Reactivity of CuI and CuBr toward Et 2 S: a Reinvestigation on the Self-Assembly of Luminescent Copper(I) Coordination Polymers (original) (raw)
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Crystal Growth & Design, 2014
Bis(phenylthio)methane (L1) reacts with CuI to yield the 1D-coordination polymer [{Cu 4 (μ 3-I) 4 }(μ-L1) 2 ] n (1) bearing cubane Cu 4 I 4 clusters as connecting nodes. The crystal structures at 115, 155, 195, and 235 K provided evidence for a phase transition changing from the monoclinic space group C2/c to P2 1 /c. The self-assembly process of CuI with bis(p-tolylthio)methane (L2), bis(4-methoxyphenylthio)methane (L3), and bis(4-bromophenylthio)methane (L4) affords the 1D-coordination polymers [{Cu 4 (μ 3-I) 4 }(μ-Lx) 2 ] n (x = 2, 3, or 4). Compounds 2 and 4 are isostructural with C2/c low temperature polymorph of 1, whereas the inversion centers and 2-fold axes are lost in 3 (space group Cc). The use of bis(m-tolylthio)methane (L5) has no impact on the composition and overall topology of the resulting 1D ribbon of [{Cu 4 (μ 3-I) 4 }(μ-L5) 2 ] n (5). Even the coordination of the sterically crowded dithioether bis(5-tert-butyl-2-methylphenylthio)methane (L8) does not alter the network topology generating the 1D polymer [{Cu 4 (μ 3-I) 4 }(μ-L8) 2 ] n (8). The 1D polymer [{Cu(μ 2-Br) 2 Cu}(L1) 2 ] (9) results from the coordination of L1 with CuBr in a 1:1 metal-to-ligand ratio. In contrast to the mean Cu•••Cu distances, which are <2.8 Å noted for the Cu 4 (μ 3-I) 4 clusters in the 1D polymers 1−8, the Cu•••Cu contact within the Cu(μ 2-Br) 2 Cu rhomboids of 9 [2.9194(8) Å] is above the sum of the van der Waals radii of two Cu atoms. The structural arrangement of 1D polymer [{Cu(μ 2-Br) 2 Cu}(L3) 2 ] n (11) is quite similar to that of 9. While the reaction of CuBr with L5 results in a similar 1D polymer [{Cu(μ 2-Br) 2 Cu}(L5) 2 ] n (12), the reaction of CuBr with L2 leads to the dinuclear complex [{Cu(μ 2-Br) 2 Cu}(η 1-L2) 4 ] (10) ligated by four pendent bis(p-tolylthio)methane ligands. The ligation of bis(o-tolylthio)methane, L6, on CuBr also yields a discrete complex [{Cu(μ 2-Br) 2 Cu}(MeCN) 2 (η 1-L6) 2 ] (13) bearing MeCN and dangling dithioether ligands. A strong luminescence is detected for all CuI polymers, all exhibiting emission lifetimes in the microsecond time scale (i.e., phosphorescence). The polymers containing the Cu 4 I 4 core (1−8) exhibit the typically observed low-energy band and sometimes a weaker high-energy band. The nature of the low-energy band was proposed based on literature DFT and TDDFT computations and is predicted to be a mixture of cluster-centered (CC*) and metal/halide-to-ligand charger transfer (M/XLCT). An approximate relationship between the Cu•••Cu distance and the emission maxima corroborates the CC* contribution to the nature of the excited states. The emission of the rhomboid-containing materials is assigned to M/XLCT based on literature works on similar motifs.
Luminescent Coordination Polymers Built Upon Cu4 X4 (X=Br,I) Clusters and Mono- and Dithioethers
Macromolecular Rapid Communications, 2010
was born in Montréal, Canada. He graduated from the Université de Montréal in 1981 for his B.Sc. in chemistry and in 1983 for his M.Sc. in Photophysics where he studied the photophysical properties of carbazole derivatives. He obtained his Ph.D. in 1985 at McGill University in the field of solid state vibrational and NMR spectroscopy of organometallics submitted at very low temperatures and high pressures under the supervision of Prof. Ian S. Butler and Prof. Denis Gilson. Between 1986 and 1988 he then pursued his career at the California Institute of Technology with Prof. Harry B. Gray in the area of organometallic photochemistry and then at the Massachusetts Institute of Technology with Prof. Mark S. Wrigthon in the area of microelectro-chemistry. He was then appointed assistant, associate, and full professor at the Université de Sherbrooke in 1989, 1993, and 1998, respectively. He published over 180 research articles and 7 book chapters, and co-edited one book. His research interests include the photophysics, catalysis, electrochemistry, electrocatalysis of coordination and organometallic polymers, clusters, and host-guest assemblies. He is currently enjoying a research chair from the Agence National de la Recherche (ANR in France) at the Université de Bourgogne for 2 years where he is preparing and studying the photophysical properties of bio-inspired organometallic/porphyrin hybrids. He is also serving on two Editorial Boards of international journals. Michael Knorr was born in Würzburg, Germany. Graduate of the University of Würzburg in 1985, his Master's degree was followed by a Ph.D in chemistry (1988) under the supervision of Prof. Ulrich Schubert on the synthesis and reactivity of silyl and stannyl complexes of iron and manganese. As post-doctoral fellow (fellowship of the Deutsche Forschungsgemeinschaft DFG) and associate researcher, he spent the next 5 years in France (with Pierre Braunstein, Laboratoire de Chimie de Coordination) at the Université Louis Pasteur (Strasbourg) and spent also some months in the research group of Prof. R. J. P. Corriu at the Université de Montpellier. In 1994, he jointed the Institute of Inorganic Chemistry of Prof. Michael Veith at the University of the Saarland (Saarbrücken, Germany) to complete his habilitation thesis on the activation of unsaturated organic molecules by heterobimetallic transition metal complexes. After appointment to assistant professor (Privat-Dozent) in 1997, he moved back to Strasbourg to collaborate with P. Braunstein's laboratory and the Institute Charles Sadron. Since 1999 he leads, first as associate professor (PR 2), then as full professor (PR 1), a research group working on molecular materials and the deposition of nano(micro) particles/thin films on surfaces/interfaces at the Université de Franche-Comté (Besançon, France). At present, he is leader of the research group Matériaux et Surfaces Structurés and vice-director of the Institute UTINAM-UMR CNRS 6213. Scheme 1. Drawing of the closed cubane-liked and open-cubane tetramers. Scheme 2. View of the Et 2 S-bridged 1D [(Et 2 S) 3 {Cu 4 (m 3-I) 4 }] n polymer. The Cu-S distances are 2.331(8) and 2.337(6) Å , and terminal Cu-S distances are 2.297(10) and 2.298(9) Å .
Inorganic chemistry, 2016
The organometallic synthon trans-[p-MeSC6H4C≡C-Pt(PMe3)2-C≡CC6H4SMe] (L1) reacts with CuX (X = Cl, Br, I) in PrCN and PhCN to form 1D- or 2D-coordination polymers (CP) with a very high degree of variability of features. The copper-halide unit can be either the rhomboids Cu2X2 fragments or the step cubane Cu4I4. The CP's may also incorporate a crystallization solvent molecule or not, which may be coordinated to copper or not. Their characterizations were performed by X-ray crystallography, thermal gravimetric analysis (TGA), and IR, absorption, and emission spectra as well as photophysical measurements in the presence and absence of solvent crystallization molecules. The nature of the singlet and triplet excited state was addressed using DFT and TDDFT computations, which turn out to be mainly ππ* with some minor MLCT (Cu4I4 → L1) contributions. The porosity of the materials has been evaluated by BET (N2 at 77 K). The solvent-free 1D CP's are not prone to capture solvent molec...
CrystEngComm, 2015
In this article, the synthesis, structural studies, and luminescence properties of Cu I , Ag I , and Au I complexes of pyrimidine-based phosphine [C 4 H 3 N 2-2-NH(CH 2 PPh 2)] (1) are described. The reactions of 1 with CuX led to the isolation of one-dimensional (1D) chain, tetranuclear ladder, or cyclic derivatives. The structural features of these complexes are greatly influenced by the metal-to-ligand ratio, reaction conditions, and CuX (X = Cl, Br or I) employed. In the case of CuCl and CuBr, one-dimensional coordination polymers [{CuCl}{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] ∞ (2) and [{CuBr}{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] ∞ (3) were obtained, whereas CuI afforded tetracopper complex [{CuI} 4 {C 4 H 3 N 2-2-NH(CH 2 PPh 2)} 2 (NCCH 3) 2 ] (4) having Cu 4 ladder structure supported by P∩N-bridging coordination of 1. The reaction of 1 with AgOTf yielded unprecedented one-dimensional chain structure [{AgOTf}{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] ∞ (5), whereas the reaction with AgBF 4 produced a 12-membered dinuclear complex, [{Ag}{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] 2 [BF 4 ] 2 (6), with each silver atom having a linear geometry. Gold complex [{AuCl}-{C 4 H 3 N 2-2-NH(CH 2 PPh 2)}] 2 (7) was synthesized by reacting 1 with [AuCl(SMe 2)]. Compounds 2−4 were also prepared using a pestle and mortar by grinding method in almost quantitative yield. Complex 4 with a Cu•••Cu distance of 2.828(5) Å shows high luminescence due to the nonbonded metal•••metal interactions.
Journal of Cluster Science, 2013
The CuX salts (X = Br, I) react with 1,4-bis(cyclohexylthio)butane, L2, in a 1:1 ratio to form the corresponding isostructural and weakly luminescent 1D coordination polymers [(Cu 2 X 2)(l-L2) 2 ] n (X = Br, 4; X = I, 3) as determined by X-ray crystallography. The previously reported reaction of CuI with 1,4-bis(phenylthio)butane, L1, in a 2:1 metal-to-ligand ratio provides a 2D polymer [(Cu 4 I 4)(l-L1) 2 ] n , 1 (Knorr et al., Dalton Trans 38:948-955, 2009), where the Cu 4 I 4 unit exhibits the common cubane structure and an intense luminescence centered at 555 and 565 nm respectively at 298 and 77 K. When CuI reacts with L2 in a 2:1 metal-to-ligand ratio, a new material 2 is formed but no X-ray structure was obtained. The intense and characteristic luminescence of polymer 2 is strongly indicative of the formation of the cubane Cu 4 I 4 unit. The new materials have been characterized by solid-state UV-Vis rasing-angle transmittance spectroscopy, luminescence spectroscopy and emission lifetime measurements.
Journal of Coordination Chemistry, 2017 VOL. 70, NO. 23, 3907–
a hubei Collaborative innovation Center for advanced organic Chemical materials, ministry of education Key laboratory for the synthesis and application of organic functional molecules, school of Chemistry and Chemical engineering, hubei university, Wuhan, Pr China; b state Key laboratory of Physical Chemistry of solid surfaces, and fujian Provincial Key lab of theoretical and Computational Chemistry, College of Chemistry and Chemical engineering, Xiamen university, Xiamen, Pr China; c Chemistry department, faculty of science, King abdulaziz university, Jeddah, saudi arabia; d state Key laboratory of inorganic synthesis and Preparative Chemistry, College ABSTRACT Copper(I) halide complexes having thermally activated delayed fluorescence (TADF) and phosphorescence have attracted much attention. Here, a series of four-coordinate dinuclear copper(I) halide complexes, [CuX(bpbp)] 2 (bpbp = 2,2′-bis(diphenylphosphino) biphenyl, X = I (1), Br (2) and Cl ), were synthesized, and their molecular structures and photophysical properties were investigated. The structural analysis reveals that two copper(I) centers are bridged by two halogen ligands to form a dinuclear structure with a fourmembered Cu 2 X 2 ring. These complexes exhibit yellow to blue emission in the solid state at room temperature and have peak emission wavelengths at 575-487 nm with microsecond lifetimes (τ = 6.2-19.8 μs) and low emission quantum yields (<0.01%). The emissions of 1-3 originate from MLCT, XLCT, and IL (intraligand) transitions. Three complexes displayed good thermal stability.
Journal of Inorganic and Organometallic Polymers and Materials, 2015
The CuBr salt reacts with the acetylenic dithioether 1,4-bis(p-tolylthio)but-2-yne (L1) to generate the 1D [{Cu(l 2-Br) 2 Cu}(l-p-MeC 6 H 4 SCH 2 C:CCH 2 SC 6 H 4 Me-p) 2 ] n coordination polymer (1), contrasting with the previously reported reaction with CuI, which provided a 2D network [{Cu 4 (l 3-I) 4 } (l-p-MeC 6 H 4 SCH 2 C:CCH 2 SC 6 H 4 Me-p) 2 ] n. (JIOPM, 2014, 24, 190-200). The ribbons of 1 incorporate two different types of alternating centrosymmetric Cu(l 2-Br) 2 Cu rhomboids displaying loose CuÁÁÁCu contacts of 2.9306(14) and 2.9662(14) Å. The reaction of CuI and CuBr with the isomeric dithioether ligand 1,4-bis(benzylthio)but-2-yne (L2) yields the isomorphous dinuclear 0D complexes [{Cu(l 2-X) 2 Cu}(l-PhCH 2 SCH 2 C:CCH 2 SCH 2 Ph) 2 ] (2a: X = I; 2b: X = Br). These species represent the first examples of dinuclear [S 2 {Cu(l 2-X) 2 Cu}S 2 ] complexes spanned by a dithioether ligand. In contrast, treatment of CuCl with L2 gives rise to the formation of an unusual 2D coordination polymer [{Cu 2 (l 2-Cl)(l 3-Cl)}(l-PhCH 2 SCH 2 C:CCH 2 SCH 2 Ph)] n (3), in which the layers are assembled both by dative Cu-S thioether bonds and organometallic Cup -acetylenic interactions via the triple bond of the L2 ligand. Furthermore, the Cu(I) centers are interconnected through l 2-and l 3-bound chloro ligands. Finally, thermal stability and photophysical proprieties were studied. This investigation demonstrated the interesting luminescent behavior of CuCl-containing coordination polymer (3).
Journal of Coordination Chemistry, 2017 VOL. 70, NO. 16, 2916–
a ministry of education Key laboratory for the synthesis and application of organic functional molecules, hubei Collaborative innovation Center for advanced organic Chemical materials, school of Chemistry and Chemical engineering, hubei university, Wuhan, P. r. China; b faculty of science, Chemistry department, King abdulaziz university, Jeddah, saudi arabia; c institute of molecular functional materials and department of Chemistry and institute of advanced materials, hong Kong Baptist university, ABSTRACT Three-coordinate copper halide complexes with a bidentate phosphine ligand have received much attention. Here, a series of three-coordinate dinuclear copper halide complexes containing a diphenylamino monodentate phosphine ligand, [CuX(dpnp)] 2 (dpnp = N-[2-(diphenylphosphino)-4,5-dimethylphenyl]-Nphenylaniline, X = I (1), Br (2) and Cl (3)), were synthesized, and their molecular structures and photophysical properties were investigated. The structural analysis reveals that two copper(I) centers are bridged by two halogen ligands to form a dinuclear structure with a four-membered Cu 2 X 2 ring. Crystal structures of 1-3 contain 1-D supramolecular arrays constructed by intermolecular C-H⋯π interactions. These complexes exhibit blue emission in the solid state at room temperature and have peak emission wavelengths at 483-487 nm with microsecond lifetimes (τ = 13.9-38.1 μs) and low emission quantum yields (<0.01%). The emission of complex 1 mainly originates from intraligand (IL) transition, whereas the emissions of complexes 2 and 3 are from a combination of MLCT, XLCT and IL transitions. The three complexes displayed good thermal stability.
Control of Structures and Emission Properties of (CuI)n 2-Methyldithiane Coordination Polymers
Inorganic Chemistry, 2018
A structurally unique and strongly luminescent non-porous 3D coordination polymer (CP) [Cu 8 I 8 (methyldithiane) 4 ] n , CP3, has been prepared in a quasi-anticipated manner from 2-methyl-1,3-dithiane, L1, and CuI. This CP incorporates the unprecedented Cu 8 I 8 cluster built upon two side-fused open cubanes. The crystal structure of CP3 has been determined at 100, 150, 200, 250, 300, 350 and 400 K to study the temperature dependence of the Cu•••Cu distances. Two other topological 1D and 2D CPs isomers of formula [{Cu 2 I 2 }(L1) 2 ] n featuring dinuclear {Cu 2 ( 2-I) 2 } rhomboids were also obtained independently by control of the reaction conditions. These two CPs convert into CP3 in hot PrCN thus indicating that this latter material is the thermodynamic product. While CP1 and CP2 are not emissive, CP3 exhibits an intense luminescence due to the incorporation of the octanuclear Cu 8 I 8 clusters as secondary building units (SBUs) within the network. The photophysical properties of CP3 have been investigated and rationalized by means of DFT and TDDFT computing. Furthermore, the thermal stability of these materials has been studied by ATG and DSC analyses. The Raman spectra of CP1-3 have been recorded in the solid state in the 50-500 cm-1 region.