TY - JOUR
T1 - Dinuclear Cu(I) Halides with Terphenyl Phosphines: Synthesis, Photophysical Studies, and Catalytic Applications in CuAAC Reactions
AU - Beltrán, Álvaro
AU - Gata, Inmaculada
AU - Maya, Celia
AU - Avó, João
AU - Lima, João Carlos
AU - Laia, César A. T.
AU - Peloso, Riccardo
AU - Outis, Mani
AU - Nicasio, M. Carmen
N1 - We thank MINECO (Grants CTQ2014-52769-C3-3-R, CTQ2017-82893-C2-2-R, and CTQ2016-75193-P) for financial support.
This work was also supported by the Associate Laboratory for Green Chemistry-LAQV, which is financed by national funds from FCT/MCTES (UIDB/50006/2020). M.O. acknowledges Ph.D. Grant SFRH/BD/120985/2016 financed by FCT (the Portuguese national funding agency for science, research, and technology).
We are grateful to Mr. Francisco Molina for assistance with X-ray diffraction studies of complexes 1b, 1c, 2c, 4c, and 5c and to Dr. Joaquin Lopez-Serrano and Ms. Mari ' a M. Alcaide for performing and discussing DOSY experiments. Thanks are also due to Centro de Investigacion, Tecnologia e Innovacion de la Universidad de Sevilla (CITIUS).
BioISI-Biosystems & Integrative Sciences Institute for computer time and Dr. Vanessa Otero are acknowledged for assistance with Raman spectra.
J.A. acknowledges Fundacao para a Ciencia e a Tecnologia (FCT, I.P.) for funding under grant SFRH/BPD/120599/2016 and project PTDC/QUI-QFI/32007/2017.
PY - 2020/8/3
Y1 - 2020/8/3
N2 - Several dinuclear terphenyl phosphine copper(I) halide complexes of composition [CuX(PR2Ar′)]2 (X = Cl, Br, I; R = hydrocarbyl, Ar′ = 2,6-diarylterphenyl radical), 1-5, have been isolated from the reaction of CuX with 1 equiv of the phosphine ligand. Most of them have been characterized by X-ray diffraction studies in the solid state, thus allowing comparative discussions of different structural parameters, namely, Cu···Cu and Cu···Aryl separations, conformations adopted by coordinated phosphines, and planarity of the Cu2X2 cores. Centrosymmetric complexes [CuI(PMe2ArXyl2)]2, 1c, and [CuI(PEt2ArMes2)]2, 3c, despite their similar structures, show very distinct photoluminescence (PL) in powder form at room temperature. The photophysical behavior of these compounds in liquid solution, solid-solid Zeonex solution and powder samples at room temperature and 77 K have been investigated and supported by DFT calculation. Identification of vibronic coupling modes, done by group theory calculations and the technique of projection operators, shows that the manifestation of these modes is conditioned by crystal packing. Complexes [CuI(PMe2ArXyl2)]2, 1c, and [CuI(PEt2ArMes2)]2, 3c, display remarkable activity in copper-catalyzed azide-alkyne cycloaddition reactions involving preformed and in situ-made azides. Reactions are performed in H2O, under aerobic conditions, with low catalyst loadings and tolerate the use of iodoalkynes as substrates.
AB - Several dinuclear terphenyl phosphine copper(I) halide complexes of composition [CuX(PR2Ar′)]2 (X = Cl, Br, I; R = hydrocarbyl, Ar′ = 2,6-diarylterphenyl radical), 1-5, have been isolated from the reaction of CuX with 1 equiv of the phosphine ligand. Most of them have been characterized by X-ray diffraction studies in the solid state, thus allowing comparative discussions of different structural parameters, namely, Cu···Cu and Cu···Aryl separations, conformations adopted by coordinated phosphines, and planarity of the Cu2X2 cores. Centrosymmetric complexes [CuI(PMe2ArXyl2)]2, 1c, and [CuI(PEt2ArMes2)]2, 3c, despite their similar structures, show very distinct photoluminescence (PL) in powder form at room temperature. The photophysical behavior of these compounds in liquid solution, solid-solid Zeonex solution and powder samples at room temperature and 77 K have been investigated and supported by DFT calculation. Identification of vibronic coupling modes, done by group theory calculations and the technique of projection operators, shows that the manifestation of these modes is conditioned by crystal packing. Complexes [CuI(PMe2ArXyl2)]2, 1c, and [CuI(PEt2ArMes2)]2, 3c, display remarkable activity in copper-catalyzed azide-alkyne cycloaddition reactions involving preformed and in situ-made azides. Reactions are performed in H2O, under aerobic conditions, with low catalyst loadings and tolerate the use of iodoalkynes as substrates.
UR - http://www.scopus.com/inward/record.url?scp=85089183483&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.0c01397
DO - 10.1021/acs.inorgchem.0c01397
M3 - Article
C2 - 32691590
AN - SCOPUS:85089183483
VL - 59
SP - 10894
EP - 10906
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 15
ER -