Self-assembly of gold(i) with diphosphine and bitopic nitrogen donor linkers in the presence of trifluoroacetate anion: formation of coordination polymer versus discrete macrocycle

Deák, Andréa; Tunyogi, Tünde; Tárkányi, Gábor; Király, Péter; Pálinkás, G.

doi:10.1039/b707579k

Cited by 22 publications

(6 citation statements)

References 13 publications

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“…A strong intramolecular aurophilic interaction is evident in 4 [Au(1)··· Au(2) 2.9811(4) Å] and contrasts that of (AuCl) 2 (µ-dppe) in which only large intramolecular Au···Au separations (Ͼ 6 Å for all polymorphic forms) are present. [29,30] There are no significant intermolecular Au···Au separations observed in 4, again different from the previously reported X-ray structures for (AuCl) 2 (µ-dppe) which display short intermolecular Au···Au contacts. [29,30] As would be expected for 1 adopting a bridging mode, the P···P separation in 4 of 3.796 Å is enlarged with respect to that found in 3.…”

Section: Coordination Studiescontrasting

confidence: 77%

“…[29,30] There are no significant intermolecular Au···Au separations observed in 4, again different from the previously reported X-ray structures for (AuCl) 2 (µ-dppe) which display short intermolecular Au···Au contacts. [29,30] As would be expected for 1 adopting a bridging mode, the P···P separation in 4 of 3.796 Å is enlarged with respect to that found in 3. (2) 2.2996(17) P(1)-C (1) 1.828(6) C(1)-C (2) 1.550(9) C(2)-P (2) 1.822(6) Cl(1)-Au(1)-P (1) 175.55(7) Cl(2)-Au(1)-P (2) 176.78(7)…”

Section: Coordination Studiescontrasting

confidence: 71%

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Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage

et al. 2008

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The new nonsymmetric ditertiary phosphane, Ph2P(CH2)2PAd (1), was prepared in one‐step from Ph2PCH=CH2 andH‐PAd (H‐PAd = 1,3,5,7‐tetramethyl‐2,4,8‐trioxa‐6‐phosphaadamantane) by a hydrophosphination reaction using 2,2′‐azo‐bisisobutyronitrile (AIBN) as free radical initiator. The sterically encumbered phosphaadamantane cage in 1 was found to influence the coordination capabilities of this ligand. The reaction of 1 with [PdCl2(cod)] or [Pt(CH3)2(cod)] (cod = cycloocta‐1,5‐diene) gave the corresponding κ2‐P,P′‐chelate complexes cis‐[PdCl2(1)] (2) and cis‐[Pt(CH3)2(1)] (3), respectively. The dinuclear gold(I) complex [Ph2P(AuCl)(CH2)2PAd(AuCl)] (4) was prepared from 1 and 2 equiv. of [AuCl(tht)] (tht = tetrahydrothiophene). In contrast, the cleavage of the chloro‐bridged dimers {RuCl2(η6‐p‐cymene)}2 or {MCl2(η5‐Cp*)}2 (M = Rh, Ir) with 1 gave the κ1‐P‐monodentate complexes [RuCl2(η6‐p‐cymene)(1)] (5), [RhCl2(η5‐Cp*)(1)] (6) and [IrCl2(η5‐Cp*)(1)] (7), respectively, in which the ‐PAd group is non‐coordinating. Chloride abstraction from 6 (or 7) can be accomplished upon addition of Na[SbF6] to generate the cationic κ2‐P,P′‐chelate complexes 8b (and 9b). Alternatively 8a (or 9a) could be observed, as their chloride salts, by 31P{1H} NMR spectroscopy upon addition of several drops of CH3OH to CDCl3 solutions of 6 (or 7). The reaction of 5–7 with [AuCl(tht)] gave the dinuclear complexes [κ2‐P,P′‐μ‐RuCl2(η6‐p‐cymene){Ph2P(CH2)2PAd(AuCl)}] (10), [κ2‐P,P′‐μ‐RhCl2(η5‐Cp*){Ph2P(CH2)2PAd(AuCl)}] (11) and [κ2‐P,P′‐μ‐IrCl2(η5‐Cp*){Ph2P(CH2)2PAd(AuCl)}] (12). Reaction of two equiv. of 5 with the labile precursors [PdCl2(CH3CN)2] or [PtCl2(PhCN)2] gave instead the novel trinuclear Ru2Pd and Ru2Pt complexes trans‐[{κ2‐P,P′‐μ‐RuCl2(η6‐p‐cymene){Ph2P(CH2)2PAd}}2PdCl2] (13) and trans‐[{κ2‐P,P′‐μ‐RuCl2(η6‐p‐cymene){Ph2P(CH2)2PAd}}2PtCl2] (14), respectively. All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore the structures of 3·CHCl3, 4, 5, 7·CHCl3, 10·CH2Cl2·0.5C2H10O and 13·2CH2Cl2 have been elucidated by single‐crystal X‐ray crystallography. The X‐ray structures of 10·CH2Cl2·0.5C4H10O and 13·2CH2Cl2 demonstrate how nonsymmetric ditertiary phosphane complexes bearing one pendant phosphaadamantane moiety can be used as metalloligands in the controlled syntheses of novel bi‐ and trimetallic complexes.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Coordination Studiescontrasting

confidence: 77%

Section: Coordination Studiescontrasting

confidence: 71%

Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage

et al. 2008

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“…The Au-N bond lengths of 2.083(4) A ˚for 8 and 2.088(10) A ˚for 9 are close to those found in [Au(py)(PPh 3 )] + (2.073(3) A ˚), 15 in [Au(dmpy)(PPh 3 )] + (2.091(3) A ˚, dmpy is 2,6-dimethylpyridine) 16 or in the structurally related macrocycle [Au 4 (dppbz) 2 (bipyen) 2 ] 4+ (2.073(5) and 2.101(5) A ˚; dppbz is 1,2-bis(diphenylphosphino)benzene; bipyen is 1,2-transbis(4-pyridyl)ethylene). 17 The Au-P bond lengths of 2.2271 (15) and 2.225(3) A ˚, respectively, for 8 and 9, are within normal ranges for phosphino pyridine gold complexes. 15,16,17 The azo functional groups are in a trans configuration and the triflate anions are non-coordinating, as expected.…”

Section: Methodsmentioning

confidence: 77%

Photosensitive azobispyridine gold(i) and silver(i) complexes

2011

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The neutral and cationic dinuclear gold(I) compounds [(μ-N-N)(AuR)(2)] (N-N = 2,2'-azobispyridine (2-abpy), 4,4'-azobispyridine (4-abpy); R = C(6)F(5), C(6)F(4)OC(12)H(25)-p, C(6)F(4)OCH(2)C(6)H(4)OC(12)H(25)-p) and [(μ-N-N){Au(PR(3))}(2)](CF(3)SO(3))(2) (N-N = 2-abpy, 4-abpy, R = Ph, Me) have been obtained by displacement of a weakly coordinated ligand by an azobispyridine ligand. The corresponding silver(I) dinuclear [(μ-2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] and polynuclear [{Ag(CF(3)SO(3))(4-abpy)}(n)] compounds have been obtained. The molecular structures of [(μ-2-abpy){Au(PPh(3))}(2)](CF(3)SO(3))(2) and [(μ-4-abpy){Au(PMe(3))}(2)](CF(3)SO(3))(2) have been confirmed by X-ray diffraction studies and feature linear gold(I) centers coordinated by pyridyl groups, and non-coordinated azo groups. In contrast the X-ray structure of [(2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] shows tetracoordinated silver(I) centers involving chelating N-N coordination by pyridyl and azo nitrogen atoms. The gold(I) compounds with a long alkoxy chain do not behave as liquid crystals, and decompose before their melting point. The soluble gold(I) derivatives are photosensitive in solution and isomerize to the cis azo isomer under UV irradiation, returning photochemically or thermally to the most stable initial trans isomer. The silver(I) derivative [(2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] also photoisomerizes in solution under UV irradiation, showing that its solid state structure, which would block isomerization by azo coordination, is easily broken. These processes have been monitored by UV-vis absorption and (1)H NMR spectroscopy. All these compounds are non-emissive in the solid state, even at 77 K.

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“…on gold(I) compounds can be used to control their solid-state luminescent properties. [2,[8][9][10][11] Experimental studies have shown that the strength of the attractive Au•••Au interaction in binuclear gold(I)complexesisc omparable to that of hydrogen bonding. [10] Aurophilic interactions are, however,l ess directional than conventional hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

Anion‐, Solvent‐, Temperature‐, and Mechano‐Responsive Photoluminescence in Gold(I) Diphosphine‐Based Dimers

Deák

Jobbágy

Marsi

et al. 2015

Chemistry A European J

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A series of [Au2 (nixantphos)2](X)2 (nixantphos=4,6-bis(diphenylphosphino)-phenoxazine; X=NO3, 1; CF3 COO, 2; CF3 SO3, 3; [Au(CN)2], 4; and BF4, 5) complexes that exhibit intriguing anion-switchable and stimuli-responsive luminescent photophysical properties have been synthesized and characterized. Depending on their anions, these complexes display yellow (3), orange (4 and 5), and red (1 and 2) emission colors. They exhibit reversible thermo-, mechano-, and vapochromic luminescence changes readily perceivable by the naked eye. Single-crystal X-ray studies show that the [Au2 (nixantphos)2](2+) cations with short intramolecular Au⋅⋅⋅Au interactions are involved as donors in an infinite N-H⋅⋅⋅X (X=O and N) hydrogen-bonded chain formation with CF3 COO(-) (2 C) and aurophilically linked [Au(CN)2](-) counterions (4 C). Both crystals show thermochromic luminescence; their room temperature red (2 C) and orange (4 C) emission turns into yellow upon cooling to 77 K. They also exhibit reversible mechanochromic luminescence by changing their emission color from red to dark (2 C), and orange to red (4 C). Compounds 1-5 also display reversible mechanochromic luminescence, altering their emission colors between orange (1) or red (2) to dark, as well as between yellow (3) or orange (4 and 5) to red. Detailed photophysical investigations and correlation with solid-state structural data established the significant role of NH⋅⋅⋅X interactions in the stimuli-responsive luminescent behavior.

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Self-assembly of gold(i) with diphosphine and bitopic nitrogen donor linkers in the presence of trifluoroacetate anion: formation of coordination polymer versus discrete macrocycle

Cited by 22 publications

References 13 publications

Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage

Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage

Photosensitive azobispyridine gold(i) and silver(i) complexes

Anion‐, Solvent‐, Temperature‐, and Mechano‐Responsive Photoluminescence in Gold(I) Diphosphine‐Based Dimers

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