Synthesis and characterization of dinuclear silver(I) complexes with exchangeable nitrile ligands

Hobbollahi, Elnaz; Himmelsbach, Markus; List, Manuela; Monkowius, Uwe

doi:10.1016/j.inoche.2016.07.016

Cited by 8 publications

(8 citation statements)

References 46 publications

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“…The broad feature is presumably due to the dynamic behavior of the ligand scrambling reactions. A very similar NMR behavior of a dinuclear silver complex was published very recently [52]. The 1 H NMR was in a similar range with that of the ligand apart from small shifts.…”

Section: Structural Studiessupporting

confidence: 79%

Structural, photoluminescence, and theoretical DFT studies of gold(I) and silver(I) metallacycle dinuclear complexes of 1-methylbenzimidazolediphenyl phosphine (MBDP) ligand

Jenkins

Assefa

2017

Journal of Molecular Structure

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The synthesis and structural characterization of the bridging ligand, 1-methyl benzimidazole diphenylphosphine (MBDP) and its coordination with Au(I) and Ag(I) metal ions is reported. Two ligands coordinate to the metal ions in head to tail fashion forming a metallacycle coordination consisting of strong MM bonding interaction with Au-Au = 2.808 and Ag-Ag =3.017 Å. Linear coordination is observed for the gold, while the silver shows distorted tetrahedral arrangement. X-ray crystal data of [(MBDP) 2 Au 2 ](CH 3 CN)(BF 4) 2 (2) crystallizes in the monoclinic system with the space group of P2 1 /n with cell constants of a = 8.9993 (8) Å, b = 19.6166 (18) Å, c = 13.4484 (12) Å, β = 100.966 (2)°, R = 0.026, and R w = 0.064. The structure of [(MBDP) 2 (CH 3 CN) 4 Ag 2 ](BF 4) 2 , (3) crystallizes in the P(-)1 space group and the unit cell is a = 10.5423(10) Å, b = 10.7638(10) Å, c = 12.3530(12) Å; α = 88.592(3)°, β = 73.097(3)°, γ = 84.422(3)°, V= 1334.8 (2) Å 3 with Z= 1, R = 0.034 and R w = 0.093. The coordinating ligand as well as both dinuclear compounds reported here are luminescent in the near UV region. As supported by the DFT theoretical work,the emission is suggested to be primarily ligand based ππ* transition. Keywords: benzimidazole, Au(I) dimer, Ag(I) dimer, phosphine Over the past four decades attention has been given to bifunctional ligands with regards to bringing two metal atoms in close proximity [15-18]. Several types of ligands have attracted attention including the N-, P-type ligands. Diphenylphosphinopyridine (dppy), dimethylphosphinopyridine (dmpp), and 2-(diphenylphosphino)-1-benzylimidazole (BzImPh 2 P) are representative of the mixed-donor species commonly used to prepare Au(I) dimers[12-14, 19-20]. These ligands follow the Lewis soft acid/base chemistry when coordinating with group 11 metals. Although N is a lesser soft base than P, its ability to bind with Au(I) is well documented [21-25] including the work conducted by Fackler et al. on amidinate ligands [26-27]. The ability to bring two Au(I) atoms in close proximity is a goal for many research groups because of the fascinating photoluminescence these types of compounds reveal. Hence, the bridging N, P ligands not only coordinate as monodentate ligand, they also have the ability to act as bidentate ligands through the two donor atoms and bring homo-and hetero-nuclear atoms together with short distances. Burini and co-workers have extensively studied the N, P type ligand of (1-benzyl-2imidazolyl) diphenyl-phosphine (BzimPh 2 P) to understand the behavior of coordination with various metal systems [15-18]. They were able to utilize the monodentate and bidentate feature of the BzimPh 2 P by examining complexes with Au(I), Ag(I), Cu(I), Rh(I), Ir(I), Hg(II), Zn(II), and Cd(II) metal ions. In the Au (I) structure, the coordination is found to be monodentate with a near linear geometry of the P-Au-Cl bond angle with the ligand unassisted intermolecular Au-Au distance of 3.306 Å. Bachechi along with Burini and co-workers also studied the X-ray cry...

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Section: Structural Studiessupporting

confidence: 79%

Structural, photoluminescence, and theoretical DFT studies of gold(I) and silver(I) metallacycle dinuclear complexes of 1-methylbenzimidazolediphenyl phosphine (MBDP) ligand

Jenkins

Assefa

2017

Journal of Molecular Structure

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“…Other promising candidates for NIR-emitters are luminescent complexes of the 11th group metals (Cu, Ag, Au). This class of compounds garnered significant attention in the past decade due to their low cost, low toxicity, and intense and long-lived luminescence in the solid state at ambient temperatures with emission range spanning the visible spectrum. − The rich photoluminescence of copper group complexes is caused by involvement of metal-to-ligand charge-transfer (MLCT), ligand-to-ligand charge-transfer (LLCT), and metal-halide-to-ligand charge-transfer (M + X)LCT transitions in the emissive state; thus, the emission color of these complexes can be easily tuned by systematic variation of a ligand system . From this point of view, P,N-hybrid ligands, particularly phosphinopyridines and their N-heterocyclic analogues, seem to be an invaluable tool for the effective complexation with a transition metal where the N-heterocyclic group implies effective charge transfer between a metal center and ligand(s) and provides luminescence from the obtained complexes.…”

Section: Introductionmentioning

confidence: 99%

“…From this point of view, P,N-hybrid ligands, particularly phosphinopyridines and their N-heterocyclic analogues, seem to be an invaluable tool for the effective complexation with a transition metal where the N-heterocyclic group implies effective charge transfer between a metal center and ligand(s) and provides luminescence from the obtained complexes. Copper group metal complexes based on P,N-hybrid ligands exhibit a high structural diversity and as a result rich photoluminescent properties. ,,− The NIR-emissive d 10 transition-metal complexes are represented mainly by polynuclear Cu(I) clusters bearing S,N-hybrid ligands ,− and by homo- and heteropolynuclear clusters based on S,N- or P,N-hybrid ligands. − …”

Section: Introductionmentioning

confidence: 99%

“…Typically, P,N-ligands (diphenyl(2-pyridinyl)phosphine (PyPPh 2 ) and its N-heterocyclic analogues) form binuclear charged or neutral complexes with two bridged molecules of ligand in “head-to-tail” arrangement. ,− ,, As a rule, these complexes demonstrate luminescence with emission maxima in the range of blue to yellowish-green color of the visible spectrum (λ em of ca. 370–500 nm). ,,− ,,, Herein we present the detailed report concerning the synthesis and characterization of a series of charged binuclear silver(I) complexes based on pyridylphospholanes, and their unique solid-state NIR luminescence at room temperature.…”

Section: Introductionmentioning

confidence: 99%

“…370− 500 nm). 27,32,[47][48][49]53,55,56 Herein we present the detailed report concerning the synthesis and characterization of a series of charged binuclear silver(I) complexes based on pyridylphospholanes, and their unique solid-state NIR luminescence at room temperature.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Intriguing Near-Infrared Solid-State Luminescence of Binuclear Silver(I) Complexes Based on Pyridylphospholane Scaffolds

et al. 2019

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A series of novel charged disilver(I) complexes with pyridyl-containing phospholanes was synthesized. These complexes were characterized using a range of spectroscopic techniques and single-crystal and powder X-ray diffraction. The complexes demonstrate solid-state near-infrared (NIR) luminescence (765–902 nm) that is unique for dinuclear AgI complexes. Combined spectroscopic/quantum chemical analysis suggests that the NIR luminescence of complexes 4–6 in the solid state is mainly due to crystal packing effects.

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Enlightening developments in 1,3-P,N-ligand-stabilized multinuclear complexes: A shift from catalysis to photoluminescence

Rong

Holtrop

Slootweg

et al. 2019

Coordination Chemistry Reviews

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Synthesis and characterization of dinuclear silver(I) complexes with exchangeable nitrile ligands

Cited by 8 publications

References 46 publications

Structural, photoluminescence, and theoretical DFT studies of gold(I) and silver(I) metallacycle dinuclear complexes of 1-methylbenzimidazolediphenyl phosphine (MBDP) ligand

Structural, photoluminescence, and theoretical DFT studies of gold(I) and silver(I) metallacycle dinuclear complexes of 1-methylbenzimidazolediphenyl phosphine (MBDP) ligand

Intriguing Near-Infrared Solid-State Luminescence of Binuclear Silver(I) Complexes Based on Pyridylphospholane Scaffolds

Enlightening developments in 1,3-P,N-ligand-stabilized multinuclear complexes: A shift from catalysis to photoluminescence

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