K.; Sanders, S. F.; Almotawa, R. M.; Otten, B. M.; Bhat, S.; Alamo, D. C.; Marpu, S. B.; Golden, T. D.; Omary, M. A. "Are Metal Complexes "Organic", "Inorganic", "Organometallic", or "Metal-Organic" Materials? A Case Study for the Use of Trinuclear Coinage Metal Complexes as "Metal-Organic Coatings" for Corrosion Suppression on Aluminum Substrates", Comments Inorg. Chem. 2019, 39, 1-26; and c) Smith, J. B.; Otten, B. M.; Derry, P. J.; Browning, C.; Bodenstedt, K. W.; Sandridge, J. H.; Satumtira,N. T.; Zilaie,M.; Payne, J.; Nuti, R.; Omary, M. A.; Smucker, B. W. "Luminescent, Redox-Active (Dithiolato)Bis(Imine)Platinum(II) Divergent Complexes with Exchangeable Imine Ligands: An Experimental/Computational Study versus Their (Diimine) (Dithiolato)Platinum(II) Convergent Congeners", Comments Inorg. Chem. 2019, 39, 188-215.) Herein, the dinuclear complexes {Cu[3,5-(CF_3)_2Pz](μ-dppm)}2 and {Cu[3,5-(CF_3)_2Pz](μ-dppm)}2?3THF were studied structurally, spectroscopically and via density functional theory (DFT). They were synthesized by reacting bis-(diphenylphosphino)methane (dppm) with the cyclic trinuclear complex {μ-[3,5-(CF_3)_2Pz]Cu}_3 to effect nuclearity reduction. Two forms of crystalline solids, {Cu[3,5-(CF_3)_2Pz](μ-dppm)}2 and {Cu[3,5-(CF_3)_2Pz](μ-dppm)}2?3THF have been obtained using diffe